The evolution of opinions is a complex mechanism. The evolution of individual opinions is not only influenced by own and others but also by psychological effects. Therefore, based on the classical bounded confidence model and the sleeper effect, a new opinion evolution model is proposed in this paper. In this new opinion evolution model, we increase the opinions on every step and take into account the “discount opinions.” Since mental states for human are not easy to measure, we assumed three different initial networks and carried out simulation experiments. To verify the rationality on our model, we compared the effects with and without the sleeper effect, different thresholds, and discounting opinion ratio on opinion aggregation and convergence. Finally, we found the sleeper effect can differently affect the convergence of opinions in different opinion environments. The development of the information society better meets the mass needs of economic, political culture, and so on; meanwhile, the masses of the requirements in public opinion are also growingly increasing. Therefore, the research in public opinion can help the government to supervise and control the polarization phenomenon of public opinion , then inEarly scholars used discrete opinion dynamics equations to fit the rule of viewpoint change. In 2006, Grabowski and Kosiński –5, SznajSome scholars have studied the convergence of bounded confidence models and their modified model. In the study, Schawe et al. considered the heterogeneity confidence level of HK model and found the counterintuitive behavior mechanism in a homogeneous situation in a certain regional stage . Chen etSome scholars combine opinion leaders –21, netwTo improve the shortcomings that simulations explain models oversimply and defectively, the scholars began to introduce the psychological theories into the opinion dynamics model to strengthen the rationality on their proposed models –33. Li eThe remainder of the paper is organized as follows: we review some relevant knowledge about opinion dynamics model and the sleeper effect review in N individuals, each of which has opinion value xi and xi ∈ . When the difference between the opinions of agent i and j is less than or equal to the threshold ε, xi will change, otherwise it stays the same. The rules of opinion evolution are as follows:The DW model was proposed as early as 2004 and belongs to the category of bounded confidence model, which is used to study the formation, evolution, splitting, and convergence of opinions. The classical Deffuant model holds that the population contains μ represents the acceptance of the difference of opinions, generally  μ ∈ . When μ is close to 0, it indicates that the agent i is not easy to accept to others' opinions. On the contrary, it indicates that the agent i is more likely to accept to others' opinions.The parameter Since the 1930s, with the development of social psychology, scholars' research on attitudes has expanded to multiple disciplines and directions. Among other things, in studies of the temporal effects of persuasion, the researchers found an anomaly: the effects of persuasion sometimes improved over time rather than decreased over time, as was commonly thought.The Battle of Britain on the respondents' attitude change, he found that the effect on attitudes was greater after nine weeks than after five days. The effect of attitude change increases rather than decreases over time . (b) The initial opinions are distributed at one extreme partly. In this distribution, some agents have extreme opinions and gather in 0 or 1. (c) The initial opinions are distributed at two extremes partly. In this distribution, some agents have extreme opinions and gather in 0 and 1, respectively. At the same time, for the convenience of expression, we call the agents whose opinion value is 1 as “one extremists,” and the agents whose opinion value is 0 as “zero extremists.” Finally, to ensure the comparability of simulation experiments under different distributions, we set the initial number of agents ε1, respectively, and constant threshold ε2 to run the simulation according to formulas ,,ε1, respformulas  where boε1. This indicates that the larger the ε1 value is, the more tolerant the agent is to different opinion, and the more likely they are to reach social consensus. It is worth noting that this keeps true in our proposed new model. We can also find that the cluster number with the sleeper effect are larger than that without the sleeper effect under the same bounded confidence ε1. These observations can be explained by the sleeper effect. Under the sleeper effect, opinions in the vicinity of the extreme are subtly drawn in the opposite direction, which coincides with the philosophy that things will develop in the opposite direction when they become extreme.From ε2 and control experiment without the sleeper effect. Then, we run the simulation, respectively, to obtain the final cluster number under different bounded confidence ε1, which are shown in ε1, the final number of opinion clusters will decrease correspondingly, which is consistent with the result in ε1 ≤ 0.05, the convergence is weak; when ε1 > 0.05, the convergence is better. It also suggests that a larger ε1 contributes to consensus.Next, in another experiments, we set the threshold different ε2, the number of opinion clusters decreased faster. The observation can be explained by the number of discount opinions. A smaller threshold ε2  results in agents being exposed to more discount opinions, which makes aggregating easier, especially with a smaller ε1. In other words, in a society where agents are affected by the sleeper effect, agreement can be reached more easily even in a relatively smaller bounded confidence environment.Furthermore, as shown in r be the ratio of the extremists, where 0 ≤ r ≤ 1. And we assume that initial N∗r agents areone extremist, namely, x(0)i=1,  i=1,2,…, N∗r. The initial opinions of rest agents are distributed uniformly within the interval , namely, xi(0) ∈ ,  i=N∗r+1, N∗r+2,…, N.In this simulation, we set r, different ε1, and the same ε2 value, then run the simulation 500 times to obtain average stabilized opinions of extremists with or without the sleeper effect, which