The LiCl-doped samples keep their original spherical morphology as pure ZnSn(OH)6, with some LiCl particles stuck to its surface, providing more active sites for the adsorption and desorption of water molecules. The influence of LiCl doping on the humidity-sensing properties was explored by varying the dopant concentration. The 16 wt% LiCl/ZnSn(OH)6 showed a better humidity-sensing performance than that of the pure ZnSn(OH)6 and other doped samples, including a high resistive sensitivity, a relatively small hysteresis, and a fast response speed. Through the FTIR analysis, the number of hydroxyl groups on the surface structure after aging has been found to decline markedly. These hydroxyl groups provide a platform for the adsorption of water molecules on the surface and promote the dissociation of water molecules. The detriment of aging to sensor performance should not be underrated. The complex impedance spectrum explains the mechanism of the sensor. These results demonstrate that ZnSn(OH)6 has potential application in fabricating humidity sensors, and the sensing performance of the sensor is enhanced by the dopant LiCl.Pure zinc hydroxystannate (ZnSn(OH) In recent years, sensors have played an essential role in technological development of human society as the devices to record, transmit, process, and store information . As one 6, (ZHS) is a typical perovskite-structured hydroxide material [6 and Zn(OH)6 polyhedra, which share their “O” corners to build the structural framework [ZnSn(OH)material . In thisramework . At the ramework ,20,21, gramework , flame rramework , lithiumramework ,25, biolramework , etc. Itramework ,28. The ramework , it is framework  endows hIn order to make the ZHS sensing material fully utilized, one of the most effective ways is to fabricate materials by combining ZHS with other humidity-sensing material dopants. The precious metals gold and silver are often selected as dopants and have been successfully doped into ZHS ,31. We hThe types of electrodes we commonly use are Dunmore, “sandwich”, interdigital electrode, and conventional sintered electrodes. Interdigital electrodes have the advantages of a wide humidity measurement range, high sensitivity, short response time, simple preparation process, good stability, and easy mass production ,37,38,39However, as per our knowledge, the humidity properties of ZHS have been seldom involved. Here, ZHS nanocrystalline was synthesized as a sensing material. The humidity sensor is fabricated by coating this material on Ag-Pd interdigitated electrodes. Humidity-sensing research into impedance sensitivity and response speed was carried out. The complex impedance and infrared spectrum characteristics were recorded to explain the sensing mechanism and the effect of surface hydroxyl variation on humidity-sensing properties.4·7H2O), potassium stannate trihydrate (K2SnO3·3H2O), ammonium hydroxide (NH3·H2O), lithium chloride (LiCl), magnesium chloride (MgCl), potassium carbonate (K2CO3), magnesium nitrate (Mg(NO3)2), copper chloride (CuCl2), sodium chloride (NaCl), potassium chloride (KCl), potassium nitrate (KNO3), formaldehyde (HCHO), ethanol (C2H6O), acetone (C3H6O), and hydrogen peroxide (H2O2) were purchased from Sinopharm Chemical Reagent Co., Ltd., Beijing, China. All the reagents used in this experiment were of analytical grade.Zinc sulfate heptahydrate  of LiCl were added. After being aged for 3 h at room temperature, the resulting material were named 8 wt%, 12 wt%, 16 wt%, 20 wt%, and 24 wt% LiCl/ZHS. The synthesis process of ZHS and LiCl/ZHS is shown in −1 and performed at an angle range of 15–80°. The specific surface areas of the products were measured and analyzed by means of a nitrogen adsorption–desorption instrument (BET) . The morphologies of all of the samples were characterized by a field emission scanning electron microscope  at an accelerating voltage of 5 kV. The Fourier transform infrared spectroscopy (FT-IR) spectra of the materials were recorded with a Nicolet IS5 spectrometer . A KBr pellet  was used to prepare the samples for FTIR measurement the range of 500–4000 cm−1 and averaged 32 times.The crystal structure of the samples was characterized by X-ray diffraction  with Cu Kα radiation (λ = 1.5418 Å) at a scan rate of 4.5° min2, K2CO3, Mg (NO3)2, CuCl2, NaCl, KCl, and KNO3 with the relative humidity of 11%, 33%, 43%, 54%, 64%, 75%, 85%, and 95%, respectively. In the humidity study, the voltage was set at 1 V AC, and the frequency changes from 40 Hz to 100 kHz. During the humidity sensitivity measurement, the prepared sensor was put into some chambers with different humidity, which were carried out by switching the sensor from one chamber quickly into another one. The sensors were aged in 100% RH chamber at 1 V AC and 100 Hz for about 3 h. All of the humidity-sensing measurements were carried out at 25 °C. The tests based on LiCl/ZHS sensors are similar to those reported previously [2H6O, C3H6O, H2O2, and NH3 five gases at a concentration of 500 ppm was tested at room temperature. The ambient humidity at room temperature is 30 RH%.To obtain the humidity sensors, the as-synthesized sample was mixed with deionized water in a weight ratio of 5:1 to form a paste. The paste was coated on a ceramic substrate  with five pairs of Ag-Pd interdigitated electrodes (electrodes width and distance: 0.15 mm) to form the sensitive film. The film was dried in air at 60 °C for 6 h. Finally, the humidity sensor was obtained. To test the humidity sensor characteristic, the ZAHNER-IM6EX electrochemical workstation  was used to measure the electrical properties of the sensors. The sensors were placed into eight chambers with different relative humidity at room temperature. The relative humidity of 11–95% RH was obtained using different saturated salt solutions as humidity sources. The saturated salt solutions were made from LiCl, MgCl6, according to the Scherrer formula: D = kλ/βcos θ. When the amount of dopant is 0–24 wt%, the crystal size of LiCl/ZHS shows a downward trend. The full peaks of ZHS and LiCl/ZHS shift less than 1 degree to the high angle, indicating that the crystal plane spacing is decreasing. As for LiCl-doped ZHS samples, fraction peaks corresponding to the dopant were not found, indicating that the introduction of LiCl dopant does not change the original crystal structure. The strong diffraction peaks with no impurities indicate the good crystallinity and high purity of the samples. The crystal structure of pure and LiCl-doped ZHS samples was confirmed by the XRD analysis, as shown in 2/g. From the element mapping analysis in 2 + 31.5562X − 34.6291, and the regression coefficient R2 = 0.98092. Generally speaking, the lower the water vapor pressure, the higher the impedance of the sensing material. However, the maximum impedance can be seen on the fitted image at a water vapor pressure of 0.4 kPa, which may be caused by the statistical error of low relative humidity measurement not considered in the numerical fitting.Response time refers to the time required for the sensor to reach 90% of the total impedance change during the moisture absorption and desorption. −1, especially a strong absorption peak at 3217 cm−1, was observed, which is attributed to the stretching of the hydroxyl groups [−1 [−1 is originated from the hydrogen bond between water molecules and the stretching modes of Sn-OH [The structure and functional groups are the key factors affecting the conductivity of sensing materials. In order to determine the functional groups on the film surface, Fourier infrared spectroscopy was performed, as displayed in l groups . In addioups [−1 . The absof Sn-OH , respect−1 shows distinct changes before and after aging. Compared with the decreased number of hydroxyl groups after aging, a large number of hydroxyl groups that exist before aging enable the samples to possess a strong adsorption capacity for water molecules. Such changes in the number of hydroxyls were also proved by analyzing the ZHS crystal structure and humidity characteristics before and after aging of the sensors, as shown in −1 [2 or CO2 adsorbed on the ZHS sample. The absorption peak at 1632 cm−1 [2 hybrid.It is worth mentioning that the absorption peak at 3217 cmwn in −1  is a res632 cm−1  is relat2H6O, C3H6O, H2O2, and NH3 at a concentration of 500 ppm to conduct the cross-sensitivity test, as shown in 2H6O, C3H6O, and NH3 can be observed to be very small. Among all the gases, the sensor exhibits the highest response toward NH3. At the same time, the sensor has good repeatability and stability after different testing cycles. After introducing LiCl, the response of the 16 wt% LiCl/ZHS sensor to these gases improved dramatically, which is attributed to the active site induced by doping nanoparticles on the ZHS surface. Moreover, the response of the 16 wt% LiCl/ZHS-based sensor to NH3 (2.0 × 106 Ω) is equivalent to that at 43% RH. Hence, the 16 wt% LiCl/ZHS humidity sensor before aging was immune to these gases in the 64–95% RH range. With regard to the highest response of ammonia, according to the widely accepted gas sensing theory, the sensitivity of the resistance gas sensor is related to the change of electron depletion layer. When the 16 wt% LiCl/ZHS sensor is exposed to the target gas, the surface will absorb oxygen  with the following reaction equations:To ensure the anti-interference of the ZHS and 16 wt% LiCl/ZHS humidity sensor in the presence of some other gas molecules in the air, we selected HCHO, C2−, resulting in the formation of an electron depletion layer at the ZHS surface and the sample with a high resistance. When the sensor is placed in ammonia (NH3), O2− would oxide ammonia molecules, and then, captured electrons are released back to the sample surface. The electron depletion layer narrows, the resistance decreases, and the current increases.When the sensor is exposed to air, oxygen molecules capture electrons to form OThat means that the fabricated humidity sensor would work more stably in a high humidity environment.According to the above analysis of humidity-sensitive characteristics, the high sensitivity of the 16 wt% LiCl/ZHS humidity sensor mainly relies on the rich hydrophilic function groups on the material surface. Due to some hydrophilic functional groups (OH) on the surface of 16 wt% LiCl/ZHS, more water molecules can be adsorbed on the surface. Additionally, these water molecules can accelerate the dissociation ability of conductive ions, which has achieved the purpose of enhancing ion conduction. To better analyze the humidity-sensing mechanism, we tested the complex impedance spectrum (Cole–Cole diagram) of the 16 wt% LiCl/ZHS samples and fitted an equivalent circuit to study the electrical characteristics of the 16 wt% LiCl/ZHS sensor. The real part ReZ and the imaginary part ImZ of the device impedance were measured under different ambient humidity in the frequency range from 40 Hz to 100 kHz, as shown in w) is the impedance caused by diffusion, which usually occurs in the low-frequency band. The CIS curve of 11% RH and 33% RH displays a straight line approximately parallel to the Y-axis. The impedance of sensors is very large. A few water molecules would be chemisorbed at a low humidity environment on the active sites of the 16 wt% LiCl/ZHS surface to form hydroxyl groups. Protons are transferred from these surface hydroxyls to water molecules to form H3O+. At this time, the proton works as the major carrier to realize hopping conduction. Around 43–54% RH, the impedance decreases further. The curve is semicircular. With the increase in adsorbed water molecules, the impedance decreases continuously, the protons and water molecules bind together to form H3O+. At the same time, some Li+ are ionized from the 16 wt% LiCl/ZHS sample. Hence, both H3O+ and Li+ participate in the conduction. Hence, at low RH levels (<54% RH), the EC can be regarded as a parallel connection of capacitor Cf and resistor Rf in this situation, as shown in w. As the humidity increases further, more and more water molecules are adsorbed onto the surface, tending to form a liquid layer. H3O+ releases a proton to a neighboring water molecule in the liquid water layer, which receives it while releasing another proton. Protons can move freely in a continuous layer of liquid water known as the Gaussian conduction mechanism (H2O + H3O+ → H3O+ + H2O) [w in Based on the physical theory of electrolytes, we know that in the equivalent circuit (EC), the resistance represents the conducting process, the capacitance represents the polarization process, and the Warburg impedance (Z+ + H2O) . The Gro2O) w in .