To develop an estimate of self-reported last 30 day alcohol use by university students in China.A search of papers published in English and Chinese between 2006 and 2015, following pre-established selection criteria, identified 30 papers that were included in this meta-analysis. Nine moderator variables were preselected for this analysis.A total of 749 papers were identified in the keyword search, and 30 studies  met all selection criteria and were included in the meta-analysis. The self-reported last-30-day alcohol use for undergraduate university students was 66.8% for males and 31.7% for females. Meta-regression identified three moderators associated with the different drinking rates reported: the definition of drinking, the origin of the questionnaire used in the survey, and the geographic region where the survey was conducted. These three moderators explained 56% of the heterogeneity of reported drinking rates for the male students and 47% of the heterogeneity of reported drinking rates for the female students.The results of this meta-analysis provide an estimate of last 30 day alcohol use by university students (age 18–23) and increase our understanding of drinking by young people in China. The meta-analysis suggested three variables that could have affected the results and which are worthy of further study. The discussion places these results in the context of Chinese drinking culture and university life. The World Health Organization (WHO) suggests a 36% increase in per capita alcohol consumption in liters of pure alcohol in China between 2003–2005 and 2008–2010 . For exaTo further explore the trajectory of adolescent to adult drinking, this project was developed to analyze last 30 day alcohol use among Chinese undergraduate university students that were reported in papers published between 2006 and 2015 in English and Chinese.gaokao) at the end of their 3rd year. This is a highly competitive educational path, and the gaokao result determines which universities will accept a student’s application for admission. The higher the student’s score on the gaokao, the greater his/her chance of being admitted to one of the more prestigious universities. Students with lower scores will apply to less prestigious universities or to community colleges/city colleges. The community/city college option results in a three-year degree, the university option results in a four-year degree.Students who enter university in China follow a specific educational path. The nation provides compulsory general education through middle school (age 15). At the completion of middle school, university-bound students enter a regular high school, and the other students enter a vocational high school. Vocational high schools prepare students with the technical skills to directly enter the workforce after 2 to 3 years. The regular high school students, meanwhile, attend high school for three years and take the national university entrance exam .The Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) guided this project  , WanfangFive pre-established criteria were determined for a study’s inclusion in the analysis. Papers had to 1) be based on original data, 2) report the last 30-day drinking rate, 3) report drinking rates by gender, 4) describe students attending a university/college in Mainland China, 5) be published in a peer-reviewed journal in English or Chinese between 2006 and 2015.To increase the integrity of the data used in the meta-analysis we selected only papers reporting on original survey data. Articles using duplicated data or secondary sources were excluded.Previous studies have estimated drinking rate in the past seven days, 30 days, three months, six months and last year. We selected the past 30 day recall because it was the most frequently used, because it allowed sufficient time to capture drinking behaviors, and because it was less subject to memory error than longer recall periods . AlcoholPrevious surveys of drinking behavior in China have suggested there are significant differences in the drinking rates of males and females , 18, 20.Hong Kong, Macau and Taiwan were excluded because their recent history differs significantly from that of the Mainland. Studies of Chinese students in other countries were excluded.We recognize there may be relevant studies published in other languages, but we lacked the resources to seek them out.Quality Assessment of Systematic Reviews and Meta-Analyses (NIH) was used  . The moderator of definition of drinking explained 20% of the heterogeneity. Surveys that used investigator-developed questionnaires reported higher drinking rates for males than surveys based on the more standardized YRBS questionnaire , and the moderator for questionnaire explained 21% of the heterogeneity. Surveys of central China university students reported higher drinking rates than surveys of east China university students . Surveys of west China university students reported higher drinking rates than surveys of east China university students . The moderator for geographic region  explained 21% of the heterogeneity.According to the results from the bivariate meta-regression analysis, the definition of drinking, the origin of the questionnaire, and the geographic region of the survey were associated with the heterogeneity across the selected studies on the logit male drinking rate Table . SurveysA multiple meta-regression model was used to assess all the significant moderators in one meta-regression model. The variables of a clearly stated definition of drinking, the origin of questionnaire, and geographic region were still significant after the Bonferroni correction and explained 56% of the heterogeneity in male drinking rate.p < .001). The pooled drinking rate for male students was 64% for using YRBS questionnaire and 60.1% for using investigator-developed questionnaire. The pooled drinking rate for male students in the east, central and west regions was 52.1%, 74.8%, and 67.5% respectively (Q (2) = 1252.67, p. < 001). The group difference is significant for the logit male drinking rate (Q (1) = 257.30, p < .001)  on the heterogeneity, a follow up test was performed to determine whether the pooled drinking rate for male university students differs between groups. In the subgroup analysis, the pooled drinking rate for male students was 70% using definition of alcohol drinking and 63% without definition. A significant Q value indicates a significant group difference in the logit drinking rate of males (Q (1) = 227.12, 2 = 99.19, Q = 3566.0, df = 29, p < .001) among reported drinking rates.The pooled estimates for the drinking rate in the past 30 days among female university students was 31.7%, 95% CI 27.8, 35.8] . The moderator of definition of drinking explained 14% of the heterogeneity. Surveys that used investigator-developed questionnaires reported higher drinking rates than surveys based on the more standardized YRBS questionnaire , and the moderator for questionnaire explained 12% of the heterogeneity. Surveys of central China university students reported higher drinking rates than surveys of east China university students . Surveys of west China university students reported higher drinking rates than surveys of east China university students . The moderator for geographic region  explained 22% of the heterogeneity.According to the results of the bivariate mega-regression analysis, the definition of drinking, the origin of the questionnaire, and the geographic region of the survey were associated with the heterogeneity across the selected studies on the logit female drinking rate Table . SurveysResults from the multiple meta-regression analysis indicated that only the variable ‘a stated definition of alcohol drinking’ is significant after the Bonferroni correction, and this variable explained 47% of the heterogeneity.p < .001)  = 492.86, This meta-analysis provided an estimate of Chinese undergraduate university student drinking rates in the last 30 days of 66.8% for male university students and 31.7% for female university students. As expected, the estimated drinking rate is higher for males than for females. While many papers on alcohol use by university students have been published, this is the first to present an estimate of last 30 day drinking rates based on surveys of Mainland China undergraduate university students, published in English or Chinese, and describing male and female alcohol use separately. The results reflect the best estimate of last-30-day alcohol use by Chinese undergraduate university students.This estimate for university students’ alcohol use is higher than WHO’s estimates of per capita drinking in the previous year for persons 15 years and older in China: 58.4% male, 28.9% females [gaokao).This estimate for university students’ alcohol use is also higher than the last 30 day drinking rates estimated for high school students: 36.5% males and 22.2% females attending regular high schools, and 44.7% males and 28.8% females attending vocational high schools . The siggaokao, while the vocational high school students typically are not. Preparation for the gaokao is rigorous and begins before the last year of high school. Students pressure themselves to a strict discipline of study, reinforced and supervised by parents and teachers. There is little time for any recreational activities. By comparison the vocational high school students have more discretionary time to be involved in activities that include alcohol. Once high school students have finished the gaokao and have been accepted to universities, they are under much less pressure and have more freedom to engage in activities that could include alcohol. In this manner the gaokao may be protective for high school students by delaying their drinking until they enter university. There are likely other individual-specific explanations for these rates that have not been identified and studied.Studies of Chinese high school students’ drinking have found that vocational high school students report higher drinking rates than regular high school students . One of The university student drinking rates need to be interpreted in the context of Chinese university life and Chinese alcohol culture. China is a relationship society, meaning the social structure is based first on relationships. Actions that build, maintain and protect relationships are important, and sharing alcohol is an important part of this process. Alcohol use in moderation is considered good for health, it is a part of meals, ceremonies and celebrations, and it is an important part of Chinese medicine. It is legal for university students to purchase and consume alcohol. Chinese universities, with the exception of the newest campuses, are walled compounds with everything inside the walls that students need: housing, recreational facilities, food