are shown in ε1 under the same initial opinion distribution. While, in the relatively larger ε1, average opinions of extremists with and without the sleeper effect are consistent within certain range. These observations indicate that, for the extremists, the sleeper effect is more pronounced in changing opinions in a relatively smaller bounded confidence environment.Firstly, we set different ratio of the extremists r and ε1, and then run the simulation 500 times to obtain relative size of the largest cluster when all opinions stay stable, which are shown in Next, we set different r, but the uprate decreases gradually and approaches to r value. It can be explained that the increase of r leads to the increase of extremists in the group, which trigger for the increase in the relative size of the largest cluster inevitably. However, when the sleeper effect exists, it enhances the interaction between ordinary agents and extremists, making it easier for most agents to reach a consensus.From ε1 to ensure the comparability of each experiment group and different ε2 and r. Then, we run the simulation 500 times to obtain the standard deviation and mean under different parameters, which are shown in We set constant bounded confidences r and the decrease of ε2, the standard deviation of the opinions decreases gradually; otherwise, the standard deviation gradually increases. Meanwhile, the mean of opinions does not change as ε2 changes when r is constant. It indicates that, the smaller ε2 is, the stronger the opinion aggregation is, when the initial opinion distribution is the same. Particularly, when ε2=0.55 and r=0.9, the standard deviation is smallest and the mean is largest, which is easy to cause group polarization.From r0 and r1 be the ratios of zero extremist and one extremist, respectively, in the two polar distribution of initial opinions and assume that the number of one extremist is equal to the number of zero extremists, namely, r0=r1 and 0 < r0, r1 < 0.5. Subsequently, we hold that initial N∗r1 agents are one extremists, where x(0)i=1,  i=1,2,…, N∗r1, and that initial N∗r0 agents are zero extremists, where x(0)i=0,  i=N − N∗r1+1, N − N∗r1+2,…, N − N∗r1+N∗r0. The initial opinions of the rest agents are distributed uniformly within the interval .In this simulation, we set ε2=0.85 and r0=r1=0.1 and then run the simulation 500 times to obtain the average stabilized opinions of extremists under different ε1, which are shown in ε1 increases, while the values on opinion for one extremists increase as the ε1 increases; however, they keep steady at the 0.5. Compared with First, we set stationary parameters r0(r1),  ε1, and constant threshold ε2 and then run the simulation 500 times to obtain average standard deviation of all agents' opinions, which are shown in ε1 when r0(r1) is constant. Importantly, when ε1=0.2 and r0(r1)=0.35, the standard deviation of the final opinion drops to 0. It manifests that, although the initial opinions are extreme and scattered, due to the increase of discount opinions, it is still possible to reach an agreement in a relatively small ε1. In addition, under the sleeper effect, the more extreme the initial opinion distribution is, the more likely it is to form social consensus.We set different ε2, we set the same ε1 and different r, ε2, and then we run simulation 500 times to obtain average standard deviation and the average number of clusters with different initial opinion distribution, which are shown in r0(r1) increases and ε2 decreases. It can be explained that, when A is small and the initial opinion distribution is severely extreme, agents will be exposed to a larger number of discount opinions, which leads to the mutual attraction of extremists unconsciously. Thus, agents will reach a social consensus more quickly.Finally, to study the influences of threshold Based on the classical bounded confidence model and the sleeper effect, a new opinion dynamics model is constructed in this paper. Its main characteristics are as follows: (a) considering the characteristics of individuals in network social interaction, we break the limitation that the classical DW model interacts with a single agent. (b) The sleeper effect is combined with the opinion evolution model, which expands the scope on agents' interaction. (c) In the simulation experiments, we constructed the distribution of different initial opinions and verified the rationality of the model from multiple dimensions.The main experimental results presented in this paper are as follows: (a) in the uniform distributions of initial opinions, the larger in the bounded confidences is, the less opinion clusters are formed, because of the increase on tolerance for other people. Meanwhile, under the sleeper effect, the relatively more discount opinions can accelerate to achieve opinion convergence. (b) In the one polar distributions of initial opinions, there are more extreme and larger extreme groups as bounded confidences increases. Meanwhile, the tendency on agents' opinions polarization will be accelerated with the increase of discount opinions. (c) In the two polar distributions of initial opinions, larger bounded confidence will yield a larger probability for reaching a consensus. And, unlike an extreme distribution, agency opinions tend to converge to the center as discount opinions increase and generate to reach a strong social consensus.Although the sleeper effect is difficult to detect, it can be used for reference in the governance of ideas. For example, the “Melatonin,” as a health care product that Chinese people are familiar with, its slogan is deeply rooted in people's hearts. People know that is a marketing strategy for businesses, but they often first choose it as a gift. It inspired that relevant departments need to pay more attention to the number and influence of extremists, because they could exert the profound influence on the ordinary public when controlling public events. The simulation experiments verify the validity of the model, which can provide reference for future information dissemination and public opinion management. In future studies, dynamic networks and dynamic parameters of dynamic with the new dynamical model can be considered to study more complex public opinion.