+ and Cl- also act as conduction carriers. At 95% RH, the CIS curve shows a semicircle and an upward tail. More and more water molecules are adsorbed at this time. The ion conduction of H3O+ and Li+ is further enhanced, resulting in a sharp reduction in the impedance. As a result, through the analysis of complex impedance spectrum at low and high humidity ambient, both proton and ionic conduction are found to exist in the humidity-sensing mechanism of the 16 wt% LiCl/ZHS sample.LiCl would dissolve in the formed liquid water layer, and the dissociated Li+ have a small radius and produce a large polarization force to attract electron-rich water molecules in oxygen atoms. The dopant LiCl dramatically improved the specific surface area of the pure ZHS sample and greatly enhanced the humidity-sensing response of the sensors. Among all the doping samples, the 16 wt% LiCl/ZHS exhibits a high sensitivity of about four orders of magnitude, the best linear correlation from 11–95% RH, a narrow humidity hysteresis of less than 9.5% RH, and a favorable response speed shorter than 10.2 s. According to Fourier infrared functional group analysis, the number of hydroxyl groups after aging is significantly reduced compared with that before aging. These hydroxyl groups contribute much to the adsorption of water molecules, which is highly consistent with the analysis of the ZHS crystal structure before and after aging. The complex impedance spectrum analysis reveals that the protons and introduced Li ions are the major conductive carriers. Protons and Li ions play a prominent role in low humidity and high environment, respectively. Both protons and Li ions work at a medium moisture ambience. These results demonstrate the superior performance of ZHS in effective humidity detection and the obvious improvement of humidity properties by LiCl doping.In conclusion, the synthesis and characterization of pure ZHS and LiCl/ZHS samples were explored. After that, sensors based on ZHS with different doping content were fabricated, and their humidity-sensing properties were measured. As a typical electrolyte material, Li


Despite significant evidence base on quantifying ecosystem services, the role of biodiversity in supporting such services in diversified landscapes, and how indigenous communities exploit, utilize and manage plant resources in a biocultural regime, remains understudied. This study examines the role of wild edible plants (WEPs) in meeting the food, nutrition and household income of indigenous communities under the biodiversity rich landscape of the Achanakmaar-Amarkantak Biosphere Reserve (AABR—22°15′ to 22°58′ N latitudes and 81°25′ to 82°5′ East longitudes) of Central India. Results revealed remarkable differences among Baiga, Gond, Kol, and Oraon ethnic communities and also location  effect on utilization pattern of wild edibles. A sum total of 172 WEPs comprising 60 vegetables, 70 fruits, seeds and nuts, 23 underground tubers and 19 mushrooms were collected, consumed, and surplus were marketed by the communities. On average, the number of wild edibles collected annually by households were in the following quantities: 40–240 kg leafy vegetables, 125–386 kg flowers, 120–250 kg fruits, 12–125 kg legumes, 24–120 kg tubers, 5–35 kg mushrooms. Among ethnic groups, the Baiga primitive community utilized 70–90% followed by Gonds (58–81%), Kols (52–78%), Oraons (43–79%), and other communities (38–68%) in different zones. WEPs have contributed to 5–24%  of household income, which was highest in the core zone and lowest in the transition zone. It was observed that WEPs were complemented the diets rather than being a substitute for staple foods. They supplied only 3.7–8.3% of energy and 1.1–4.9% protein requirements; however, they significantly supplemented ascorbic acid, thiamine, calcium, and iron by 38.1–73%, 13.7–35.4%, 17.2–29.1%, 2.6–13.5%, respectively. Significantly higher quantities of nutrients were supplemented in the core zone compared to other zones. WEPs were currently underutilized (less intake) especially in buffer and transition zones, complementing the staple foods and partially supplementing the essential macro- and micro-nutrients. However, these have the potential to fulfill the dietary needs and ensure balanced nutrition, if consumed in recommended portions and sizes. The paper discusses policy implications that ensure coherence and coordination of local indigenous communities for conservation and sustainable utilization of WEPs of AABR, Central India. Mainstreaming biodiversity and ecosystem services into food production systems involves strong trade-offs and is critical for balancing livelihoods, culture, habitability, and ecological diversity across heterogeneous landscapes. Biodiversity plays an indispensable role in the maintenance of ecosystem services interlinked to complex socio-economic and biocultural regimes of indigenous communities who have unique values, traditions, beliefs, and lifestyles ,2,3. WilIndia has one of the largest concentrations of indigenous people comprising ~104 million people represented by 705 ethnic groups among whom 75 are vulnerable tribal groups. These tribal groups derive multiple products and services from wild habitats ,17. The WEPs have become critical for the sustenance and household income of these groups; moreover, the lower returns from farms necessitate the diversification of income from the sale of WEPs. However, unscientific, concentrated, and over-exploitation of few species degenerating the native diversity of WEPs, while increasing rates of deforestation, epidemics of pests and forest fires in the last few years caused severe genetic erosion disrupting the cultural and traditional food habits resulting in an increase of the incidences of malnutrition and chronic diseases especially among the children and women of indigenous communities. Up until now, very little comprehensive work has been made on the diversity and utilization of WEPs; moreover, studies were concentrated on traditional knowledge for primary health care using herbal drugs in Central India ,22. NeveThe present investigations were carried out in AABR, the 8th biosphere reserve and declared as a natural heritage site by United Nations Educational, Scientific and Cultural Organization (UNESCO) in the year 2012. It lies between 22°15′ to 22°58′ North latitudes and 810 25′ N to 820 5′ East longitudes and spread over 383,551 ha, of which 68% area covered by Chhattisgarh and 32% by Madhya Pradesh . The bioNearly, 27 communities comprising Baiga, Gond, Dhanwar, Kol, Kanwar, Oraon, Chamar, Sais (Sarthi), Basore, Lonia, Muslim, Sindhi, Brahmin, Rajput, Goswami, Baraith, Kalar, Kumhar, Kewat, Nai, Ahir (Raut), Panika, Sondhiya, Lohar, Maratha, Sonar, and Baniya inhabit core and buffer zones of the biosphere. A sum total of 8168 traditional ethnic tribal inhabitants live in the villages of the core zone, mainly comprising Baiga, Gond, Kol, Pradhan, and Oraons are indigenous communities .The sample was obtained utilizing a stratified two-stage design. The villages were grouped into three strata  where each stratum represented a biosphere zone. In the first stage, three representative villages were selected from each of the strata considering demographic features, location, ethnicity, market avenues. Thus a total of nine villages (three from each zone) were selected for household surveys from three zones of the biosphere . A totalN (2168) denotes the population size i.e., total number of households in all the villages, Z (1.96) is the critical value of the normal distribution for rejecting a null hypothesis at 5% level of significance, p (0.5) is the estimated proportion and e (0.05) is the selected margin of error. Using the above expression, the minimum sample size required for the study is 327.Our study investigates the contribution of wild edible foods (WEF) to the income, energy and nutritional intake of households. A preliminary investigation by the investigators found that the weight of the proportional contribution of WEF in the intake of the households is about 0.5. This proportion is utilized to calculate the minimum sample size (of households) required for the present study. The following expression by Snedecor and Cochran  is utiliIn the second stage, households were sampled from each of the villages selected in the first stage. The probability proportion to size (PPS) method was utilized for the second stage sampling with household size as weight. The criterion was to obtain a sample of 20 or more households from each of the villages depending upon the feasibility as permitted by the terrain. In this process 332 households were selected. In each sample village, households were selected randomly among the communities.In addition to 332 households, 45 key informants , 9 focus group members (9 villages × 10 members/group and 30 market vendors (3 markets from each zone × 10 vendors/market) were also questioned to collect information on the list of species, diversity of collection, preparation of recipes, the order of preference and availability of wild edible plants and marketing pattern of WEPs.Information on qualitative data on collection and utilization of WEPs was obtained through participatory rural appraisal techniques (PRA), direct observation, semi-structured schedule, and key informant interviews. Assistance from local translators and forest department staff was also taken in gathering desired information as most of the female and old respondents were illiterate and conversed in the local tribal dialect. A semi-structured schedule with open-ended questions and a schedule for focus group discussion (FGD) was designed by the stakeholders and a team of experts. The methodology adopted for collecting quantitative information of WEPs are presented in the following section.The survey schedule comprises three parts, namely Part-I, Part-II and Part-III. Part-I of the schedule deals with the general socio-economic and demographic profile of the village and households. Part-II of the schedule consists of enquiries pertaining to provisioning services of WEPs, patterns of collection, utilization, sale and marketing pattern of WEPs. It also includes enquiries related to the knowledge of edible plants and their parts. Furthermore, the information on the habitat, the season, typical recipes used in cooking etc. was also collected in Part-II. The specimens of species were collected from the wild with the help of community members and identified. These were matching with records of local flora. The unidentified specimens were photographed and a herbarium was prepared. The unidentified specimens were later identified by expert taxonomists. Part-III of the schedule comprised the questions related to dietary habits, food consumption, and nutrient intake. Parts-I and II of the schedule were carried out in all the households in the sample.The investigators found that there was no organized marketing with specified market channels for wild edible plants and products. The commodities were traded in local weekly markets popularly known as hat markets. Marketability of wild edibles was studied in three local hat markets of Achanakmaar, Birjhakachar, and Shivtarai villages located in the core, buffer and transition zones respectively. The markets are operated mostly by middlemen and local vendors, who buy raw WEPs along with other commodities in bulk from collectors of indigenous communities at a nominal price on market days and sell them after bundling and washing with a significant margin of profits to local and non-local customers. A marketing survey was conducted in peak hours of the market between 11 a.m. to 3 p.m., where a total of 30 vendors (10 from each market) were interviewed to collect information on the trade of WEPs. The vendors in each of the hat were selected using a systematic sampling plan.The Part-III of the schedule was canvassed for a randomly selected subsample of 10 households from among the sample of households selected in the second