services, health services, educational services, post offices, small shops and banks. During the week there is little need to leave the campus. On weekends students will often go off-campus with friends to eat a lunch or dinner at local restaurants. Eating with friends is a typical occasion for drinking alcohol, usually beer. In this context, the last-30-day rates reported here are not surprising and do not necessarily represent high risk drinking.2 suggests caution in interpreting these results. Nine moderator variables were examined in the meta regression, and three of the moderators should be considered in interpreting these results: whether the survey stated a definition of drinking, whether the questionnaire was based on YRBS or was investigator developed, and the geographic region where the data were collected.The moderator analysis showed that the heterogeneity observed affected the results, and the significant I A clearly stated definition of drinking as having “at least one cup” of an alcohol beverage (yes vs. no) was associated with the logit drinking rates of male and female university students. Surveys with stated definitions of drinking reported lower drinking rates compared to surveys without definitions Table . This fiLogit drinking rates for males were related to whether or not the questionnaire was developed by the investigator or based on YRBS. Studies that used YRBS-based questionnaires reported higher drinking rates for males compared to studies using investigator-developed questionnaires. There was no significant difference in female last-30-day drinking based on type of questionnaire Table . We beliThe most likely variations in questionnaire development that affect these differences relate to 1) how alcohol is defined, 2) how quantity is measured, and 3) how frequency is measured, and 4) the way Western questions are translated into Chinese.huangjiu  or low strength rice wines and porridges. Distilled spirits are popularly classified by the grains used to make them and by their strength . Locally-made varieties of unlabeled, unrecorded spirits are legal, inexpensive and readily available, especially in rural areas [In the West, alcohol questionnaires are generally organized around three types of alcohol: beer, wine, and spirits. In China, the classification of alcohol types is more complicated: there are more types of beverage alcohol and there is no widely accepted understanding of a standard drink. Beer is comparable, with beer strength and packaging being fairly similar in China and the West. In China “wine” can mean fruit wines , but it also refers to traditional wines such as al areas . Medicinal areas , 18.Alcohol survey questions ask if a respondent has drunk alcohol at least once “including one sip,” some questions specify “at least one cup.” There is an absence of a widely accepted understanding of a “standard drink” both in terms of the drinking cup size and the beverage container size. Beer is sold in reasonably uniform-sized containers, ranging from 300 ml to 1 L, so survey data on beer consumption can probably provide useful information on quantity. Fruit wine  is often in standard bottles and served in wine glasses; however, wine currently makes up less than 3% of alcohol consumed in China . Spiritsjiu, 酒) is used as a generic term for all types of alcohol. Beer is sometimes not thought of, by survey respondents, as a form of alcohol. Because alcohol use, even by very young people, is an unremarkable event, especially at festivals, unless carefully specified in the questionnaire many drinking events may be overlooked by respondents when answering questions about alcohol use.Translating Western alcohol survey questions is challenging, and the accuracy of the translation directly affects the validity of the data collected. There are many Chinese words for different types of alcohol. In everyday conversation “wine”  was associated with the logit drinking rates for male university students. Surveys of students at central China universities reported higher drinking rates. Surveys of students at eastern China universities reported lower drinking rates, and surveys in western China reported drinking rates in between.A meta-analysis of studies of high school student alcohol use also found higher drinking rates were reported from surveys of west China adolescents. That meta-analysis of high school surveys found surveys from central China reported lower drinking rates, and surveys from eastern China were in between . NeitherBecause high schools enroll local adolescents, we expected to find some geographic differences that reflected regional differences in alcohol use. Universities, on the other hand, especially the more prestigious universities, serve students from all parts of the country, so accounting for differences due to the geographic region of the survey is more difficult.The very suggestion of drinking rates varying at universities in different regions of the country begs exploration, as does the effect of geographic region on male drinking but not on female drinking. Geographic differences in drinking rates in a country as large and diverse as China calls into question the usefulness of national drinking rate estimates in alcohol policy development.Many technical issues, not assessed in this analysis, could have affected the results. Survey research is relatively new in China and surveys of populations like university students are often conducted by well-meaning investigators with little experience. We have no information on the conditions under which the data were gathered, how confidentiality was assured, how any assurance of anonymity was interpreted or the methods used for data collection. We have no information on how the samples were identified and how individuals who completed surveys were recruited. We have no information on the times of the year the surveys were conducted. Timing could have affected survey results if data were collected within 30 days of significant festivals, rites of passage and other significant events in which alcohol is a traditional part. The diversity of the students in the samples represented in these papers may not have been truly representative of the Chinese university student population. We know little about data management and analysis techniques used in the studies included in this analysis.This meta-analysis of 30 studies published in Chinese and English between 2006 and 2015 of self-reported alcohol use by Chinese undergraduate university students (approximate age 18–23 years old) provided an estimate alcohol use in the last 30 days of 66.8% for males and 31.7% for females.


Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. The lithium solvation structure in the electrolyte solution for lithium-ion batteries has not been fully understood. Here, the authors show ultrafast fluxional exchange of carbonate solvent molecules in and out of lithium-ion solvation sheath utilizing coherent two-dimensional infrared spectroscopy. Typical electrolyte solutions used in LIB are composed of non-aqueous carbonate solvents that have certain advantages. For instance, the oxidation potential can be matched to the output voltage of LIB and carbonate solvents are also building blocks of solid-electrolyte interphase78910Electrolyte solvent capable of dissolving lithium salt is an integral part of Li-ion battery (LIB) that has become an indispensable power source for current mobile ecosystem and electrical vehicles123+ conductivity, mixed solvents have often been used not only because they increase the solubility of lithium salt but also because they serve as excellent media facilitating fast transport of Li-ion+ transport. To enhance Li+ ion mobility as well as to improve low-temperature performance, linear alkyl carbonates like diethyl carbonate (DEC) and dimethyl carbonate (DMC) are added to the LIB electrolyte solutions as co-solvents. It has long been believed that such low viscosity co-solvents act as a medium for transporting the sheaths of Li+ ion-solvent complex6, is dissolved in organic carbonate mixed solvents consisting of equal volumetric amounts of DEC, DMC and EC. Li+ is believed to be preferentially solvated by EC, and DEC and/or DMC provides the medium for large Li–EC complexes to flow between electrodes during charging and discharging processes. However, to our surprise, detailed microscopic solvation structures and ultrafast solvation dynamics around Li+ in such electrolyte solutions have not been fully understood and even they are still the key subjects under intense scholarly debate.To achieve high Li+ would, without a doubt, help one to better understand the working principles of LIB and to eventually design an improved LIB. Most of the previous studies primarily focused on the equilibrium structure of the first solvation shell of Li+, which has often been referred to as solvation sheath due to its rigidity13141516+ in mixed solvent electrolyte solutions18et al.17O NMR experiments show that Li+ makes a direct electrostatic interaction with carbonyl oxygen atoms of surrounding carbonates. Even in the case that Li+ is preferentially solvated by EC or PC, the participation of co-solvent molecules, such as DEC and DMC, in the solvation sheath is possible not only because of their high-mole fractions but also because of extra entropic gain. Therefore, it is by now clear that such co-solvents could potentially play a dual-role of low-viscous medium and solvating molecule. Co-solvents like DEC and DMC would add an extra flexibility to solvation sheath, because they comparatively weakly interact with Li+ and have many conformational degrees of freedom+ solvation sheath has been reported due to their ultrafast nature and experimental difficulties in finding an appropriate spectroscopic probe.Therefore, elucidating the molecular solvation structure of organic carbonates around Li+ ion. Here considering the carbonyl stretching vibration of DEC as an infrared probe, we carried out Fourier transform infrared (FTIR), femtosecond infrared pump-probe and two-dimensional (2D) infrared studies of chemical exchange processes between DEC molecules with and without Coulombic interaction with Li+. One of the most difficult problems in the present linear and nonlinear infrared spectroscopic investigations is that the infrared probe, DEC, itself is the solvent too. Thus, with normal infrared cells with several micrometre thickness at best, the linear absorption is saturated and the nonlinear infrared signal fields are self-attenuated, which renders a difficulty in detecting weak 2D infrared signal. To overcome this, we prepared a home-built thin sample cell coated with SiO2, using radio frequency magnetron sputtering technique , O−C−O asymmetric stretching , and O−CH2−CH3 asymmetric stretching  vibrations. As