Veksler , and Frank E. Ritter (Pennsylvania State University). To showcase how cognitive science has not just benefitted from advances in AI, but can and should inspire AI development, Cassenti, Veksler, and Ritter bring together contributions from researchers actively using cognitive modeling to tackle a wide range of cognitive phenomena.The call for rapprochement is clearest in the first topic, 19th International Conference on Cognitive Modeling, a conference devoted to computational systems that are aimed at reflecting the internal processes of the mind. In their introduction, Stewart and de Jong point out how these papers, despite their diversity in content, still complement one another in terms of focus and approach: by refining and advancing computational models to better reflect empirical data, or by using such models to better explain data. Congratulations to their authors for their awards––we hope you continue the outstanding work you are doing!Incidentally, the other topic in this issue seconds this call for greater attention to and consideration of cognitive models by presenting spearheading work in this very field. For their topic, Terrence C. Stewart  and Joost de Jong (Maastricht University) have assembled revised and expanded versions of the five best papers presented at last year's topiCS encourages letters and commentaries on all topics, as well as proposals for new topics. Letters are not longer than two published pages (ca. 400–1000 words). Commentaries (between 1000 and 2000 words) are often solicited by Topic Editors prior to the publication of their topic, but they may also be considered after publication. Letters and commentaries typically come without abstracts and with few references, if any.topiCS. Feel free to open communications with a short note to the Executive Editor (Andrea.Bender@uib.no) or a member of the SEB 1756‐8765/homepage/EditorialBoard.html).The Executive Editor and the Senior Editorial Board (SEB) are constantly searching for new and exciting topics for In conclusion, we remind our readers that our publisher, Wiley, allows us to offer the Topic Editors’ introduction to their topic to all our readers as a free download.


Bombus ignitus. The levels of dopamine and its precursors in the brain peaked at the late pupal stage, but the dopamine peak extended to adult emergence. The tyramine and octopamine levels increased from the mid-pupal to adult stages. The locomotor and flight activities, and light preference increased with age. Injection of octopamine and its receptor antagonist had significant effects on the locomotor and flight activities, whereas dopamine injection did not, indicating that these activities can be regulated by the octopaminergic system. We also determined the dynamics of dopamine-related substances in honey bee (Apis mellifera) drones. The changes in the dopamine level in the brains of honey bee drones exhibited two peaks from the pupal to adult stages, whereas the bumble bee males had only one peak. These are consistent with the behavioral functions of dopamine in honey bee drones and ineffectiveness of dopamine injection at the adult stage in bumble bee males.To compare the behavioral roles of biogenic amines in the males of primitive and advanced eusocial bees, we determined the levels of dopamine- and octopamine-related substances in the brain, and the behavioral effects of these monoamines by drug injection in the primitive eusocial bumble bee,  In eusocial hymenopterans, social behaviors involving cooperation among colony members are only observed in females. Male eusocial hymenopterans specialize in reproduction and they do not participate in nest construction, brood care, or colony defense5, although males in eusocial bees contribute to colonial thermoregulation7. Therefore, the behavioral repertories of males are much smaller than those of workers. Investigating the behaviors of males and the associated physiological mechanisms may provide important insights into the specialization of behavior for reproduction in males in highly social environments.Eusociality is the most complex social system, with division of labor among genetically related individuals, and it has been reported in various species in a wide range of insect taxaApis mellifera) drones have been investigated in various research fields, including genetics, endocrinology, reproductive biology, and evolutionary biology8. Honey bee drones mature sexually for a week after emergence and start flying to mate with virgin queens9. The locomotor and flight activities associated with reproduction in drones increase with age during their sexual maturation10. Honey bee drones return to the mother colony, whereas bumble bee males do not learn the colony’s location and never return to the colony12. After leaving the nest, bumble bee males forage for themselves while searching for gynes to mate. This may be due to the male production at the end of