stage. Food intake data were collected from the selected households representing different indigenous communities in each village by a 24 h recall method repetitively for 3 days each in summer, winter, and rainy seasons. Data were exclusively collected from the women and elderly members as they are involved in cooking and serving food to members of their respective households. The total weight of the prepared dish was recorded and the weight of each raw ingredient was calculated as a percentage of total cooked weight of the dish. The food consumed from conventional and wild edible sources was recorded separately for different food groups. The mean daily per capita intake of foods (average of household members) was recorded and compared with recommended national dietary standards of households  as prescribed by the Indian Council of Medical Research (ICMR), Government of India ,28,29. T2) was employed for parameters on frequency of collection, utilization and marketing pattern of wild edibles, while a t-test for food and nutrition intake was made to compare the significant differences in relation to location and also ethnicity (p < 0.05) [Descriptive statistics pertaining to the population , biosphere zone, number of households  and literacy are provided for each of the nine sampled villages. Data on the number and percentage of species and families of WEPs, as well as their life forms and the parts consumed were analyzed using descriptive analysis and frequency calculation techniques . The Chi < 0.05) . The meaThe population of studied villages ranged from 429 to 2244, of which 29% to 95% of people represented indigenous communities . The numThe WEPs resources were essentially categorized into five food categories according to the plant parts utilized by the respondents. A total of 172 WEPs comprising 60 leafy and shoot vegetables, 70 fruits, seeds and nuts, 23 underground tubers, 19 mushrooms. Most of these were consumed by communities and few edibles in demand were locally marketed for securing livelihood and household income a. The wiAmaranthus species were highly preferred and cooked as baajis are frequently found in traditional diets of all communities; however, frequency was higher in Baigas compared to other groups. The tender shoots of bamboos, locally known as Bans kareel, were highly preferred in local diets and soft shoots often directly eaten after roasting and young shoots cooked as a vegetable and also pickled during the rainy season besides the roasted kareel and shoot sold at 80–100 Rs./- in local markets in different zones of the biosphere. The fresh chutneys were also prepared using mint (Mentha arvensis L.) leaves and leaves of amari baji (Hibiscus sabdariffa L.) in combination with salt, peppers and spices. Leaves and floral parts of four species viz. Mentha arvensis L., Murraya koenigii Spreng, Eryngium foetidum L. and Phyllocephalum indicum K. Kirkman were used as spices to enhance the flavor and taste of traditional dishes by Baigas and Gonds. Based on the culinary value, taste and edible values, the 60 species of leafy vegetables were ranked where 11 and 24 were very high and highly preferred species among the communities, of which 25 species had good market value and locally sold in hat markets. Moreover, 18 species and 6 species were ranked as moderate to least preferred, which were consumed by households in core and buffer zones for their subsistence in times of food scarcity; however, these were seldom found in diets of transition zones, where many cultivated vegetables substitute low valued wild edibles. Fifty percent (50%) of the total wild leafy vegetables (60) were extracted during the rainy season followed by 25% in winter, 17% in summer, and 8% throughout the year, while 58% of these were used variously for religious, timber, non-timber and other edible purposes  is the most preferred and highly valued species, almost all parts of the tree including flowers, fruits and seeds were collected, consumed and marketed economically by communities. Flowers were eaten as raw and also made into chapatis and porridges by mixing with wheat, jowar, and rice flour. This is popular wine usually consumed by all the groups of indigenous communities regularly as the part of cultural heritage. Furthermore, it is also customary to serve liquor to people especially for enjoyment and entertainment during cultural festivals. It is also traditional to serve this drink during ceremonies of marriage, child birth, death, inauguration and opening of new houses, shops etc. The drink is also offered to gods or goddesses as part of the rituals and consumed as a sacred drink. The unripe fruits of Mahua are cooked as vegetables, while ripe ones were collected and seeds were recovered after removing pulp and kernels from Mahua seeds and dried to extract the oil, which is used as edible oil for cooking and occasionally for lighting purposes. Mango is another important fruit yielding species valued for its both ripe and unripe fruits as young unripe fruits were used in making chutney in summer, while the unripe fruits are peeled and dried to make amchoor, which is usually added in vegetable curries and dals to give a sour taste. The unripe mature fruits were boiled with water to prepare ampana as a drink to protect from dehydration during summer. The unripe fruits are also used in making mango pickles, while ripe fruits are directly eaten or juice is prepared and consumed along with rice/wheat chapattis. The leaves and shoots are used in rituals, religious functions and cultural festivals, symbolizing purity, prosperity and spiritual goodness. The mature fruits of Indian goose berry—aonla —were directly eaten, pickled and murabba prepared by mixing with syrups of sugar or jaggery, besides being used in rituals by communities, considered as a sacred tree. Another commercially important species is char (Buchanania lanzan Spreng.), where the ripe fruits are directly eaten and kernels extracted from seeds have immense commercial value mixed in sweet dishes and taken along with milk. Munga is another popular species, where young flowers are cooked as vegetables and pods also cooked as vegetables in combination with pulses and soya nuggets. Moreover, ripe fruits harvested from Diospyros melanoxylon Roxb. Tamarindus indica L., Aegle marmelos L. correa, Annona squamosa L. etc. were eaten as raw, which have immense potential for commercial exploitation making food and beverages. Of the 70 species, the products of 10 and 12 were very high to highly preferred, which were not only consumed but also sold in local markets due to their commercial value. A total of 25 and 23 of fruits were moderately and least preferred consumed in subsistence but not marketed, while 44 species offer diverse provisioning services, 9 species as religious and cultural, and 7 species provide timber and non-timber products to communities , honey, gums, dyes > tubers > mushrooms (The collection of wild edible plants by households was in the order: flowers > fruits > leaves > legumes and pods > other NTFP (non-timber forest product) , aonla , sitaphal (Annona squamosa L.), jamun (Syzygium cumini (L.) Skeels), mangoes (Mangifera indica L.), seeds of char (Buchanania lanzan Spreng) etc. were major contributors for household income, whereas the very highly preferred leafy vegetables such Amaranthus sp., Mushrooms  and tubers wild yams, bamboo shoots possessing good demand in local markets had also significantly contributed for household income. The price list of 71 WEP species commonly sold in local hat markets are summarized in Among the annual household income generated from the trading of WEPs, the sale of flowers and fruits alone contributed 60–70% (Rs 2700- Rs 8220/- 1 US$ = Rs 73) of household income across three zones of biosphere followed by mushrooms ), leafy vegetables  and tubers , and legumes and pods  a. The flThe communities derive household income from diverse sources including agriculture and allied sectors, labour and trade of wild edibles, and other NTFPs. The household annual income ranged from different sources ranged from 12,000 ± 1240 Rs. to 14,000 ± 1380 Rs., 7000 ± 840 Rs. to 24,000 ± 2460 Rs. and 3559 ± 840 Rs. to 26,400 ± 2840 in core, buffer, and transition zones, respectively b. It wasShorea robusta Roth.), tendu (Diospyros melanoxylon Roxb.) aonla , char (Buchanania lanzan Spreng) etc. also provide WEPs. On the other hand, the construction of minor dams, protected mining and expansion of roads has been recognized as not a major threat by communities  pattern revealed that, except for cereals, all other food items were consumed in lower quantities in comparison to recommended dietary allowances (RDA) prescribed by the Indian Council of Medical Research (ICMR), Government of India . The perThe per capita intake of macro- and micro-nutrients by indigenous communities was lower than recommended quantities . It was p ≤ 0.05) to supplementing micro- and macro-nutrients  were nationalized with a proper institutional arrangement of procurement by the state forest department. Numerous researchers have argued for the need to improve market facilities and support prices for smooth trading of a range of WEPs to avert the ongoing exploitation of indigenous communities by middlemen [The primary collectors in the study area are indigenous communities who sell their products to middlemen at nominal prices. Ahirwar et al.  while stiddlemen ,43.Mangifera indica L.), ber (Ziziphus jujuba Mill), bael (Aegle marmelos L. correa) lasorda (Cordia myxa L.), aonla , seethaphal (Annona squamosa L.), tendu (Diospyros melanoxylon Roxb.). wood apple (Limonia acidissima L.), char (Buchanania lanzan Spreng), karonda (Carissa carandas L.), imli  etc. shoots of bamboos, yams (Dioscoreas) thikhur (Curucuma angustifolia Roxb.), spices, mushrooms, etc have strong potential for processing and value addition.The study also revealed that wild edibles contributed to 5–24%  for annual household income  across three zones in AABR, Central India. Although the contribution of WEPs for income was significant but quite low, this could be increased through primary processing and value addition, which will not only augment economic returns but also enhance the shelf life of perishable commodities. A number of fruits and vegetables that were sold as raw in the markets at low prices could be easily processed in the form of pickles, chutney, jam, jelly, squash dried fruit, dried powder, dried seed, marmalade, etc. with minimum costs and ordinary skills. At least 20–30% of locally popular wild edible fruits such as mango (The food consumption (g/day) pattern revealed that diets of indigenous communities of AABR were purely cereal based, while the intake of pulses, vegetables, fruits, tubers, milk, meat, sugar, and fats were rather less than the recommended dietary allowances (RDA) prescribed by ICMR. The non-availability of foodstuffs in core and buffer zones or prevailing access to the public distribution system are the main causes of inadequate consumption below the recommended dietary allowances compared to transition zone. The scientific agriculture practices, marketing facilities, along with effective public distribution and better socio-economic conditions propmted the use of adequate quantities of conventional foods resulting in lesser dependency on WEPs in the transition zone. Moreover, people are changing their indigenous lifestyles and accepting the alternative sources of foods, gradually shifting from tradtional food habits. The divergent variations in dietary consumption and low intake of food-stuff were not uncommon, which had also been reported previously among indigenous communities in India ,48,49.Turning our attention to the pattern of consumption of foods and nutrients, it was evident that intake of macro and micro-nutrients by indigenous communities were less than desired allowances, as a consequence of lower consumption of recommended food groups, especially those that meet the requirement of proteins, vitamins, and mineral nutrients are lacking in their diets. Although WEPs especially leafy vegetables, legume pods, other vegetables, fruits, flowers, mushrooms, roots and tubers significantly supplemented the household food requirements in the core and buffer zone, these were still inadequate. Studies