LiPF6 concentration in the DEC solution increases, two distinctively new peaks at 1,715.4 and 1,305.6 cm−1 appear. The frequencies and spectral widths of the main peaks at 1,747 and 1,258.9 cm−1 do not change much on increasing lithium salt concentration. Therefore, the two new peaks at 1,715.4 and 1,305.6 cm−1 can be safely assigned to the C=O stretch and O−C−O asymmetric stretch modes of DEC molecules directly interacting with Li+.The infrared absorption spectra of the C=O stretch and O−C−O asymmetric stretch modes in LiPF+. They are two ester ether oxygen atoms and one carbonyl oxygen atom. Therefore, at least two structures in 17O NMR experiment provided evidence that the ester ether oxygen atoms do not strongly interact with Li-ion−1 and 1,235.5 cm−1, respectively  of C=O frequency and red shift (96.8 cm−1) of O−C−O asymmetric stretch frequency. These results can be understood by noting that the Li+ ion interacting with carbonyl oxygen atom makes the double bond character (or bond length) of C=O group decrease (increase), which concomitantly makes the C−O bond lengths short  DEC surrounded by other DECs, (ii) DEC interacting with free Li+ and (iii) DEC interacting with Li+ in the CIP state, Li+:PF6−. In addition, the existence of two different types of anions, either PF6− solvated by DECs or PF6− in CIP imposes yet another complexity to the interpretation of linear and nonlinear infrared spectra. However, because the negatively charged PF6− tends to be away from the carbonate part of DEC due to Coulomb repulsion and preferentially surrounded by the DEC ethyl groups6− does not strongly affect the DEC carbonyl stretch infrared spectrum.The number of solvent molecules in the first solvation shell of a solute molecule is an important quantity providing information on the size and structure of Li-ion solvation sheath. Often, a series of lithium salt concentration-dependent spectroscopic experiments has been used to determine the solvation number around a Li+:PF6− as compared to DEC···Li+, we further analysed density functional theory calculation results of DEC interacting with Li+:PF6−  of free DEC and the positive 0–1 peak (ground state |0> bleach and stimulated emission from |1> to |0>) of Li–DEC complex at around 1,720 cm−1. Another notable feature is the prolonged positive signal  is found to be much shorter than that of free DEC (2.1±0.1 ps). Detailed discussion on the origin of such increased vibrational relaxation rate of DEC upon its electrostatic interaction with Li6 DEC solution at different waiting times. Each 2D infrared spectrum was normalized to the largest positive 0–1 peak magnitude. At a very short waiting time of Tw=0.3 ps, there are only two peaks on the diagonal line (see the upper-left panel in ωt) axis are the excited state absorption contributions. Both positive and negative peaks are elongated along the diagonal line at short waiting time up to Tw=1.0 ps. However, after 2.0 ps, all peaks become round in shape due to the spectral diffusion process. Diagonally elongated peaks at short waiting times indicate structural heterogeneity, distribution of coordination number and ethyl side-chain conformational distribution +. We found that the C=O stretch frequency–frequency correlation decays on a few picosecond timescale, which could result from ultrafast internal rotations of the ethyl groups in DEC and hindered rotational motions of carbonates.−1, which is slightly broader than that of free DEC (FWHM=18.9 cm−1). However, the vibrational lifetime of Li–DEC is just half of that of the free DEC, which means that the lifetime broadening of Li–DEC is larger than that of free DEC. These observations indicate that the inhomogeneous linewidth of Li–DEC may be narrower than free DEC, which is consistent with the notion that DEC molecules in Li–DEC complexes have stable conformers and the side-chain structure can be correlated with its solvation propertyIn principle, the inhomogeneous structural distribution can be studied by analysing the centre or nodal line slope and/or diagonal ellipticities of 2D infrared peaks3233+ could be affected by the presence of co-solvents in the first solvation shell. In a recent 17O NMR experiment, NMR peak of carbonyl oxygen atom in EC or DMC shows a motional narrowing behaviour, indicating the existence of fast equilibrium dynamics between free carbonate and Li-complexed carbonate molecules in nanosecond or even shorter timescales5+ in LIB electrolyte solutions. To date, however, little has been understood about how fast the solvation dynamics and the structural fluctuation of solvation sheath.In a real LIB electrolyte solution, detailed solvation dynamics around LiTw>2 ps), one can clearly observe cross peaks  induced by conformational transitions between different solvation structures. Indeed, at longer waiting time n–1 and DEC···Li+:PF6−(DEC)n–2. However, DEC in DEC···Li+(DEC)n–1 and that in DEC···Li+:PF6−(DEC)n–2 are neither spectrally nor kinetically resolvable, due to the similarity in solvation structures. This led us to use a simple two-state exchange model between DEC and DEC···Li+(ligands)n–1, where ligand refers to either DEC or PF6− and n varies depending on lithium salt concentration and solvent composition. Here the chemical exchange dynamics is therefore the dynamical equilibrium between Li+(ligands)n and Li+(ligands)n–1+free DEC (The Li–DEC coordination breaking and forming dynamics are manifested in the free DEC .+(ligands)n–1 can be obtained from the infrared spectral peak analyses after extracting information on the corresponding transition dipole ratio from the LiPF6 concentration-dependent infrared data (+(ligands)n–1 is 1.7 times larger than that of free DEC, which is in excellent agreement with quantum chemistry calculation results (+(ligands)n–1 to DEC is found to be 0.138, that is, [DEC···Li+(ligands)n–1]/[free DEC]=0.138. From the peak volumes  1.0 M LiPF6 in DMC:PC (1:1 in volume percent) solution, (ii) 1.5 M LiPF6 in DMC:PC (1.5:1) solution and (iii) 2.0 M LiPF6 in DMC:PC (1.5:1) solution. Here it should be noted that we considered DMC:PC mixed solvents instead of DEC:PC mixed solvents because of the following reasons. First, since the C=O stretching vibrational lifetime of DMC is comparatively longer than that of DEC, we could observe measurable diagonal and cross peaks of free DMC and Li–DMC complex in our 2D infrared spectra at long waiting times. Second, we here show that the chemical exchanges observed in Li–DEC (single carbonate solvent) solution do occur in different mixed solvent systems too.Despite that the ultrafast chemical exchange dynamics between free DEC and Li–DEC complex was observed in pure DEC solutions, typical LIB's use mixed solvents instead. To elucidate the separate roles and solvation properties of co-solvents with DMC and PC and to investigate the possibility of DMC playing dual roles both as a solvent medium for mobile Li–PC(DMC) complexes and as a ligand participating in the first solvation shell around LinPCm complex with n DMC and m PC molecules in the first solvation shell and free DMC molecules even in the DMC and PC (1:1 in volume percent) mixed solvents with 1.0 M LiPF6 –(iii) can be found in Despite that the 2D infrared spectra appear to be spectrally congested, we could clearly observe real-time chemical exchange processes between Li–DMCiPF6 see . The 2D ωτ=1,725 cm−1 and ωt=1,760 cm−1 increases (see the 2D infrared spectra inside the red boxes in + in LIB electrolyte solutions is stronger than that between DMC (or DEC) and Li+, which is consistent with the notion that the PC molecule with large dipole moment compared to that of DEC molecule tends to make a stable and rigid solvation sheath around a lithium cation in LIB electrolyte solutions.As waiting time increases, the cross peak amplitude at 6/DMC:PC (1:1 in volume percent) solution, we fitted the 2D infrared peaks with a 2D Gaussian function  vibrational lifetimes, (iii) rotational relaxation times and (iv) survival probabilities of the two species within the waiting time. The cross peak intensity, denoted as |μLi–DMC|2|μDMC|2, (ii) vibrational lifetimes, (iii) rotational relaxation times and (iv) condition probability of finding free DMC after finite waiting time when it was initially in a Li–DMC complex form. Therefore, the ratio of the cross peak intensity to the square root of the product of the two diagonal peaks, that is, To approximately examine the timescale of chemical exchange processes between Li–DMC complex and free DMC in 1.0 M LiPFfunction , which a6/DEC solution shown in 6/DMC:PC (1:1) solution in 6/DMC:PC (1.5:1) and 2.0 M LiPF6/DMC:PC (1.5:1) solutions, the intensity ratios are found to be 0.69 and 0.71, respectively (6/DEC solution is quantitatively similar to that in mixed solvents consisting of DMC and PC.From the 2D Gaussian fit to the 2D infrared spectra (at 10 ps) for 1.0 M LiPFectively . Our obs+ and PF6− solvation shells and ion aggregates, we carried out classical MD simulations for 1.0 M LiPF6/DEC solution using the force field parameters for PF6− in refs + is represented by a yellow sphere and PF6− is by an octahedron. At this high lithium salt concentration, ions form not just CIPs but also large aggregates with a polydisperse distribution. 