the colony season when the nutritional status of the bumble bee colonies declines. Thus, the dependence of males on the colony differs between the honey bee and bumble bee, which might reflect the adaptation of male behavior to different social environments.In advanced eusocial environments, the behaviors of honey bee  males. We also compared the mechanisms in the bumble bee and honey bee to determine whether the mechanisms mediated by biogenic amines differ between the two species.Bumble bees comprise a large group of primitive eusocial bees, and they are ideal species for investigating the missing link between solitary and advanced eusocial species, although the multidimensional analysis of social behaviors suggests the small difference of social complexity between honey bees and bumble beesH = 106.500, df = 9, P < 0.001, Steel–Dwass: P < 0.05, Fig. H = 88.300, df = 9, P < 0.001, Steel–Dwass: P < 0.05, Fig. H = 88.599, df = 9, P < 0.001, Steel–Dwass: P < 0.05, Fig. We initially determined the levels of dopamine, octopamine and their precursors in the brains of bumble bee male pupae and adults by using high-performance liquid chromatography with electrochemical detection (HPLC-ECD) systems. The levels of two dopamine precursors  and dopamine exhibited similar trends, and they depended on age during the pupal stage Fig. A,B,C. Th23. However, there have been no previous reports of the biogenic amine levels in the brain and behavioral assays by application of biogenic amines in bumble bee males. The present study is the first determination of the functions of dopamine and octopamine in the behavioral activities of males in a primitive eusocial bee.Investigation of the physiological mechanisms that underlie the male reproductive behavior has been required for monophyletic clade species such as the corbiculate bees. In honey bee drones, the modulation of reproductive behavior by biogenic amines have been investigated23. Octopamine injection enhanced the flight activity in drones23. The changes in the octopamine levels and behavioral functions of octopamine have been shared between bumble bee males and honey bee drones.In bumble bee males, the octopamine level in the brain increased from the mid-pupal to adult stages. The locomotor and flight activities in adult males also increased with age up to sexually mature age (8 days old). These results suggest that octopamine is a potential neuroactive substance that coincides with age-related increases in behavioral activities. We then tested the effects of biogenic amines on the behavioral activities by drug injection. Octopamine injection increased the locomotor activity, whereas epinastine decreased the locomotor activity and increased the latency of flight initiation. Since epinastine acts through octopamine receptors as an antagonist, the results indicate that the blockade of octopaminergic signaling decreases the locomotor and flight activities, and therefore, octopamine enhances these activities in bumble bee males. In honey bee drones, the brain levels of octopamine and locomotor and flight activities increased with ageIn contrast to octopamine, the dopamine levels in the brain during the adult stage decreased immediately after adult emergence and dopamine injection did not affect the behavioral activities in bumble bee males. These results suggest that dopamine is not involved in the increase of the behavioral activities of bumble bee males at least at the day 4 of adult life.22. Therefore, the dopamine levels in the brains of honey bee drones had two peaks from the pupal to adult stages . In solitary insects, dopamine enhances the locomotor activity and sexual behavior in D. melanogaster31, as well as the locomotor and flight activities in the large carpenter bee, X. appendiculata24. These results suggest that the dopamine effects on the locomotor and flight activities might be shared among males in several solitary species and the honey bee, but not in the bumble bee. It is required to be determined whether the ancestral characteristic is one or two dopamine peaks from the pupal to sexually mature adult stage.We determined the changes in the dopamine levels in the brains of honey bee drones during the pupal stages to compare with those in bumble bee males. The dopamine levels in honey bee pupae increased with age and peaked immediately before adult emergence (P10–11). It was previously reported that the dopamine levels during the adult stage increased with age and peaked at 8 days after emergence8. The JH titer in the hemolymph increases with age until sexual maturation as the dopamine levels in the brain34. JH enhances the gene expression of enzymes involved in dopamine biosynthesis and increases the levels of dopamine in the brain35. In bumble bee males, the JH titer may not increase during early adult stage and not stimulate dopamine biosynthesis. Intakes of foods containing tyrosine from nurse bees can also enhance