conducted in the past suggested that WEPs were important in native food systems and contribute to food and nutrition security of the poor ,6,8,50.Oxalis corniculata and Cassia obtusifolia are nutritionally rich in crude protein (20.2–22.3%), lipids (23–23.7%), and total sugars (4–12.1%). Nutrient-rich neglected WEPs could help transform food systems, if science and policy are well connected with better coordination among the diverse stakeholders working on conservation and sustainable utilization [Our study showed that the contribution of wild foods to total food consumption was rather low among indigenous communities of AABR.This has resulted as a consequence of intake of lower quantities of WEPs thus only meeting the partial requirements of micronutrients leaving a big deficit, which could be fulfilled by increasing their quantities in traditional diets in core and buffer zones. There is vast potential to exploit nutrient-rich underutilized WEPs in large quantities than the present level of consumption in AABR. Jain and Tiwari  emphasizlization ,23,52.The present study demonstrated the significant role and contribution of a wide array of WEPs (172) for meeting dietary needs and household income (5–12%) of indigenous communities, however, these have been largely underscored and have not received enough attention in government programs. WEPs and their products need to be promoted and incorporated into various nutritional and food supply schemes of the government comprehensively, especially under integrated women and child development programs, mid-day meals of schoolchildren, and a public distribution system for meeting diverse needs leading to the holistic development of indigenous communities. The National Food Security Act of Government of India, 2013 has included highly nutritious and climate resilient minor millets in the public distribution systems to benefit millions of schoolchildren and the wider population, and in a similar way the potential nutritious wild foods could be linked to these programme and fostered in habitats that are consumed along with staple foods in addressing the problems of undernourishment. There is an immense potential for bioprospecting of genetic resources of WEPs and traditional knowledge for developing herbal medicines, crop protection, cosmetics, horticulture, agricultural seeds, environmental monitoring, however the ethical consideration in fair and equitable sharing benefits to the indigenous communities are often neglected, undermined and that often create conflicts among stakeholders ,54,55.The collection of wild edibles viz. Buchanania lanzan Spreng., Emblica officinalis Gaertn., Terminalias, Syzygium cumini (L) Skeels, Ziziphus jujuba Mill., Cordia dichotoma G. Forst., Asparagus racemosus Willd., Dioscorea bulbifera L., Boswellia serrata Roxb., etc. were done by heavy lopping of branches, plucking twigs, removal of immature tubers, and sometimes even scarifying trees by felling. The unscientific and over-harvesting have been widely recognized as potential threats for eroding the diversity of WEPs along with other trade in AABR thus affecting the food and nutritional security of communities, which coloborate with the finding of the earlier studies ,38,42,52In-situ conservation of rare, endangered and threatened species like aonla , char (Buchanania lanzan Spreng.), lasooda (Cordia myxa L.), mahua (Madhuca indica J.F. Gmel.), tendu (Diospyros melanoxylon Roxb.) karaya (Sterculia urens Roxb.), salai (Boswellia serrata Roxb.) etc. needs to be promoted by planting species communities under various programmes. The payment to communities rendering services of conservation and restoration of degraded forests shall be ensured through REDD+ (Reducing Emissions from Deforestation and Forest Degradation) and JFPM (Joint Forest Planning and Management) programmes. Domestication of WEPs in buffer and transition zones needs to be encouraged to ensure continued availability; thus, it would provide multiple benefits, promote their livelihoods and income [The past few decades has witnessed rapid degradation of native forests of AABR, Central India , lead tod income . The enc+ and MGNREGA  programmes. The management and promotion of WEPs systematically and sustainably would not only improve food and nutrtional security but also build socio-economic resilience and create novel opportunities for bioprospecting of potential resources. However, sensitive policies and programmes should be evolved to ensure fair and equitable sharing of benefits between communities of AABR and users of biological resources and indigenous knowledge.A total of 172 WEPs providing leafy vegetables, fruits, seeds, nuts, roots, shoots, rhizomes, tubers, mushrooms, etc. were utilized as a source of foods by indigenous communities across different zones of AABR, Central India. The study showed that people living in core and buffer areas of AABR mostly rely on wild edibles supplenenting the requirements of food and nutrition. Baiga, an underprivileged primitive community, possess more traditional knowledge on diverse uses of WEPs, thus exploiting comparatively a higher number of wild edibles for meeting household food and nutrtional needs. The study revealed that livelihoods and economy are intricately linked to traditions and values that are deeply rooted in the culture of Baigas, Gonds, Pradhans, Oraons, Kols of the AABR, while WEPs contributed significantly to the household incomes of these communities; however, the income levels were much lower in transition and buffer zones. The middlemen were key players, exploiting poor communities by procuring the valuable WEPs at nominal prices; therefore it is suggested to develop appropriate mechanisms and evolve institutional arrangements for marketing of WEPs at assured support prices at least for a range of popular commodities so that legitimate benefits could be realized. The processing and value addition of wild flowers, fruits, nuts, mushrooms, etc. needs to be promoted through cooperatives or self-help groups of communities that could not only increase quality, shelf life but also ensure higher income than current levels. The study also indicated that diets of indigenous communities were cereal-based, while the consumption of other commodities was in inadequate quantities, whereas WEPs were supplementing food, essential macro- and micro-nutrients. Nonetheless, the present levels of intake appear to be inadequate but they have potential to meet the total dietary needs if taken in recommended portions and sizes, which will not only add dietary diversity but also overcome the nutrient deficiencies especially in core and buffer zones, where both indigenous populations and WEPs are largely concentrated. The unscientific approach and overexploitation leading to degeneration of valuable wild edible fruit-yielding species like aonla, char, mahua, tendu, bohar etc. affect their frequency and abundance, therefore suitable management interventions were suggested to conserve the vulnerable species by involving the indigenous communities. Moreover, the illegal expansion of agriculture into forested landscapes also eroding the diversity of WEPs in AABR. The Forest Rights Act (2006) will provide a solution to permanent land tenure to communities and discourgae the evil practices affecting the abuandance and diversity of WEPs. In situ and ex situ conservation measures could help in regeneration and preservation of endangered and threatened species, which can ensure financial incentives to local stakeholder communities through JFPM, REDD


We report a novel graphene transfer technique for fabricating graphene field-effect transistors (FETs) that avoids detrimental organic contamination on a graphene surface. Instead of using an organic supporting film like poly(methyl methacrylate) (PMMA) for graphene transfer, Au film is directly deposited on the as-grown graphene substrate. Graphene FETs fabricated using the established organic film transfer method are easily contaminated by organic residues, while Au film protects graphene channels from these contaminants. In addition, this method can also simplify the device fabrication process, as the Au film acts as an electrode. We successfully fabricated graphene FETs with a clean surface and improved electrical properties using this Au-assisted transfer method. T2/V·s . Utilizi2/V·s ,7, gas a2/V·s ,9, and t2/V·s ,11. Unfo2/V·s ,13, chem2/V·s , and che2/V·s ,16. Whil2/V·s , the ele2/V·s ,18. Thes2/V·s .2O and O2 and consequently p-doping of graphene [More recently, the incorporation of new catalysts and optimizations into the CVD process has allowed for the synthesis of single-crystal graphene that does not suffer from these problems ,21. Howegraphene ,23,24.2/Ar [Various processes are employed to eliminate this extrinsic factor. The most widely used method is vacuum thermal annealing at 300~400 °C in ambient H2/Ar ,26,27,282/Ar ,28,29,302/Ar ,29 or ph2/Ar . However2/Ar . While tIn this study, we propose a novel transfer method that resolves the drawbacks associated with conventional approaches. We completely avoid organic contamination by transferring graphene after a thin Au film was deposited on the graphene as-grown on a Cu substrate. As a noble metal, Au prevents any property changes to the graphene and can be easily etched using an ionic solvent. We transferred graphene onto the target substrate via this method and then analyzed its surface using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We confirmed the removal of organic residues by evaluating the electrical properties of a graphene field-effect transistor (GFET) fabricated using the proposed method. Ultimately, we report the fabrication of a GFET with enhanced electrical properties and a clean graphene surface.4 (25 sccm) and H2 (10 sccm) gas at 1000 °C. After growth, the as-grown graphene layer on Cu foil was cut into two parts and used for following PMMA- and Au-assisted transfer. Au film (30 nm) was deposited on the as-grown graphene substrate by thermal evaporator or PMMA  was coated by spin coater for comparison. The backside graphene of Cu foil was removed by oxygen plasma treatment for 10 s at a power of 10 W. The Cu foil underlying the graphene layer was removed by floating on an aqueous solution of (NH4)2S2O8 for 1 h. Graphene supported on Au or PMMA layer was cleaned three times by floating on DI water for 30 min. Graphene was grown on Cu foils by CVD. After annealing a Cu foil at 1000 °C for 15 min, graphene was synthesized for 30 min with CH2 plasma etching and finally depositing a metal electrode (2/KI/H2O), and O2 reactive ion etching (RIE) to etch unwanted graphene. Finally, residue-free GFETs are fabricated through the chemical etching of Au film at the channel area Au film  images were acquired with a Park System NX10 using non-contact mode. Scanning electron microscopy (SEM) images were acquired with a JEOL JSM-6701F field emission scanning electron microscope (FESEM). Raman spectroscopy  with the wavelength of 532 nm (Ar-ion laser) was used to characterize the graphene on 300 nm SiO2/Si substrates using the Au-assisted and the PMMA-assisted methods. XPS in a wide area (beam diameter ~8 mm) can detect not only the C-C sp2 hybridized carbon of graphene layer but also sp3 carbon peaks caused by organic contamination on the graphene′s surface. Through this XPS analysis, the effects of the supporting film and the etchant used to remove the supporting film on the graphene surface were compared  was also calculated using the following Equation (1):w is the width of the Hall-bar-channel, d is the distance between the voltage leads x2 and x1, I is the current flowing between x2 and x1. Carrier density (sn) values can be obtained from Equation (2):Cox is gate oxide capacitance, and q is Coulomb unit charge. Based on these values, mobility can be obtained using Equation (3):To highlight the performance improvements by our proposed approach, we fabricated back-gated GFETs using PMMA-assisted and Au-assisted transfer methods. Previously, improvement of the contact resistance of graphene using Au assisted transfer similar to our approach . Howeverw) of our Hall-bar device was 5 µm, and the length between x2 and x1 was 20 µm. Devices were measured at room temperature with a high vacuum condition of 1 × 10−6 Torr. 