4 and NaBF4 show a strong propensity to form a large-scale spatially extended networks that are tightly intertwined with water H-bonding networks39+ and PF6− ions form three-dimensional ion networks in LIB electrolyte solutions could be a key to understand detailed mechanism of Li+ ion mobility, since Li+ can jump from one to the other neighbouring anions in the same or different ion networks in the presence of non-zero gradient of electric potentialTo examine the structures and dynamics of Li+ solvation sheath structures in LIB electrolyte solutions are for the first time observed here with employing chemical exchange 2D infrared spectroscopic method. Combining FTIR spectroscopy, infrared pump-probe measurement and quantum chemistry calculation results, we completely characterized the vibrational properties of free DEC and Li–DEC complexes in both pure DEC solvent and mixed solvents consisting of DEC and PC. Subsequent 2D infrared data analyses revealed the ultrafast nature of chemical exchange dynamics in the immediate vicinity of Li+ in DEC solution. Here one of the most difficult challenges was to prepare very thin solution samples because the infrared probes are the C=O stretch modes of DEC and PC molecules that are also solvents. Using RF magnetron sputtering technique, we could control the thickness of coated SiO2 layer on CaF2 window for linear and nonlinear infrared spectroscopic studies. The picosecond Li–DEC complex making and breaking dynamics in both pure DEC solution and DMC:PC mixed solution suggest that the macroscopic Li transport during both charging and discharging processes might be interrelated to microscopic solvation fluctuation and discrete transitions between different solvation states of Li+ in LIB electrolyte solutions. We anticipate that the present ultrafast chemical exchange dynamics should also play an important role in solvation and de-solvation of Li+ at the solid-electrolyte interface on electrodes because of the following reason. If the rigidity of each Li+ solvation sheath is very high, any de-solvation of Li+ on the anode surface may not be efficient, which potentially restricts the function of LIB due to lowering the rate of lithium deposition on the anode. On the other hand, if the Li+ solvation sheath is not sufficiently stable due to a low dissolving power of solvent, the rate of Li+ release from the cathode could be slow. Therefore, it is naturally expected that ideal LIB solvent molecules should interact with Li+ with a properly balanced strength. Overall, the unexpected ultrafast fluxional solvation processes around Li+ in the LIB electrolyte solution is turned out to be prerequisite for optimally achieving the functional role of carbonate solvent in LIB. We anticipate that a further 2D infrared investigation on the Li-solvent fluctuation dynamics during both charging and discharging processes would provide critical information on the fluctuation-dissipation relationship between equilibrium microscopic solvent fluctuation and non-equilibrium macroscopic charge transport phenomenon.Ultrafast fluxional changes of Li6, Battery grade, purity >99.99% trace metal basis) and DEC (purity >99%) was purchased from Sigma-Aldrich. DEC was dried using thermally activated 3 Å molecular sieves. The water content of the sample determined by Karl-Fisher method was less than 50 p.p.m. All solution electrolyte preparation and injection into the infrared cell holder was carried out in Ar-filled glove box . The low water content in sample for infrared absorption measurement was confirmed by examining the water O–H stretch band at around 3,500 cm−1 in the infrared spectra.Lithium hexafluorophosphate  magnetron sputtering system  or −45° (perpendicular) by a linear polarizer on a computer-controlled rotator, sent through a polarizer fixed to 0° into the spectrograph, and detected by a 32-element array detector.Experimental details of pump-probe and 2D infrared spectroscopy employed in the present study have been described elsewhere. Briefly, 800 nm pulses with duration of ∼100 fs and 1.0 mJ were generated from Ti:Sapphire oscillator and regenerative amplifier operating at 1 KHz, which were then used to produce near- infrared pulses at ∼1.4 and ∼1.9 μm. With AgGaS nonlinear optical crystal, the signal and idler pulses are mixed to generate mid-infrared pulses with ∼8 μJ per pulse and ∼100 fs duration centred at 2,070 cm6-DEC solutions at 1.0 M LiPF6 concentration, where 378 LiPF6 molecules were dissolved in 1,000 DEC molecules. The force field parameters developed by Lopes and Pádua406− ion and DEC molecule. respectively, where the corresponding restrained electrostatic potential charges were obtained by carrying out B3LYP/6-311++G calculations. The particle mesh Ewald method was used for long-range electrostatic interaction and the cutoff distance for nonbonding interaction was set to be 10 Å. The solution system was first energy-minimized with the steepest descent method and the conjugate gradient method before running equilibrium MD simulations. Subsequently, a constant N, p and T ensemble simulation at 1 atm and 298 K was carried out for 2 ns to adjust the solution density. An additional 10 ns N, V and T ensemble simulation at 298 K was performed to make each LiPF6-DEC solution system to reach its thermal equilibrium state. Finally, the production run was performed for 10 ns at constant N, V and T conditions, where the simulation time step was set to be 1 fs, and atomic coordinates were saved for every 1 ps.Molecular dynamic (MD) simulations were performed for LiPFThe data that support the findings of this study are available from the authors on reasonable request, see author contributions for specific data sets.How to cite this article: Lee, K.-K. et al. Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery. Nat. Commun.8, 14658 doi: 10.1038/ncomms14658 (2017).Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.Supplementary Figures 1-12, Supplementary Tables 1-2, Supplementary Notes 1-6 and Supplementary References


Research has identified drinking motives as the final common pathway to alcohol use, and associations between specific drinking motives and drinking patterns have consistently been demonstrated. Data on drinking motives can be used for research, in the planning of prevention strategies and for treatment purposes. The Drinking Motives Questionnaire-Revised (DMQ-R) has become the most used measure of drinking motives. So far, the questionnaire has not been investigated with qualitative methods. The aim of this study was to investigate acceptability, accuracy and usability of the DMQ-R among persons receiving outpatient psychiatric care by studying how responders perceive and interpret the questionnaire.A cognitive interviewing technique, the think-aloud method, was used to collect data from 16 non-alcohol dependent patients seeking outpatient psychiatric care . To analyse data, Qualitative Content Analysis was applied in which themes were formed from data only and not from predetermined areas of interest.Overall, acceptability of the DMQ-R was high although answers were sometimes given with low accuracy. Responders pointed out that they perceived the questionnaire as non-confrontational and exhaustive. Further, the DMQ-R seemed to launch processes of self-reflection.Taken together, the results suggest a support for the use of DMQ-R also in the group of psychiatric outpatients. Still, when interpreting the DMQ-R, a certain insecurity of the exactness of answers should be considered. The graphic design should be particularly clear in this group of patients.The online version of this article (10.1186/s13722-018-0109-1) contains supplementary material, which is available to authorized users. Drinking motives have drawn increasing interest because of their role in the development of alcohol-related problems. Research has identified drinking motives as the final common pathway to alcohol use , 2. AssoThe Drinking Motives Questionnaire-Revised (DMQ-R)  is a selTo evaluate the performance of a questionnaire, direct study of the question-and answer process is recommended , 12. StiThe DMQ-R has not been investigated with qualitative methods. To extend the knowledge about the psychometric properties, the usability and utility of the DMQ-R in different settings, a project called “Motives for drinking” was initiated . ThData were collected among patients visiting a psychiatric outpatient clinic for mood and anxiety disorders at a university hospital in Sweden. The hospital’s procedure includes referring those patients who have a substance use disorder or psychosis as a main diagnosis to separate specialist clinics and those patients did not take part in this study. In the eligible group of patients with mood and anxiety disorders, co-morbidity with personality disorders or ADHD/autism spectrum disorders may occur, but no patient was diagnosed with any substance use disorder. The only criterion for inclusion was having consumed alcohol during the last 12 months. All staff at the outpatient unit were asked to inform and invite their patients to participate in the study. No compensation was offered. The project was approved by the Ethical Review Board of Uppsala University (Reg. No. 2015/434).Enhancement motive for alcohol consumption (e.g. drinking to feel high). Drinking to reduce negative affect reflects an internal, negative-reinforcement Coping motive (e.g. drinking to forget problems). Alcohol consumption to avoid negative social consequences reflects an external, negative-reinforcement Conformity motive (e.g. drinking to fit in with others). Drinking in order to obtain social rewards reflects an external, positive-reinforcement Social motive (e.g. drinking to celebrate with friends).The Drinking Motives Questionnaire-Revised (DMQ-R)  measuresThe DMQ-R consists of 20 items, five per dimension. Participants rated the frequency of drinking for each item on an ordinal scale with six response categories . To avoid space-demanding iterations, all items were not fully written out. The questionnaire and its graphic design is presented in Additional file The think-aloud method was used to collect data. This method, also known as protocol analysis, was introduced in the field of psychology in the 1980s as a way to understand elementary cognitive processes as they unfold over time , 17. To Participants in this study were offered oral and written information by their ordinary caregiver and those who chose to participate were scheduled for a session with one of the researchers MW or CN. The information pointed out that the study focused on the thoughts while answering a questionnaire rather than on the actual answers. At the session, participants were informed again and signed a consent form. They were instructed to think aloud: to say whatever came into their mind while responding to the questionnaire. They were informed that they could be reminded to keep talking, and that questions about items would not be answered by the researcher. If participants remained silent for 5–7 s when completing the DMQ-R, they were asked what they were thinking about. In case verbalized thoughts were unclear, participants were asked to explain more explicitly. At the end of the session, participants were asked what they thought of filling out the questionnaire and what its pros and cons were. They were also asked if they thought something was missing. All sessions were recorded with MP3-players and transcribed verbatim.To analyse the think-aloud data, the researchers conducted Qualitative Content Analysis using an inductive approach . Themes The transcripts were read several times by authors CN and MW separately. Meaning units—words and sentences of interest for the aims of the study—were coded. Following a joint discussion, codes were sorted into themes. The material was re-read by both authors CN and MW and themes were used to sort the codes. The analysis continued until all themes were deemed to be clearly defined and distinct from one another. All authors discussed the coding of data until consensus was achieved and themes were perceived as describing the content concisely. In addition to being researchers, all authors have extensive experience in the field of psychiatric care and/or substance use treatment.Of the 16 individuals included, 12 were women and four were men None of them was diagnosed with an alcohol use disorder but all had consumed alcohol during the past 12 months. All those approached except for one patient consented to take part. Ages ranged from 26 to 67; mean age (SD) was 45.2 (10.9), median was 46.5 years. All participants were diagnosed with a mood or anxiety disorder (ICD-10 F30-48 ) as a maInterpretation of the questionnaire, Experiences rather than motives and Self-reflection.The results are presented under the three identified themes with verbatim quotes to illustrate the findings. The themes are How often do you drink…here, I am probably not supposed to fill in on the dotted lines, but in the box… [reads the response options]. So this is some kind of headline to this section… The fact that questions could be posed repeatedly in similar forms produced 17 comments.In all, 88 verbalizations concerned the interpretation of the questionnaire: the graphic design (43 comments), the formulation of questions (31 comments) and the lack of suitable response options (14 comments). The graphic design was initially confusing to some participants, a subject that generated 16 verbalizations.