2/Si substrate for each of PMMA and Au-transfer graphenes, we determined the distribution of sheet resistance at the Dirac point and the mobility distribution at sn = 3 × 1011 cm−2. While the average sheet resistance of the Au-transferred GFETs was 4300 ± 400 Ω/sq., PMMA-transferred GFETs had a higher sheet resistance of 8400 ± 3300 Ω/sq.  and G band (~1580 cm−1) in the Raman mapping image (I(D)/I(G) value indicates a higher defect density in the graphene area [I(D)/I(G) of our GFETs. Compared with the mapping image of the GFET transferred with Au, I(D)/I(G) values are non-uniform in the GFET transferred to PMMA. In addition, a distribution graph of I(D)/I(G) on graphene shows that the average I(D)/I(G) value is also larger in the GFET transferred with PMMA (Raman mapping of the graphene channels of the GFETs provided the most detailed analysis. The distribution of organic residue on the graphene surface can be characterized by the intensity ratio of D band (~1350 cmng image . In geneene area . PMMA-trene area , and theene area . Figure ith PMMA c.The channel map of the GFET fabricated using PMMA reflects a broad distribution of 2D position, while the channel map of the Au-using GFET is relatively uniform d–f. Addi2/V·s, which are much improved values than the characteristics of devices fabricated from PMMA-transferred graphene. This proposed Au-assisted approach for fabricating GFETs may have significant practical value in the development of graphene-based device applications.In this paper, we compared graphene transferred using Au and PMMA via XPS and Raman mapping. We also examined the electrical properties of back-gated GFETs fabricated with both methods. As a result, it was confirmed that the graphene transferred by the Au-assisted transfer has a cleaner and more uniform surface than the graphene transferred using the conventional organic supporting film. The electrical characteristics of the graphene transferred with PMMA and Au film were measured by fabricating Hall-bar type back-gated GFETs. The GFET fabricated using Au-transferred graphene exhibited an average sheet resistance of 4000 Ω/sq and average mobility of 4500 cm


Lymantria dispar L. (Lepidoptera: Erebidae)) is a serious pest of hardwood forests. In the search for an environmentally safe means of its control, we assessed the impact of different concentrations of essential oils (EOs) from the seeds of three Apiaceae plants  on behavior, mortality, molting and nutritional physiology of gypsy moth larvae (GML). EOs efficacy was compared with commercial insecticide NeemAzal®-T/S (neem). The main compounds in the Eos were trans-anethole in anise; carvone, limonene, and α-phellandrene in dill; and trans-anethole and fenchone in fennel seed. At 1% EOs concentration, anise and fennel were better antifeedants and all three EOs were more toxic than neem. Neem was superior in delaying 2nd to 3rd larval molting. In the 4th instar, 0.5%, anise and fennel EOs decreased relative consumption rate more than neem, whereas all three EOs were more effective in reducing growth rate, approximate digestibility and efficiency of conversion of food into body mass leading to higher metabolic costs to GML. Decrease in consumption and metabolic parameters compared to control GML confirmed that adverse effects of the EOs stem from both pre- and post-ingestive mechanisms. The results indicate the potential of three EOs to be used for gypsy moth control.The gypsy moth ( Lymantria dispar L. (Lepidoptera: Erebidae) is a polyphagous insect that feeds on over 500 plant species within 73 families, but the most suitable hosts are oaks (Quercus spp.) [Gypsy moth us spp.) ,2. In Seus spp.)  and overus spp.) ,7. Gypsyus spp.) ,9.The use of conventional insecticides, often in an inappropriate manner, bears the risk of evolution of insect resistance and may lead to severe environmental disturbances due to pollution and adverse effects on non-target organisms ,13,14,15Plant secondary metabolites are diverse chemical compounds synthesized through metabolic pathways derived from primary metabolism . AlthougAthamanta haynaldii (Borb. Et Uecht.) the EOs provoked almost three times lower leaf damage by GML than in the control group [Pimpinella anisum L., dill Anethum graveolens L., and fennel Foeniculum vulgare Mill.) against GML by assessing their insecticidal and antifeeding activity as well as influence on larval molting, growth and food utilization. It was expected to find a new candidate for developing ecofriendly EO-based insecticide against GML.Apiaceae species are rich in essential oils whose insecticidal and repellent activities have been confirmed in many studies on ticks, mosquitoes, cockroaches, stored products, and crop pests ,60,61,62ol group . This stEssential oils (EOs) were isolated from seeds of three Apiaceae species—anise, dill, and fennel. Anise seed EO is composed of twelve compounds , among which the most dominant constituent was phenylpropanoid trans-anethol . Sixteenp = 0.003; 0.1 vs. 1% and 0.5 vs. 1%: p ˂ 0.001). Significant Bot × Conc interaction indicated that GML sensitivity to increasing concentration differed among EOs and neem , concentration and their interaction on variation of absolute deterrence coefficient (ADC) A. It canand neem A. NamelyAntifeeding activity of the EOs was also confirmed in the choice assay. Variation in applied botanical type and in their concentration showed a significant impact on the relative deterrence coefficient (RDC) (ANOVA results in The sum of an absolute and a relative coefficient (Tot coefficient), showed the best antifeeding activity in anise seed oil C. ConcenThe effect of three EOs and a neem standard incorporated into the diet on larval mortality and molting was estimated after 120 h (24 h of exposure to EOs or neem followed by 96 h of feeding on control diet). As revealed by two-way ANOVA A the perLarval molting into the 3rd instar was also significantly affected by the botanical type and its concentrations . Larvae exposed to EOs and neem ate 35–74% less food  and showed 40–82% reduction in the amount of assimilated  and 24–67% reduction in the amount of metabolized food . Differences of treatment groups from the control group were mostly highly significant  and RCR  differed significantly among experimental groups and exposure to 0.1, 0.25 and 0.5% concentration of EOs and neem led to significantly lower RGR (70–119% reduction) and RCR (42–67% reduction) values comparing to the control group . Only 0.1 and 0.25% dill EO and 0.25% fennel EO acted mainly as feeding deterrents  showed negative values and food consumption relative to initial mass (RCR) had the lowest values at 0.5% EO A,B. RGR ol group . Besidesterrents .12,43.642 = 41.37, p < 0.001; ECD: F12,43.45 = 24.97, p < 0.001) leading to 8–34% and 47–184% reduction respectively. However, whereas AD was significantly reduced in the majority of EO treated groups, ECD showed significant change only at the highest EO concentration  which was most probably caused by a significant decrease in the amount of assimilated food. It can be noticed from Decreased ECI can be a consequence of a lower proportion of assimilated relative to consumed food (AD) and/or a lower proportion of assimilated food allocated towards growth (ECD). EOs and neem treatments significantly affected both indices  EOs and neem did not differ in the impact on nutritional indices A, ECI FD, AD FiE, ECD FF, and inThe impact of essential oils on behavior, survival, and reproduction of various pest insects has been widely studied ,64,65. RAthamantha haynaldii and Myristica fragrans Houtt. EOs. At concentration of 0.1% these EOs showed two times higher absolute deterrence coefficient than anise EO. Additionally, Tanacetum vulgare L. EO delayed molting more effectively than Apiaceae EOs in our study [Ocimum basilicum L. and T. vulgare EOs, and oil-in-water EO emulsions from Thymus herba-barona Loisel. and Rosmarinus officinalis L. [Aesculus hyppocastanum L. and Morus alba L. [Anise and dill seed EOs appeared to be the most effective agents against 2nd instar GML since anise EO had good antifeeding activity and both EOs induced high mortality and delayed larval molting. Kostić et al.  found stur study . On the nalis L. ,74,75,76 alba L. . Pseudaletia unipuncta Haworth [Musca domestica L. larvae [Spodoptera littoralis Boisduval [Tribolium castaneum Herbst [Our findings are in accordance with toxic, antifeeding, and molting delay effects of Apiaceae EOs described in other insect species. Anise, dill and fennel EOs had good larvicidal, repellent, and antifeeding effects on lepidopteran pests ,78,79,80 Haworth  and bett. larvae . In contoisduval  and morem Herbst . Regardim Herbst ,86,87. SAmmi visnaga L. may inhibit ecdysone and further affect the activity of acid phosphatases and molting of Schistocerca gregaria Forsskål nymphs [Comparisons of biological activity of anise, dill and fennel EOs with commercial insecticide neem revealed higher toxicity and antifeeding activity of EOs, and stronger molting delay effects of neem. It has been proved that the neem dominant component azadirachtin is very effective to inhibit the synthesis of active molting hormone 20-hydroxyecdysone, disrupts growth, may lead to incomplete ecdysis, malformations in pupae and adults and reduced fecundity . EOs mayl nymphs .T. castaneum [Spodoptera frugiperda J.E. Smith they might be involved in delayed pupation through inhibition of tyrosinase and cuticle synthesis [We showed that EOs of anise and fennel were rich in phenylpropanoid trans-anethol and dill EO was rich in oxygenated monoterpene carvone and monoterpene hydrocarbons α-phellandrene and limonene. High toxicity and antifeeding activity in insect pests are induced by major compounds of anise, dill and fennel EOs: trans-anethol ,94,95 anastaneum . In Spodynthesis ,101. Howynthesis . Besidesynthesis ,104,105.Physiological mechanisms of insecticidal activity of EOs, their compounds and/or a mixture of compounds is to act as neurotoxins and lead to the paralysis and death of insect pests through the inhibition of acetylcholine esterase (AChE), as well as through blockage of octopamine receptors and/or interference with GABA-gated sodium channels . For exaT. castaneum adults exposed to anise EO [P. unipuncta larvae exposed to trans-anethol [Obviously, exposure to EOs and EOs compounds induce numerous changes in physiological processes that may further affect pest insect behavior and life-history traits. In the present paper, we assessed how three Apiaceae EOs affected the growth and nutritional indices of GML. We showed mainly significant adverse effects of EOs and neem on GML growth (RGR), consumption (RCR), assimilation (AD) and metabolism . In difference to neem experimental group, larvae fed on 0.5% EO supplemented diet lost their mass and had negative values of growth and gross/net growth efficiencies . Therefore, GML mass change during 2 days of feeding was provoked not only by among-treatment variation in the amount of consumed and assimilated food  but also was a consequence of the EO influence on post-ingestive and post-digestive mechanisms. Our results are in accordance with findings of other studies which showed negative values of RGR and ECI in anise EO  and 4th -anethol . Reduced consumption obtained in the present paper in 2nd and 4th instars fed on anise, dill and fennel EO treated diets as well as in studies on the effects of other EOs on GML ,70,74,75Inula racemosa Hook which contained sesquiterpene lactones did not affect RCR and RMR of Spodoptera litura Fabricius larvae at the lowest examined concentration, whereas both indices were reduced at the highest concentration [P.unipuncta exposed to trans-anethol and EO from Petroselinum crispum (Mill.) Nyman ex A.W. Hill, two botanicals which induced larval mass loss. Despite the decrease in the amount of metabolized food in GML fed on EO- and neem-supplemented diets, its proportion relative to ingested and assimilated food increased leading to lower ECI and ECD values.Our results showed that RMR decreased along with a decrease in RCR. Such response depended on concentration so that RMR and RCR were not significantly changed at the lowest concentration of anise and fennel EOs. Likewise, extracts of ntration . Sousa entration  recordedS. frugiperda and Anticarsia gemmatalis Hübner limonene, carvon, estragol and anethol  are detoxified by microsomal cytochrome P-450 monooxygenases [Reduction in food utilization efficiency by botanical treatments points to their chronic toxicity which forces larvae to reallocate energy resources from growth to defense. Depletion of metabolites and adaptive increase in antioxidative and detoxification enzymes have been described in pest insects exposed to EOs ,125,126 ygenases . This enygenases .Pimpinella anisum L.), dill (Anethum graveolens L.), and fennel (Foeniculum vulgare Mill.) cultivated on the experimental fields of the Institute for Medicinal Plant Research “Dr. Josif Pančić” in Pančevo, Serbia . EOs were obtained by hydrodistillation of their seeds using a Clevenger-type apparatus [Tested EOs have been extracted from seeds of anise (pparatus .−1) and 1 μL of each solution was injected in a split-mode (1:30). Gas chromatography was performed using the GC Agilent Technologies 7890A apparatus equipped with a split-splitless injector attached to an HP-5 column  and fitted to a flameionization detector (FID). The operating conditions were: the carrier gas was H2 (1 mL/min/210 °C); the temperatures were set as follows: injector at 250 °C and detector at 280 °C, while the column temperature was linearly programmed from 40 to 260 °C at 4 °C/min. The percentage composition was computed from the peak areas, without correction factors. The essential oils samples were diluted in ethanol  and by comparing their experimentally determined retention indices  to the data from the literature [The Gas Chromatography—Mass Spectrometry was performed using the HPG 1800 C Series II GCD analytical system equipped with an HP-5MS column . The carrier gas was He (1 mL/min). Other chromatographic conditions were the same as those for Gas Chromatography with Flame-Ionization Detection. The transfer line was heated at 260 °C. The mass spectra were recorded in the EI mode (70 eV) in the range of terature .Gypsy moth egg masses were collected from natural populations in the Lipovica Forest, near Belgrade, Serbia  during the autumn. Egg masses were maintained at 4 °C until the next spring. Eggs were mechanically cleaned of hairs, disinfected by soaking into 0.1% sodium hypochlorite solution for 5 min, washed with distilled water for 10 min and air-dried . Eggs frQuercus robur L.) leaf disc (30 mm diameter) in the center of the Petri dish in the no-choice test or two discs on opposite sides of the Petri dish in the choice test. Leaf disc treatments were performed by the leaf dipping method [®-T/S (Trifolio-M GmbH) at three different concentrations  or in a solvent for 3 s. In the no-choice test leaf discs were treated with the EOs, neem or solvent, whereas in the choice test, one leaf disc was treated with the EOs or neem and the other with the solvent. After 30 minutes’ evaporation of the solvent, leaf discs were fixed to the agar layer with pins. Then one larva was introduced into the center of each Petri dish. After 48 h, the remains of the consumed discs were scanned at 200 dpi in jpg format. Quantification of the consumed surface area for each leaf disc was done by subtracting remained leaf disc area from the disc area at the start of the experiment using ImageTool software 3.0 [The antifeeding activity was assessed in the 2nd instar larvae by no-choice and choice tests. After the molting into the 2nd instar, larvae were starved for 24 h. An agar-water (2%) layer of 2 mm thickness was poured into Petri dishes (90 × 14 mm). After agar turned solid we covered it with wet filter paper and placed one oak , relative (RDC), and total (Tot) deterrence coefficients were calculated according to the formulas of ,139:ADC The total deterrence coefficient can range from −200 to +200. According to Tot values EOs can be ranged as very good , good (101–150), average (51–100), and weak deterrents (˂50). Negative Tot values suggest attractant properties of EOs. In the digestive toxicity test, EOs and neem were incorporated into the artificial diet at different concentrations . After starvation for 24 h, ten 2nd instar larvae were put into the Petri dishes and fed ad libitum either on control diet or on EOs and neem treated diets for 24 h. After that, they were transferred into clean Petri dishes and fed on control diets for another 96 h (120 h from the beginning of exposure). During the experiment, two fresh cubes of artificial diet per Petri dish were provided daily. Within each EO or neem and their concentration five replicates were analyzed . Larval mortality and molting were monitored daily and 120 h after the beginning of experiment, the percentage of mortality and percentage of molting into the 3rd larval instars were determined. The percentage of molting reduction relative to the control was calculated as (C − T)/C × 100 where C was the mean percentage of molted larvae in the control group and T was the percentage of molted larvae fed on EO or neem treated diet.After molting into the 4th larval instar, larvae were separated and exposed to 24 h starvation after which their mass was measured individually. Larvae were daily supplied with cubes of the artificial diet with incorporated EOs or neem. As preliminary study showed that larvae fed on EO supplemented diets decreased their mass at the concentration of 0.5%, the study of EO and neem influence on nutritional physiology of GML encompassed concentrations of 0 (control), 0.1, 0.25, and 0.5%. Cubes of artificial gypsy moth diet were weighed before and after the feeding trial, as well as the excrement was weighed at the end of the experiment. Larval mass was measured again 48 h after the experiment was set. All indices were estimated on a dry mass basis. Larvae, uneaten cubes and excrements were dried at 65 °C for 72 h. After this time, the mass of each larva, uneaten cubes, and excrements were weighed. A regression of dry on fresh mass in a random sample of 30 larvae and cubes of artificial diet per experimental group was used for estimating the dry mass of larvae and cubes of artificial diet at the beginning of the experiment. Based on these data the following indices were calculated according to the standard formulas ,141,142 0.5 transformed values of the absolute antifeeding index, larval mortality, larval molting reduction, and log-transformed values of the amount of consumed food, amount of assimilated food, and amount of metabolized food. Dunnett test following one-way ANOVA was used to estimate the significance of differences of treatment groups from the control group. Two-way ANOVA was carried out to evaluate the main and interaction effects of the botanical type (EOs or neem) and the botanical concentration as fixed factors on examined traits. A least square means (LSM) test with the Bonferroni correction was used for a posteriori comparisons (contrasts) of different concentration effects within each EO and neem as well as comparisons of EOs and neem effects within each concentration. Parametric one-way and two-way ANOVAs were performed by software package Statistica 7.0  on untransformed values of the relative deterrence index and (X + 0.5)p ˂ 0.0001). Therefore, significant differences of treatment groups from the control group were revealed by Welch one-way ANOVAs for each pair of comparison followed by the Bonferroni correction [For mass gain, and growth and nutritional indices assumption of homogeneity of variances was strongly violated (Levene’s test, rrection . Signifirrection . LS meanIn whole, Apiaceae EOs can be considered as promising strategy for gypsy moth control based on strong negative effects on survival and consumption in 2nd instar, and impairment of nutritional physiology in 4th instar larvae. Whereas anise EO was the best antifeedant, dill EO exhibited the highest mortality. At a concentration of 0.5%, the three Apiaceae EOs were more effective than commercial insecticide neem in reducing RGR, ECI, AD and ECD of 4th instar GML. Anise, dill and fennel are spice plants used in human nutrition, and have low toxicity to mammals and other non-target organisms ,147,148.


To overcome graphene loss, we investigated 2-D hexagonal boron nitride (h-BN) as an alternative. Unlike graphene on AlN, it was confirmed that h-BN on AlN was intact after the same high-temperature process. Moreover, the overgrown AlN layers on both h-BN/AlN and h-BN/Al2O3 could be successfully exfoliated, which indicates that 2-D h-BN survived after AlN growth and underlines its availability for the vdWE/RE of III-nitrides with further mechanical transfer. By enhancing the stability of the 2-D material on the substrate, our study provides insights into the realization of a novel epitaxy concept.A challenging approach, but one providing a key solution to material growth, remote epitaxy (RE)—a novel concept related to van der Waals epitaxy (vdWE)—requires the stability of a two-dimensional (2-D) material. However, when graphene, a representative 2-D material, is present on substrates that have a nitrogen atom, graphene loss occurs. Although this phenomenon has remained a hurdle for over a decade, restricting the advantages of applying graphene in the growth of III-nitride materials, few previous studies have been conducted. Here, we report the stability of graphene on substrates containing oxygen or nitrogen atoms. Graphene has been observed on highly decomposed Al A challenging approach, but one providing a key solution to material growth, remote epitaxy (RE)—a novel concept related to van der Waals epitaxy (vdWE)—requires the stability of a two-dimensional (2-D) material. Recently, the results of applying graphene at an interface similar to that of the homo-epitaxy have been reported using gallium arsenide (GaAs)/graphene/GaAs,21 zinc oxide (ZnO)/graphene/ZnO,22 and strontium titanate (SrTiO3)/graphene/SrTiO3;23 the structures of these materials are a result of the interaction between the grown material and the substrate. This structure  is called remote-epitaxy (RE); specifically, the exfoliation of the overgrown material occurs as a result of the weak interaction at the interface, and the dislocation-free structure is caused by graphene transparency.24 In conventional GaN growth on SiC, Si (111), and Al2O3, the high dislocation density results in a critical problem owing to lattice mismatch, which typically deteriorates the device quality. Additionally, the strong chemical bond between the epitaxially grown GaN and conventional substrates limits the possibility of using this material in various fields of application. RE can pave the way to overcoming the problems of conventional GaN growth; however, the application of RE has been very challenging for materials containing a nitrogen (N) atom, such as the structure of III-nitride/graphene/III-nitride. It has been almost a decade since the research on GaN growth on graphene was reported.6 Meanwhile, in our previous study, it was highlighted that if a substrate supporting graphene has a N atom , graphene-loss occurs under a conventional growth environment, unlike other reported N-free substrates.25,26 This graphene-loss problem remains unsolved and must be overcome in order to realize RE on III-nitride materials.Placing a two-dimensional (2-D) material at the interface between a grown material and a substrate opens novel opportunities for semiconductor devices. The epitaxy caused by a 2-D material, termed van der Waals epitaxy (vdWE), reduces the dislocation density of the grown material, which strongly affects the device properties, and also allows exfoliation of the grown material from the substrate owing to the weak chemical bond.3 bonds on graphene. Recently, N-doped graphene with carbon (C)–N bonding has been demonstrated by annealing in ambient ammonia (NH3)7,27 and using N2 plasma treatment.13,16 Feng et al. have successfully created a GaN/graphene/SiO2 structure using ambient NH3 annealing on graphene.7 Chen et al. have also shown UV-LED growth on graphene/Al2O3 using N2 plasma treatment before growth.16 These results confirm that N-doped graphene on a substrate containing an oxygen (O) atom is a promising approach to enabling vdWE. Moreover, Jeong et al. have recently shown that graphene is stable on a substate containing an O atom  and that the substrate can be reused for the remote heteroepitaxy of a