‘Some of the times’, that’s very relative. To me, ‘soon’ is within ten minutes. I have a friend, he thinks ‘soon’ is within an hour. It’s just about the same with ‘some of the times’. Another concept that was perceived equivocally was getting high (Item no. 9: “How often do you drink to get high?”) One participant interpreted “to get high” as “to be intoxicated” or “really drunk”. Another interpreted the wording as “slightly affected by alcohol”. Still another participant contemplated:…it depends on what you mean by ‘high’. To get high, that’s to be sort of upbeat to me. But I mostly want to calm down, so no… The participants sometimes had difficulty relating to the situation described in the question.…because it makes social gatherings more fun. It depends on the context…if I go out after work with some colleagues, maybe we’ll drink wine together. But other times it’s a family gathering and I may as well drink cola…What should I put here? This was really difficult. Participants were eager to fulfil their task, but in all 14 verbalizations indicated difficulty finding a suitable response option. Instead, they chose a rough estimate.…to celebrate…well, no…I put ‘almost never’, it is… it is mostly because I want to move on from the question and I don’t want to leave the questionnaire incomplete. Although participants generally understood the questions, some words and terms were perceived as equivocal. In all, 31 verbalizations concerned interpretations of the questions. The concept “how often” was sometimes difficult to quantify. It was associated with consumption level and not with comparisons to other times the person had consumed alcohol. Ten verbalizations were noted on this subject.…because it gives you a pleasant feeling. Yes, to me it does, it makes me calmer. Because it makes you feel more self-confident…yes, that is common. …because it gives you a pleasant feeling. If you drink moderately, yes. But if you drink too much, absolutely not. I get really sick from it. When participants reflected on the questions it was common to refer to practical experiences, situations the person had been in. Those experiences – rather than the motive for drinking—seemed to guide the response. This theme gathered 29 verbalizations.You really start reflecting on your drinking. Something happens to you when you’re asked these questions. […] You really confront yourself with these questions, and I think that might be a good thing. It could be a kind of an opening to your understanding that this isn’t good, maybe. I think these questions are…they make it difficult to lie. It’s easier to lie if you are asked how much, how many beers did you drink. The questions led some of the participants to reflect on their alcohol use and motives. This was spontaneously commented on six times.“To get high. [long pause]. Hm. I don’t really know. But maybe we can say “Some of the times”. The participants that ruled out conformity motives did so particularly decisively.Because your friends pressure you to drink…Never! I drink when I decide to. And if I don’t feel like drinking when somebody offers me a drink, I just say no thanks. Some participants commented that they found the questionnaire non-confrontational and exhaustive.I think…they were good questions, they were neutral. Not moralistic… they don’t ask how often you drink, and so on. And they were comprehensive, I can say. They approach the question of why you drink from all kinds of angles. Others pointed out that it covered important areas that no one had asked them about before.Participants who were insecure about how to reply often chose the alternative “Some of the times”.Five responders commented that an important drinking motive was that alcohol tastes good and goes well with food. One person felt a response option was missing for questions about which she was uncertain.This is the first study to report qualitative data from thought processes of persons responding to the DMQ-R. In our study, we were able to find out more about interpretations and reasoning among the psychiatric outpatients. Information collected using the think-aloud method would have been difficult to collect with fixed response options or by asking participants retrospective questions.The acceptability of the questionnaire was generally high; it was well understood by the participants. However, there were many comments concerning similarities among the questions and the iterations seemed to create some vexation and insecurity. Thus, a shorter version may be to prefer. In a previous study with patients seeking psychiatric care, we found psychometric properties of the short form DMQ-R SF to be valid and even with a slightly better model fit than the DMQ-R . The resA large number of verbalizations pertained to the questionnaire itself: its graphic design, the formulation of questions and the lack of suitable response options. Some respondents perceived the graphic design used in our study as confusing. For simplification, the questions were not fully written out. One patient broke off the interview after 4:30 min, as he felt his symptoms produced an uncomfortably stressful situation. Two other participants mentioned their ADHD symptoms as a possible explanation for their difficulties understanding the questionnaire. When addressing patients in psychiatric care there may be a certain need for explicitness, as their psychiatric condition may create cognitive disturbances.The verbalizations concerning difficulties finding an apt response option indicate that some tentativeness is needed when interpreting the results of the questionnaire. The option “Some of the time” was often chosen when responders were insecure about how to reply. The responses “Some of the time” may thus represent low accuracy.Before giving a response, many participants considered the effects alcohol has on them rather than their motives for drinking. It was clear that they were referring to their experiences and the consequences of drinking. In cognitive psychological theory, the frequently cited “Question-and answer model” (e.g. .) suggesIt is noteworthy that respondents spontaneously commented that the questionnaire made them start reflecting on their alcohol use. Although such verbalizations were quite rare during the interviews, considering the nature of those comments, it is likely that the questions on the DMQ-R may launch a self-reflection process. Because alcohol use even at moderate levels may impact the course of a psychiatric disorder and the treatment effects , 23, sucThe comments concerning the graphic design generated the major share of comments. This serves as a reminder that a clear and comprehensible design is of importance, in particular in the psychiatric setting. However, design issues are easily resolved. It is more problematic that respondents differed in the interpretation of questions and situations described. Previous psychometric tests of DMQ-R have pointed out variations in item factor loadings in groups of adults as well as adolescents , 24, 25.There are some issues to consider with respect to strengths and measures used to strengthen the weaknesses of the present study. The main strength of this study is that it investigates the questionnaire from the respondent’s perspective. It was conducted in a clinical setting and used a cognitive method, previously not used with DMQ-R, to examine how people understand and interpret the questionnaire.One potential weakness is the interview setting with a researcher present in the room that may have created bias; given that the subject is alcohol, social desirability may have played a role. Still, because of the non-confrontational nature of the questions we believe that risk was small. Further, it is possible that the think-aloud method may have increased the responders’ critical attitude to questions in a way that differs from a normal response situation.As with all research with qualitative analysis, there must be measures to strengthen the neutrality of the coder, which otherwise may affect the interpretations. Nevertheless, interpretation involves a balancing act between adding a perspective to the phenomenon under study and not assigning meaning to the text that is not there. The co-authors reduced that risk via a sound data analysis process with alternative coding and discussions of the data. Further, although the coders were experienced in psychiatric care and/or substance use treatment they were not members of the staff and had not met the participants before, which minimized the influence of pre-existing assumptions.This type of study design gives a good understanding of perceptions in a group of individuals, but it is not possible to generalize the results from the study in a quantitative manner. Instead, description of context, process of analysis and appropriate quotations can inform and enhance readers’ understandings of how the findings can be transferred to other settings or groups.The number of participants was relatively small, however qualitative research is often based on small sample sizes where understanding of experiences and perceptions is the subject. Nevertheless, a larger sample could have made it possible to include participants of different ages, different diagnoses and different experiences of alcohol.The results suggest a support for the use of DMQ-R in outpatients in psychiatric care for research, prevention and treatment purposes. Still, when interpreting the DMQ-R, a certain insecurity of the exactness of answers should be considered. The graphic design should be particularly clear in this group of patients.Additional file 1. The Drinking Motives Questionnaire in the version used in the study. English translation supplied.