GaN microrod light emitting diode (LED).18 Meanwhile, regarding the RE structure of III-nitride/graphene/III-nitride, the stability of the 2-D material on the decomposed III-nitride substrate warrants investigation because the growth temperature of III-nitride is higher than its decomposition temperature,28 as shown in Fig. S1a,As graphene has an extremely low surface energy, it is difficult to directly grow III-nitride materials upon it. To allow III-nitride growth on graphene, a potential approach is to generate sp2O3 and AlN were used as substrates to support the graphene. Graphene could still be observed on even the highly decomposed Al2O3 at over 1200 °C, but disappeared on the decomposed AlN at over 1300 °C. Conversely, h-BN grown on AlN was intact after annealing at 1400 °C. We further demonstrated that the overgrown AlN layers on both h-BN/AlN and h-BN/Al2O3 could be successfully exfoliated, which indicates h-BN is robust during metal–organic chemical vapor deposition (MOCVD) of III-nitrides and could be used as an alternative for vdWE.Here, we report the results of an investigation into the cause of graphene-loss and suggest an alternative 2-D material for vdWE or RE of N-containing III-nitrides. We investigated the stability of two different 2-D materials, graphene and h-BN, on substrates containing either N or O as shown in Fig. S1b2O3 and AlN and annealed over 1100 °C for 10 min in ambient hydrogen (H2) by MOCVD. Previous studies on the influence of H2 on graphene have shown that H2 passivates broken points of graphene accompanied by dangling bonds, which could help move a large atom, such as gallium,29 aluminum,30 and indium31 under graphene; however, the aforementioned studies also show that H2 does not result in graphene-loss. Therefore, we used H2 to obtain substrate decomposition at a relatively low temperature rather than ambient inert gas. The photograph of the annealing results shown in 2O3 annealed at each temperature is observed as a black sheet; however, there is no trace of graphene on AlN annealed at 1400 °C. Therefore, we investigated why and how the graphene-loss occurs on AlN. 2O3 and AlN was evaluated using Raman measurements. To analyse the effect of substrate decomposition in detail depending on the temperature, we reveal the fitting data of the D, D′, and 2D peaks at 1300–1700 cm−1 in Fig. S2.2O3 close to 1350, 1580 and 2700 cm−1, respectively. With an increase in the annealing temperature, ID/IG also increases. These defect points are closely related to the decomposition of Al2O3, the critical temperature point of which is approximately 1200 °C in ambient H2.32 Over 1200 °C, the aluminium (Al)–O bond is broken and Al, and O atoms are generated. This O atoms create the D and D′ peaks of graphene, which are similar to those of the O2 plasma-treated graphene.33,34 It is also accurately demonstrated that Al generated by Al2O3 decomposition does not lead to graphene-loss because graphene is observed across the whole surface of all samples over 1200 °C. From the Raman data alone, as shown in 2O3 substrate affects the D and D′ peak of graphene, but it does not lead to graphene-loss. However, in the case of the decomposed AlN containing the same atom, Al, even though it has a much higher decomposition temperature than Al2O3,35 graphene completely disappears at 1400 °C. Regarding the result of annealing at 1300 °C, graphene only partially remained on AlN, as shown in the scanning electron microscopy (SEM) images shown in Fig. S5.−1, which was attributed to the AlN peaks by the reference data shown in Fig. S6.2O3 surface gradually became rough as the annealing temperature increased, graphene wrinkles were still observed, even at 1400 °C. In contrast, on AlN at 1300 °C, the starting temperature of AlN decomposition, graphene wrinkles and the decomposed surface were simultaneously observed, which means that graphene could disappear owing to the decomposition of AlN containing a N atom. The voids were commonly observed on Al2O3 and AlN from 1200 and 1300 °C, respectively, and the void size increased along with the annealing temperature, which implies that voids were generated by substrate decomposition.32,35,36 Moreover, as shown in Fig. S7,2O3 at 1400 °C in ambient inert gas  as shown in Fig. S8.2, the decomposition of AlN was negligible in ambient inert gas, even though the temperature reached 1400 °C.35 As a result, graphene was observed on the AlN layer after the annealing process. Moreover, using Raman spectroscopy we also confirmed that graphene on Al2O3 is partially oxidized into graphene oxide after the same annealing process. This observation is consistent with a previous report by Akiyama et al., in which the authors found that marked decomposition of Al2O3 starts at around 1450 °C.32 It is therefore reasonable to suggest that the graphene oxide observed in this study resulted from the O atom arising from the slightly decomposed Al2O3 owing to the reduced 2D peak intensity, unlike graphene on AlN.To investigate the stability of graphene on a substrate at high temperatures, graphene was transferred to Alet al. have recently reported that N-plasma could result in N incorporation in the graphene lattice. Moreover, they demonstrated decreasing X-ray photoelectron spectroscopy (XPS) intensities of C 1s after graphene was exposed to N-plasma.92O3, demonstrating that the atomic percentage of C is relatively constant, which clearly differs from that in ID/IG and  and is thus very likely to be doped with N. Many reports showed the binding energy of the C–N bonds by measuring XPS. The N-sp2 C, N-sp3 C, and C PBM data was replaced with SVG by xgml2pxml:<glyph-data id="z.dbd" format="PBM" resolution="300" x-size="8" y-size="10" xml:space="preserve">00000000000000000000000000000000111111110000000011111111000000000000000000000000</glyph-data><svg xmlns="http://www.w3.org/2000/svg" version="1.0" width="13.200000pt" height="16.000000pt" viewBox="0 0 13.200000 16.000000" preserveAspectRatio="xMidYMid meet"><metadata>Created by potrace 1.16, written by Peter Selinger 2001-2019</metadata><g transform="translate scale" fill="currentColor" stroke="none"><path d="M0 440 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z M0 280 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z"/></g></svg>O peak positions are mainly reported at 284.9–285.9, 286.5–287.5, and 288.9–289 eV respectively.16,37–45 As shown in 2 C, N-sp2 C, N-sp3 C, and CO respectively. Meanwhile, Ryu et al. demonstrated that the decomposition of GaN generates C–N bonds in graphene oxide, but also incorporates N atoms into graphene oxide,46 which could occur during the annealing of graphene on AlN over 1300 °C in this work. In general, the N 1s of N-doped graphene is characterized by three peak positions, these are, pyridinic-N (398–399 eV), pyrrolic-N (400–401 eV), and graphitic-N (401–402 eV).7,16,37–45,47 Recently, Chen et al. demonstrated a AlN/graphene/sapphire structure using N-doped graphene.48 They observed N-doped graphene with AlN and showed sp2 C–N, and Al–N bonds in the N 1s scan using XPS, although N-doped graphene was covered by AlN. Similar findings were also observed in the N 1s spectrum, as shown in 49 Moreover, the peak expected for pyridinic-N was observed at 398.2 eV, which implies that the N atom could be incorporated in the graphene lattice. A schematic diagram of the graphene structure affected by the N atom is shown in 37,45,47,50 Additionally, with an increase in the N-doping concentration, the Raman peaks of graphene gradually fade.37,45,47 Compared with the reported N-doped graphene model based on our results, the N atom generated by the decomposed III-nitride substrates could also produce the N-doped graphene, which creates many vacancy areas with a loss of C and, thus the elimination of graphene. The O atom creates defect points on the graphene as sp3 bonding and changes graphene to graphene oxide;51 however, the influence of the O atom on the graphene-loss is not critical as comparing to that of the N atom, as shown in †When the annealing temperature reached 1400 °C, the surface was fully decomposed, and graphene completely disappeared on AlN. It is important to understand why and how graphene-loss occurs on the substrate containing an N atom. We speculate that graphene-loss is closely related to the highly N-doped graphene structure. Barbier 19,20 For comparison, we also examined the stability of the h-BN film on AlN using an identical annealing process to that used for graphene on AlN in this work. The AFM images in 2 for 10 min. Clearly, there is almost no difference between these two h-BN surfaces, and the root mean square roughness of the surface before and after annealing is 1.167 and 1.114 nm, respectively. Both the surfaces are decorated by surface wrinkles with a few tiny holes arising from insufficiently coalesced h-BN domains. The h-BN samples were further examined using Fourier transform infrared (FTIR) spectroscopy in the reflection mode. Meanwhile, the AlN/sapphire template was also characterized prior to h-BN deposition. As shown in −1, which is correlated to the transverse phonon frequency of AlN.52 Moreover, both the as-grown h-BN and annealed one exhibited a clear vibration mode at approximately 1368 cm−1, which is associated with the in-plane transverse phonon mode of the sp2-bonded h-BN.53As reported in previous studies, the 2-D h-BN layer serving as a platform for III-nitrides vdWE and/or RE could be another option to overcome the stability issue of graphene on a substrate that contains the N atom discussed above.2O3 peak because it was measured on the Al2O3 substrate after the exfoliation process. Furthermore, Specifically, the peak features for these two h-BN samples are almost the same, which indicates that the effect of the high-temperature (1400 °C) annealing process on the as-grown h-BN film on AlN is negligible. Based on these results, it was confirmed that 2-D h-BN is more stable than graphene on a substrate containing nitrogen. To further examine the stability of h-BN for subsequent AlN overgrowth, around 800 nm-thick of AlN was grown on a template of 5 nm-thick h-BN film on AlN/sapphire. c-plane Al2O3, in which the formed AlN layer almost coalesced on h-BN/c-plane Al2O3, and this can even be easily exfoliated using scotch tape, as shown in c-plane Al2O3 presents an island-like surface of the AlN layer, as shown in Fig. S11,In addition to the AlN overgrown on h-BN on AlN, we also examined the AlN growth on 3 nm-thick h-BN on sapphire and demonstrated the successful post-growth exfoliation of AlN. 2O3, graphene was observed even though Al2O3 was fully decomposed; however, graphene was not observed on the decomposed AlN, which means that the N atom generated by substrate decomposition not only causes graphene loss, but also limits the application of graphene in novel epitaxy concepts. Unlike graphene on AlN, layered h-BN grown on AlN exhibited good stability and did not show significant differences in surface features before and after the annealing process. Furthermore, it was also observed that the grown AlN layers on h-BN/AlN and h-BN/Al2O3 could be easily exfoliated. All of these results prove that h-BN is stable on the AlN surface and survives during the high-temperature AlN overgrowth process. Therefore, it is necessary to use a substrate that can avoid graphene loss and to select appropriate 2-D materials, such as h-BN, that are sufficiently robust for the realization of a novel epitaxy concept for III-nitrides.In conclusion, we investigated the stability of graphene on substrates containing O or N atoms and demonstrated that graphene was unstable on substrates containing an N atom above its decomposition temperature. In the case of graphene on AlH. Amano and D.-S. Lee directed and funded this work. J.-H. Park and X. Yang conceived and wrote the manuscript. J.-H. Park, X. Yang, J.-Y. Lee, M.-D. Park, and M. Pristovsek conducted experiments. J.-H. Park, X. Yang, J.-Y. Lee, M.-D. Park, S.-Y. Bae, and M. Pristovsek analysed data. All authors discussed the results and commented on the manuscript.There are no conflicts to declare.SC-012-D1SC01642C-s001


Reduced graphene oxide (rGO) flakes obtained by thermal annealing of graphene oxide at 300 and 600 °C exhibited electrical conductivities of 2.3 ± 1.0 and 14.6 ± 5.5 S/m, respectively, showing the effect of thermal reduction on the electrical conductivity of rGO flakes. This study demonstrates an alternative method to characterizing the intrinsic electrical conductivity of graphene-based materials, which affords a clear understanding of the local properties of individual graphene flakes.The intrinsic electrical conductivity of graphene is one of the key factors affecting the electrical conductance of its assemblies, such as papers, films, powders, and composites. Here, the local electrical conductivity of the individual graphene flakes was investigated using conductive atomic force microscopy (C-AFM). An isolated graphene flake connected to a pre-fabricated electrode was scanned using an electrically biased tip, which generated a current map over the flake area. The current change as a function of the distance between the tip and the electrode was analyzed analytically to estimate the contact resistance as well as the local conductivity of the flake. This method was applied to characterize graphene materials obtained using two representative large-scale synthesis methods. Monolayer graphene flakes synthesized by chemical vapor deposition on copper exhibited an electrical conductivity of 1.46 ± 0.82 × 10 Since the intriguing electronic properties of graphene have been experimentally observed in mechanically cleaved graphene ,2,3, it Electrical conductivity is one of the most important properties of synthesized graphene. However, the intrinsic electrical conductivity of graphene is significantly affected by its atomic and chemical structures. For example, the presence of grain boundaries in polycrystalline CVD-grown graphene deteriorates its electrical conductivity owing to the scattering at the grain boundary interfaces . GraphenThe electrical properties of monolayer graphene have been investigated using several methods. To characterize individual graphene flakes, micro-sized metal electrodes were patterned on a graphene flake using photolithography techniques. Although this method has been extensively used to study the electrical properties of graphene flakes, such as mechanically exfoliated graphene and individual GO flakes ,12, it rIn this study, we employed C-AFM to directly measure the electrical conductivity of individual graphene flakes prepared by two prominent scalable synthesis methods: CVD on copper and the thermal reduction of GO. Without using any additional materials for electrical measurements, a graphene flake connected to a pre-fabricated electrode was scanned using an AFM tip, which generated an in-plane current distribution. The current change was analyzed as a function of the distance from the electrode to extract the electrical conductivity of the individual graphene flakes. This method was applied to CVD-grown monolayer graphene flakes. Furthermore, individual rGO flakes were characterized as a function of the degree of thermal reduction.High-quality sub-monolayer graphene was synthesized on copper foil using low-pressure chemical vapor deposition (LPCVD) . Copper 2/Si . T. T2-hybr20 cm−1) ,46,47,48l groups ,50, whic2 (Wt = 4.872 nm) and 20.750 nm2 (Wt = 5.140 nm) at annealing temperatures of 300 and 600 °C, respectively. Therefore, using the given equation to fit the resistance–distance curves, the electrical conductivities were estimated to be 2.3 ± 1.0 and 14.6 ± 5.5 S/m for 300 and 600 °C annealing samples, respectively (D/IG. Several previous studies have investigated the electrical conductivity of isolated graphene flakes. Monolayer rGO flakes with a C/O ratio of ~4 synthesized by the photoreduction of GO using ultraviolet light irradiation in vacuum exhibited an electrical conductivity of 0.20 S/m, which was directly measured by C-AFM [ectively f. This iby C-AFM . Moreoveby C-AFM . A similby C-AFM . Conside2/Si exhibited a high electrical conductivity comparable to that measured by the van der Pauw method. In addition, GO flakes placed on SiO2/Si were thermally reduced at two different temperatures. Annealing the rGO flakes at higher temperatures resulted in a higher electrical conductivity, which was confirmed by an increase in the C/O ratio and a decrease in ID/IG. This study demonstrates that the C-AFM method is capable of estimating the local electrical conductivity of individual graphene flakes. In addition, this study provides a better understanding of graphene materials synthesized using the two major scalable production methods.The electrical conductivities of isolated graphene flakes were investigated using C-AFM and an analytical analysis. Monolayer graphene flakes obtained by CVD on copper foil and the thermal reduction of GO were characterized using C-AFM. High-quality CVD-grown monolayer graphene flakes transferred onto SiO


Ammonia emissions were product of ammonia concentration and air exchange rate. Temperature and relative humidity were measured to establish microclimate conditions in buildings tested to show the overall microclimatic situation in buildings. Differences between ammonia emission rates were observed in both housing systems. The highest ammonia emission rate was equal to 2.75 g·h−1·LU−1 in well-ventilated cattle barn with the largest herd size.The aim of the study was to present the scale of greenhouse gas emissions from animal production, and to provide test results from different housing systems. In three free stall buildings, two with slurry in deep channels and one with cattle in cubicles staying on shallow litter concentration of ammonia and carbon dioxide were measured in summer season by using dedicated equipment from Industrial Scientific Research. Air exchange was calculated on the base of balance carbon dioxide method. This method was used in order to estimate the air flow rate. Concentrations of ammonia and CO Milk and meat production are finally balanced with an environmental and animal welfare conditions to minimize negative influence for the environment. Major amount of nitrogen are leaching from livestock production to the environment.According to the inventories, agriculture is a significant source of greenhouse gases (GHG) . Nosek et al.  confirme2, SF6 or cryptone 85 as tracer gases  by using gas concentration meters, made by company Industrial Scientific Co.V) using validated method of carbon dioxide balance. For metabolic emission of carbon dioxide by one LU, average values were used WCO2 = 220 g·h−1·LU−1 according to the Institute of Zootechnics in Cracow.Estimation of air exchange rate (E).Calculation of ammonia emission (The methods in our research consisted of the following stages:E) was equal product of air exchange rate (V) and ammonia concentration (S):Ammonia emission , connected with concentrator LB-731 for data collecting.The following measurement equipment was used:A short characteristic of herd like herd size and system of removing manure is shown in Table The obtained results of harmful gas emission which is ammonia depend on the effectiveness of the ventilation.−1·LU−1). In contrary, the lowest emission 1.47 (g·h−1·LU−1) was observed in a cattle barn with the lowest cubage.The highest level of ammonia emission was observed from cattle barn with deep slurry channels and with the highest ventilation rate which amounted 2.75  was below than critical level of 0.05 (5%), and the statistical empirical value F = 27.494. The statistical analysis of the temperature influencing the NH3 emission level delivers that the significance level (p) was 0.01184 and the statistical empirical value F = 4.4595. The case of temperature impact on the CO2 emission level, inversely than the NH3 emission level, delivers the correlation. The obtained results were the basis for the Duncan tests that determine the temperature values to homogeneous groups. The analysis showed that each of the tested temperatures is in a different homogeneous group, which makes significant differences in the temperature impact on the level of CO2 emissions. The mean temperature for the low level of the CO2 emission was 21.5 °C, for the average level was close to the 23.2 °C, but high emission was not known. The correlation of relative humidity outside and relative humidity inside with the NH3 emissions from cattle houses was conducted. The estimated recommended levels of NH3 emissions were also used. The results of relative humidity outside and humidity inside correlation with the CO2 and NH3 levels were presented in Fig. During the statistical analysis, the expected marginal mean of temperature influence to CO2 and NH3 emission levels in both cases. Similarly, in both statistical analyses, the significance value (p) was below a critical level, which means that the correlation exists. The empirical value of statistics F during the relative humidity outside and relative humidity inside comparison with the CO2 was equal to 34.726, and the Wilks Lambs = 0.92405. In the case where the relative humidity outside and relative humidity inside were correlated with NH3, the empirical value of statistics F = 17.507 and the Wilks Lambs = 0.92201. The characteristics of homogeneous groups defining the effect of relative humidity outside and relative humidity inside comparison with the CO2 and NH3 levels were presented in Table It was statistically confirmed that the relative humidity outside and relative humidity inside had an influence on the COcs F2, 84 during t2 and NH3 emission. Statistical analysis confirmed the need for reducing the relative humidity inside to limit the CO2 and NH3 emissions. Considering the whole scope of the conducted studies, it can be noticed that the best conditions for limiting CO2 are to reduce temperature and humidity outside and inside of livestock housing. Ammonia emission could be reduced by simultaneously decreasing air humidity and decreasing air temperature. In the case of NH3 emission, reduction is necessary to increase the temperature and reduce the humidity inside the building.According to Table 3 emissions were observed. A similar situation was described by Zhang who tested ammonia emissions from 11 types of cattle barns, with different floor and manure removing systems and the highest emission was in non-littered cattle barns  despite weather conditions. In particular, in non-litter cowsheds, higher NHSimilar results were obtained by a Polish researcher, which calculated ammonia emissions by using model (not measured) from dairy cattle for particular technologies ranging from 6.4 per year for deep litter up to 28.69 kg per year for a slurry system, but these results based only on simply assuming fixed rate of nitrogen losses from manure in livestock buildings   compared to other authors’ results.Table 3 emission from litter-free barns was about two times higher than emission from barns with litter. A similar trend was obtained in our research, where the emission from the litter-free system in one of the barns was about 24 kg·year−1·LU−1∙and for the litter system 12.87 kg·year−1·LU−1.According to Demmers et al. , the annRecently, livestock production significantly increased in Central Europe that involved the need of correction of emission factors. Generally, in Poland, it is utilized emission coefficient elaborated in Northern European countries . In this study, first step was made to present Polish emission factor dedicated especially to summer season conditions.2 and NH3 emission. A completely different validity occurred in accordance to the measured temperature values, where the increase in temperature could cause the reduction of NH3 emission. However, this validity was not confirmed by statistical analysis where the lack of temperature influence on the NH3 emission level confirms the value significance level p = 0.01184. All other cases of statistical analysis have reached the significance value p below the critical level of 0.05. The main conclusion from the research is that ammonia emissions from cattle barns with slurry were higher than from cattle barn bedded with straw, but simultaneously in the night period, both emission levels were comparable.Although the change of temperature and humidity was not huge, measured values allowed estimating the levels of gas emission in order to carry out the statistical analysis. According to the study, the increase of relative humidity outside and relative humidity inside caused an increase of CO