The ability to perceive, recognize and process own and others’ emotions is crucial for efficient and effective social communication. Many different tasks have been used to investigate impairments herein in patients with schizophrenia. Evidence suggests that perception, discrimination and recognition of affective facial expressions are impaired in schizophrenia patients. Importantly, not everyone may interpret the same facial expression similarly. People match their internal representation of specific facial expressions to perceived faces and variation in these internal representations may result in a distortion of social reality. The impairments in face and/or emotion processing and the bias toward a more negative experience may be causally related to degradation of the internal representation itself or to disturbances in the higher-order evaluation of visual input against functionally intact internal representations. In an attempt to develop ways of visualizing an individuals’ internal representation of an emotional face on a computer screen, we set out to visualize the representation of a male and a female face.We use a data-driven technique, i.e. reverse correlation image classification (RCIC), which makes it possible to visualize internal representations of faces on computer screens. Participants judge noisy images of faces that are created by superimposing random noise on a single constant base face. The random noise distorts the base face at the pixel level, generating facial variation across stimuli that is fully unconstrained and unaffected by researchers’ a priori expectations. The participants’ responses to a large number of faces are used to model the facial information that was idiosyncratically diagnostic for the judgments. This analysis yields a classification image (CI) for each participant, which visualizes the facial characteristics that drive judgments of emotional expressions .We introduce an objective metric, i.e. infoVal, using gender as proof-of-principle. infoVal quantifies the probability that an observed CI was not generated by a random process and is equivalent to a modified z score. First, we test the association between infoVal and more common markers of data quality, i.e. the subjective recognizability, objective discriminability and test-retest reliability of CIs . Second, we use RCIC to investigate and reconstruct the mental representation of trustworthiness as expressed on the face in 32 patients with schizophrenia and 39 controls.Subjective ratings showed that male and female CIs were more strongly associated with masculinity and femininity, respectively, when infoVal scores where high (p<.001). Second, infoVal scores were highly correlated with test-retest reliability, i.e., higher scores corresponded with higher test-retest reliability (p<1x10-13).Preliminary analyses of the RCIC task on the internal representation of trustworthy and untrustworthy faces showed that both patients and controls are capable of performing the task adequately. Data-driven multidimensional scaling of the classification images implicate 3 clusters of images, reflecting untrustworthy, neutral, and trustworthy faces. These first analyses suggest that there is no evidence for differences in internal representation of (un)trustworthy faces between patients and controls.We showed how infoVal scores can facilitate the interpretation of CIs. This opens the way to comprehensively investigate internal representations of emotional faces in patients with schizophrenia.


The experimental data could be well fitted with Langmuir, Freundlich and Temkin isotherm models, besides the pseudo-second order kinetics model. The total quenching rate constant obtained for singlet oxygen deactivation by AMSNPs-MOR was one order of magnitude lower than the morin rate constant reported previously in neat solvents and lipid membranes. The AMSNPs-MOR have good antioxidant properties by itself and exhibit a synergic effect with morin on the antioxidant property against hydroxyl radical. This effect, in the range of concentrations studied, was increased when the amount of morin adsorbed increased.Morin  is a flavonoid with several beneficial health effects. However, its poor water solubility and it sensitivity to several environmental factors avoid its use in applications like pharmaceutical and cosmetic. In this work, we synthetized morin-modified mesoporous silica nanoparticles (AMSNPs-MOR) as useful material to be used as potential nanoantioxidant. To achieve this, we characterized its adsorption kinetics, isotherm and the antioxidant capacity as hydroxyl radical (HO•) scavenger and singlet oxygen ( The emerging discipline of nanomaterials intends to apply physical principles common in materials science to challenges in areas such as drug delivery, structure and properties of powders and manufacturing and processing of particle systems for use in novel formulations –3. Nanop2) is an attractive material for chemistry, medicine and pharmaceutical sciences because it is optically transparent, chemically inert, mechanically stable, fairly biocompatible, and its synthesis is relatively easy  plots. The deactivation of singlet oxygen with a flavonoid or other quencher, involves physical quenching (deactivation) and/or chemical (reactivity) processes. The sum of the physical quenching (ant (kT) , 39. In of morin .τ−1=τ0−kT (4.5 x 107 M-1s-1) indicates that morin is still an efficient quencher of singlet oxygen when it is immobilized on the silica surface. However this value is one order of magnitude lower than that in homogeneous media (1.3 x 108 M-1s-1 in D2O pD 7.4) and erythrocyte ghost membranes dispersed in D2O pD 7.4 (1.4x108 M-1s-1)[kq) for deactivation of singlet oxygen by efficient quenchers are smaller than in homogeneous solutions because quenching process in polymers is mainly controlled by solute diffusion to yield the singlet oxygen-quencher encounter pair [The obtained value of 8 M-1s-1). This co8 M-1s-1), the forter pair . Indeed 2O2 + UV radiation → 2 HO•). Free radicals can also be formed by the presence of xenobiotics that can contain ions Fe(II) or Cu(I) that act as a catalyst of hydrogen peroxide decomposition (H2O2 + Fe(II)/Cu(I) → HO• + HO- + Fe(III)/Cu(II)).Consequence of its function as a barrier, the skin is a potential target for oxidative stress due to production of free radicals from different sources. These free radicals threaten the integrity of skin as they do to other tissues , 86, butMorin has shown antioxidant activity against the damage caused by hydroxyl radical, through a proton-coupled electron transfer (PCET mechanism) , 88, wheThe antioxidant reactivity of AMSNPs-MOR against hydroxyl radical was studied in a system where this radical was generated in situ by hydrogen peroxide 10%v/v UV-photolysis , 91. As 2 nanoparticles and covalently-linked-gallic acid derivative against DPPH• radical [To evaluate the scavenging activity of the AMSNPs-MOR, the formation of the DMPO- HO• adduct by every component was measured; the results show that the NP possess scavenging capacity against hydroxyl radical . On the  radical . As the  radical , indicat radical , 94. The-1) was performed by Langmuir, Freundlich and Temkin adsorption isotherms.The aim of this study was to evaluate the antioxidant capacity and the kinetics and the adsorption isotherm of morin onto silica nanoparticles. Mesoporous and spherical aminopropyl-modified silica nanoparticles (~150 nm) were prepared and characterized. The maximum adsorption capacity of these nanoparticles for morin  obtained for singlet oxygen deactivation by AMSNPs-MOR was one order of magnitude lower than the morin rate constant reported in homogeneous solvents and lipid membranes. On the other hand, morin behaves as an antioxidant against hydroxyl radical generated in situ; nevertheless, NP presented also antioxidant properties by itself. Interestingly, adsorbed morin onto NP exhibits a synergic effect on the antioxidant property against hydroxyl radicals. This effect was increased when increasing the concentration of morin adsorbed, in the concentration range of work.The antioxidant properties of AMSNPs-MOR by monitoring of singlet oxygen deactivation and OH radical scavenging were studied. The total quenching rate constant (kIn summary, taken together the results suggest a complex adsorption process involving at least two ways; first, one monolayer irreversibly adsorbed like bonding-mode and then, presumably, multilayers in a piled up form physisorbed by electrostatic forces. The conjugation, can implicate an interaction between amino group from APTES with carboxyl and/or hydroxyl group on C ring of morin, leading to a resorcinol moiety accessible to react with different ROS or interact with 2´-OH group on the B ring.


Purpose: To examine the effects of deceptively aggressive bike pacing on performance, pacing, and associated physiological and perceptual responses during simulated sprint-distance triathlon.Methods: Ten non-elite, competitive male triathletes completed three simulated sprint-distance triathlons , the first of which established personal best “baseline” performance (BL). During the remaining two trials athletes maintained a cycling power output 5% greater than BL, before completing the run as quickly as possible. However, participants were informed of this aggressive cycling strategy before and during only one of the two trials (HON). Prior to the alternate trial (DEC), participants were misinformed that cycling power output would equal that of BL, with on-screen feedback manipulated to reinforce this deception.Results: Compared to BL, a significantly faster run performance was observed following DEC cycling (p < 0.05) but not following HON cycling . As such, magnitude-based inferences suggest HON running was more likely to be slower, than faster, compared to BL, and that DEC running was probably faster than both BL and HON. Despite a trend for overall triathlon performance to be quicker during DEC (4339 ± 395 s) compared to HON (4356 ± 384 s), the only significant and almost certainly meaningful differences were between each of these trials and BL . Generally, physiological and perceptual strain increased with higher cycling intensities, with little, if any, substantial difference in physiological and perceptual response during each triathlon run.Conclusions: The present study is the first to show that mid-event pace deception can have a practically meaningful effect on multi-modal endurance performance, though the relative importance of different psychophysiological and emotional responses remains unclear. Whilst our findings support the view that some form of anticipatory “template” may be used by athletes to interpret levels of psychophysiological and emotional strain, and regulate exercise intensity accordingly, they would also suggest that individual constructs such as RPE and affect may be more loosely tied with pacing than previously suggested. During sprint-distance triathlon, an athlete's overall finishing time comprises a 0.75 km swim, 20 km cycle, and 5 km run, each of which is separated by only a brief period of “transition”. Each discipline imposes unique residual demands on the next  exercise intensity as a result   would improve previous best simulated triathlon performance, irrespective of whether triathletes were made aware of this pacing strategy or not. However, it was also hypothesized that making triathletes aware of this aggressive cycling strategy would impair subsequent run and overall performance, relative to a deceptive pacing condition.SD) age, body mass, stature, and peak oxygen uptake (2peak) of 36.8 ± 8.9 years, 1.79 ± 0.08 m, 76.3 ± 7.2 kg, and 54.3 ± 5.7 ml·kg−1·min−1, respectively. Participants had been competing in triathlons for a minimum of 12 months and were all in their “off-season” throughout the study. The training completed by the group during the study period averaged 1.4 h·wk−1 (3.2 km·wk−1) swimming, 2.3 h·wk−1 (84.0 km·wk−1) cycling, 2.2 h·wk−1 (21.7 km·wk−1) running, in addition to 1.3 h·wk−1 of strength and conditioning. Before the completion of any data collection, all participants completed a medical history questionnaire and, having had the research procedures, requirements, benefits, and risks explained to them, they each provided written, informed consent. At this initial stage participants were told, incorrectly, that the intention of the study was to establish the reliability and validity of simulated sprint-distance triathlon performance, and associated physiological and perceptual responses. All study procedures were approved by the institutional ethics committee and, in line with internationally recognized ethical standards for deceptive sport and exercise science research  and performance  characteristics, and a “race pace” familiarization of the sprint-distance triathlon simulation  that they would be required to complete during subsequent experimental triathlon trials. Having completed all preliminary testing, each participant then performed an isolated cycling time-trial (TT) which required the completion of 500 kJ of work as quickly as possible. In light of the work by Suriano and Bishop  throughout all cycling and running sections. Cycling was completed on an electromagnetically braked ergometer  and running was performed on a motorized treadmill .Participant's completed a total of eight testing sessions each, with the first four consisting of an “all-out” (non-drafted) swimming time-trial performed in their usual (25 m) training pool, separate incremental running and cycling tests to volitional exhaustion to establish each participant's peak physiological . Swimming was completed at a fixed intensity equivalent to 90% of the average velocity recorded during each participant's preliminary “all-out” 750 m time-trial. As Peeling et al.  have sugThe magnitude of deception employed was selected based on the previously established coefficient of variation (CV) for power output during simulated triathlon cycling  and associated estimates of sample size requirements  which was, in turn, projected onto a large monitor positioned in front of the treadmill. This provided a virtual representation of each participants progress over a flat 5 km run course in the form of an on-screen avatar (viewed from a second person perspective), in addition to numerical feedback regarding distance covered, current speed and average speed. In addition to this feedback, participants were informed prior to HON and DEC trials that they would be racing against a second on-screen avatar during the run which represented a replay of their BL performance. More specifically, participants were instructed to try their best to beat (or at least match) this on-screen “opponent.” The view seen by each participant was always of the avatar representing their current performance. This meant that they were only able to see both avatars if they were performing worse than their BL trial . With this in mind, the distance separating both avatars was constantly displayed on-screen so that participants were able to keep track of their relative performance and respond to any changes in pace that were made during the BL trial. Upon completion of each run, the NetAthlonTM software stored distance, speed and time data at 1 s intervals for subsequent analysis.ad libitum whenever these measures were not being recorded. More specifically, participants were instructed to drink as dictated by their levels of thirst, which is suggested as a more important factor to control during triathlon simulations than specific measures of hydration status .The duration of first and second transition during HON and DEC trials replicated those recorded during BL performance  and were comparable to previous studies of simulated triathlon performance , respiratory exchange ratio (RER) and ventilation (E) were obtained , alongside heart rate  and fingertip capillary blood lactate concentration . Prior to each laboratory trial participants fitted a HR transmitter belt underneath their triathlon suit, with baseline measurements then obtained for [BLa−] and body mass. During simulated triathlon trials, measures of [BLa−] were obtained post-swim, at the end of every 100 kJ cycle section completed, and upon completion of each 1.66 km section of the run. These measures were also taken at the end of every 100 kJ during isolated TT performance. Body mass was measured immediately upon completion of each experimental trial. During isolated TT and simulated triathlon trials, the gas analysis system was fitted to participants immediately before they began cycling, by means of a leak-free face-mask and head-strap. However, to allow for fluid intake, this face-mask was removed from participants between 75–125, 175–225, 275–325, 375–425, and 475–500 kJ of the bike. During simulated triathlon trials this system  was then reapplied at the end of second transition  and was kept on for the duration of the run. Following each experimental trial, cardiorespiratory data was interpolated to 1 s averages using the manufacturer's software to match the frequency of this data with that of cycling power output and running speed. Mean HR values were determined for each triathlon discipline, whilst mean values for respiratory data were established for both the bike and run sections. In order to profile discipline-specific cardiorespiratory responses, data were averaged for 50–75 kJ of every 100 kJ cycle section completed and for each 1.66 km section of simulated triathlon running.During all laboratory trials, breath-by-breath measurements of oxygen uptake  and Microsoft Excel . A series of one-way repeated-measures ANOVA's were used to examine differences in swim, cycle, run and overall performance measures between BL, HON, and DEC triathlon trials, and to establish whether any performance differences existed between isolated cycling time-trials and the cycling section of each simulated triathlon. The same method of analysis was used to examine discipline-specific differences between trials in relation to the mean physiological and perceptual responses observed. In order to better consider the practical significance of results, data was also assessed by way of magnitude-based inferences .Two-way within-subjects  ANOVA's were used to establish main effects of cycling condition and distance completed using mean 100 kJ section values for power output, p < 0.05). As such, mean power output was significantly higher during TT, HON, and DEC, vs. BL . These power output values corresponded to 71, 65, 68, and 68% of Wpeak, for TT, BL, HON, and DEC, respectively. Mean running speed during each triathlon trial corresponded 77, 77, and 78% of Vpeak, for BL, HON, and DEC, respectively. Although these values suggest a trend for faster run performance during DEC, compared to both BL and HON, this was only statistically significant in comparison to BL (p < 0.05). Similarly, whilst there was a non-significant trend for overall triathlon time to be shorter during DEC than HON (by ~17 s), the only statistically significant differences were between each of these trials and BL, which was between 2 and 3% slower overall than both DEC and HON (p < 0.05).As summarized in Table post-hoc analysis which highlighted a consistently higher power for each 100 kJ section during TT vs. BL. Although the pacing profiles during TT and BL developed in a similar  manner for much of the cycling bout, it was also evident that the marked increase in power output observed during the final 50 kJ of TT was absent during BL. During triathlon running, repeated-measures ANOVA revealed a significant main effect on speed for distance, but no main effect for condition and no condition × distance interaction  which culminated in an apparent “end-spurt” in the final 600 m of all triathlon trials.Repeated-measures ANOVA showed no main effect on power output for cycling distance, but did reveal a significant main effect for cycling condition and a significant condition × distance interaction, indicating differences across conditions in power output profiles when plotted against distance covered Figure . This asn Figure . As suchalmost certainly better during TT, DEC, and HON, in comparison to BL . Whilst DEC and HON cycling performances were probably worse compared to that of TT , there were almost certainly no performance differences between the DEC and HON cycling . Interestingly, whilst any practically important difference appeared unclear, it was more likely that HON running performance was meaningfully slower, than faster, vs. BL . On the other hand, DEC running performance was probably faster than both BL and HON . In terms of overall triathlon performance, there was almost certainly no difference between DEC and HON , although both were almost certainly faster vs. BL .With regard to the practical significance of performance differences, magnitude-based inferences suggest that cycling time and power output were Further to these findings, post-experimental debriefing revealed that all participants; (i) failed to identify the aggressive manipulation of cycling power output during DEC and, similarly (ii) believed that cycling intensity was highest  during their HON performance.−]) elicited by the swim section of each simulated triathlon (p > 0.05). Mean cycling intensity during each trial corresponded to 91, 85, 87, and 87% of HRpeak, and 87, 81, 83, and 82% of 2peak, for TT, BL, HON, and DEC, respectively. As such, comparisons of each cycling bout revealed that physiological responses during TT were significantly higher than those recorded during BL (p < 0.05). Furthermore, the greater demands of HON and DEC cycling were reflected in a number of elevated physiological responses compared to BL, particularly that of [BLa−].Table 2 values did not significantly differ between BL, HON, and DEC cycling (p > 0.05). Although no significant physiological differences were evident between HON and DEC cycling, it is noteworthy that only HON had a mean 2 which was not significantly lower than TT (p > 0.05). Mean intensity during each triathlon run corresponded to 92, 91, and 92% of HRpeak, and 87, 86, and 88% of 2peak, for BL, HON, and DEC, respectively. As summarized in Table p > 0.05).Despite these observations, mean HR and likely to almost certain . Likewise, almost all physiological responses were possibly to almost certainly higher during DEC and HON cycling compared to BL , with mean 2 the only exception. As such, it was likely  that any difference in mean 2 between DEC and BL cycling sections was trivial. Mean physiological responses during DEC and HON cycling were of trivial or unclear difference. During running, most of the practically meaningful physiological differences were seen between HON and DEC, with 2, E, and [BLa−] values being either likely or possibly lower during HON .Magnitude-based inferences suggested that the likelihood of a practically meaningful elevation in all physiological responses during TT vs. the cycling section of all triathlon trials ranged from post-hoc comparisons. As such, significant main effects of cycling condition were found for all physiological measures, whilst there were main effects for distance on HR, 2, and E (p < 0.05). No significant condition × distance interactions were found for any physiological measure (p > 0.05). Post-hoc analysis revealed much of the disparity in physiological response to be between BL and TT trials conditions, with direct comparisons of HON and DEC data revealing no significant differences (p > 0.05). However, there was a trend for respiratory measures during HON to be higher than DEC, which was indirectly supported by the disparity in significant differences when comparing each of these trials with BL and/or TT. Significant main effects of distance on physiological responses (HR and RER) were found to be a result of significant differences in all conditions between measures taken during the first 100 kJ section and all subsequent measurement intervals. The profile of physiological response during each simulated triathlon run is detailed in Figure post-hoc statistical analysis. As suggested by Table p > 0.05). However, significant main effects of run distance were found for HR, 2, and E (p < 0.05), with all trials demonstrating significant increases in HR and E from each 1.66 km section to the next.Figure Table likely to almost certainly higher for all measures , except for affect and arousal. As such, mean affect was likely lower during TT vs. all other bouts of cycling . In the case of arousal, there were no clearly meaningful differences evident, with the most likely outcome being a trivial difference between trials . Comparisons between BL, DEC, and HON cycling revealed trivial or unclear differences in almost all perceptual responses, with thermal strain being the only exception to this. As such, thermal strain was likely higher during DEC compared to BL . During running, thermal strain was again one of few perceptual responses to meaningfully differ between trials, being likely lower during both HON and DEC , compared to BL. The only meaningful difference in perceived exertion was a possibly lower mean score during DEC vs. HON running . Further to this, differences in affect were limited to DEC being likely higher  than both BL and HON .Based on magnitude-based inferences, mean perceptual response during TT vs. the cycling section of all triathlon trials was likely to almost certain for all measures , except for affect and arousal. As such, mean affect was likely lower during TT vs. all other bouts of cycling . In the case of arousal, there were no clear or meaningful differences evident, with the most likely outcome being a trivial difference between trials . Comparisons between BL, DEC, and HON cycling sections revealed trivial or unclear differences in almost all mean perceptual responses, with thermal strain being the only exception to this. As such, mean thermal strain was likely higher during DEC compared to BL . During running, thermal strain was again one of few perceptual responses to meaningfully differ between trials, being likely lower during both HON and DEC , compared to BL. The only meaningful difference in perceived exertion was a possibly lower mean score during DEC vs. HON running . Further to this, differences in affect were limited to DEC being likely higher  than both BL and HON .Based on magnitude-based inferences, a meaningfully higher mean perceptual response during TT vs. the cycling section of all triathlon trials ranged from p < 0.05), whilst a significant main condition effect was evident for all perceptual responses except for affect and arousal (p > 0.05). A significant condition × distance interaction was only apparent for RPE and breathlessness (p < 0.05). During running, significant distance effects were found for all perceptual measures (p < 0.05), although no condition effects or condition × distance interactions were evident for any perceptual response (p > 0.05). Further to these findings, collated individual perceptual responses across the duration of each triathlon trial revealed strong correlations with the percentage of overall triathlon time completed . Repeated-measures ANOVA showed the relationship  between individual participants' perceptual status and percentage of overall triathlon time was largely unaffected by cycling condition, with no statistically significant main effects found (p > 0.05).Distance profiles  of perceptual measures during cycling and running sections of each trial are presented in Figures F = 4.5, p < 0.05, ηp2 = 0.33] and distance , although no significant condition-by-distance interaction was seen (p > 0.05). Post-hoc analysis highlighted that between-condition differences during cycling were attributable to the Hazard Scores of TT, which were significantly higher compared to HON at 200 kJ (p < 0.05), and vs. both BL and DEC at 400 kJ (p < 0.05). The same analysis of running-specific Hazard Scores , although there was a significant main effect for running distance [F = 684.2, p < 0.001, ηp2 = 0.99).As a simple index of the momentary risk perception associated with pacing behavior, the so-called “Hazard Score”  and almost certainly meaningful improvements in the overall simulated triathlon times of both HON and DEC, compared to that of previous best  performance. Similarly, the hypothesis that making triathletes aware of aggressive cycle pacing would impair subsequent run and overall performance, relative to that of a deceptive pacing condition, was also accepted. This decision was made in light of the significant (p < 0.05) and probably meaningful improvements in running time during DEC, compared to BL, and the apparent failure of triathletes to significantly or meaningfully improve on their BL run performance during HON . Furthermore, whilst the 17 s difference between HON and DEC running times did not reach statistical significance, it would appear probable or likely that this represents a meaningfully quicker run performance during DEC. Indeed, the differences in running performance between DEC and the relatively slower BL and HON trials are comparable to those observed during the deceptively manipulated triathlon running trials of Taylor and Smith  would improve previous best simulated triathlon performance was accepted. This was the case irrespective of whether or not triathletes were made aware of this relatively aggressive pacing strategy. The decision to accept this hypothesis was based on the finding of significant  pacing decisions they make in attempting to optimize performance  . They would also appear to confirm that the anticipatory process of reserve maintenance is sensitive to levels of both physiological and perceptual strain during self-paced multi-modal exercise  exercise, Cohen et al.  concludelikely meaningful trend for more positive levels of affect to be sustained throughout the quicker, more aggressive, and thus most physiologically demanding triathlon run, which followed the deceptively aggressive cycling condition. This would corroborate with the view that more negative affect is associated with reduced tolerance of physiological strain and poorer performance  may influence pace regulation more than “what” they are feeling , particularly during multi-modal exercise. With this in mind, it may also be of value for researchers to examine whether the deceptive enhancement of both single and multi-modal performance reflects a change in the specific thoughts of participants, rather than an altered interpretation of common psychophysiological scales . Whilst some form of anticipatory “template” may therefore be used by athletes to regulate the development of psychophysiological strain across a particular multi-modal exercise task, it would appear that the influence of afferent feedback on this process can be manipulated to modify pacing and enhance performance. Although these points echo previous conclusions , collecting, analyzing, and/or interpreting the data (DT and MS), conceptualizing and drafting the initial manuscript (DT), and critically reviewing/revising the manuscript (DT and MS). Further to these points, DT conducted the final approval of the version to be published (in agreement with MS) and is accountable for all aspects of the work in ensuring that questions related to the accuracy or integrity of any part of the work are appropriately investigated and resolved.The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.