the gene expression of enzymes of dopamine biosynthesis and increases the levels of dopamine during early adult stage in honey bee drones36. Adult males in the bumble bee do not receive foods from workers and may have less opportunity to intake tyrosine than honey bee drones. This may be another reason for the lack of an increase in dopamine.Dopamine effects on locomotor and flight activities in bumble bee males may have been lost or unused with a lack of a dopamine peak during the adult stage. In honey bee drones, the dopamine peak at early adult stage is generated by effects of juvenile hormone (JH) and food intakesB. ignitus) males. We also compared the associated mechanisms in the bumble bee and honey bee to obtain insights into the evolution of the regulation of reproductive behavior. The octopamine level in the brain increased with age in adults in parallel with the locomotor and flight activities and light preference, whereas the dopamine level did not. Injection of octopamine and epinastine affected the locomotor and flight activities in opposite ways, but dopamine did not. These results suggest that the octopaminergic system enhances locomotor and flight activities involved in the reproductive behavior of bumble bee males. It has been reported that dopamine and octopamine promote the flight activity of honey bee drones. Therefore, the function of octopamine in promoting flight has been shared between bumble bee and honey bee males, but the behavioral function of dopamine with dopamine increase was not observed in the bumble bee males.This study investigated the relationships between biogenic amines and the reproductive behavior of bumble bee (B. ignitus) colonies were kept in wooden boxes using the procedure described by Sasaki et al.38. Male pupae were collected from cocoons in 12 queenright colonies. To identify the pupal age, we defined a white male pupa with white compound eyes as a 0–1 day-old pupa (P0–1). We transferred 0–1 day-old pupae into plastic cups (Φ98 mm × 96 mm) kept at 28 °C under constant dark conditions, and then collected them at 0–1, 2–3, 4–5, 6–7, and 8–9 days after pupation. Newly emerged adult males  were marked on the thorax with paint  to identify their age. The marked males were returned to the mother colonies and collected from the colonies at a specific age. The collected males were used to measure the levels of biogenic amines in the brain and for behavioral experiments. The samples used for measuring the levels of biogenic amines were collected at 11:00–13:30. They were euthanized with liquid nitrogen and stored in liquid nitrogen until their analysis.Commercially reared bumble bee (A. mellifera) drones were obtained from normal queenright colonies kept at an apiary in Tamagawa University, Tokyo, Japan. To obtain drone pupae, comb frames with equal areas of drone and worker comb bases were introduced into the colonies to allow workers to build comb cells on them. After the drone comb cells were capped, the frames were taken from the colonies and transferred into an incubator kept at 33 °C. The pupal age was identified based on the method described by Jay39. Newly emerged adults were also collected from the drone comb cells. Pupae and newly emerged adult drones were collected at 11:00–13:30, euthanized with liquid nitrogen, and stored in liquid nitrogen until dopamine-related substances were measured.The pupae and newly emerged adults of honey bee  on a Peltier cooling unit  at approximately 4 °C under a microscope. The dissected brains were homogenized for 2 min with microglass homogenizers in 100 µL of ice-cold 0.1 M perchloric acid containing 0.1 ng/µL 3, 4-dihydroxybenzylamine. Each sample was then transferred into a 1.5 mL microcentrifuge tube and centrifuged at 15,000 × 40 comprised a solvent delivery pump , refrigerated automatic injector , and C18 reversed-phase column , and the temperature was maintained at 35 °C. The ECD  was set at 0.85 V and employed at 35 °C. The mobile phase contained 0.18 M monochloroacetic acid and 40 μM 2Na-EDTA, which was adjusted to pH 3.6 with NaOH, and 1.62 mM sodium-1-octanesulfonate and 5% CH3CN were added to this solution. The flow rate was kept constant at 0.7 mL/min.The HPLC-ECD system used for measuring the dopamine, octopamine, and tyramine levels developed by Sasaki et al.41 comprised a solvent delivery pump , refrigerated automatic injector , and C18 reversed-phase column , and the temperature was maintained at 35 °C. The ECD  was set at 0.84 V and used at 35 °C. The mobile phase contained 83 mM citric acid monohydrate, 17 mM sodium acetate, 13 µM 2Na-EDTA, and 2.3 mM sodium-1-octanesulfonate, and 7% methanol was added to this solution. The flow rate was kept constant at 0.7 mL/min. In both HPLC-ECD systems, external standards were run before and after the sample runs to identify and quantify biogenic amines. The peaks were identified by comparing the retention time and hydrodynamic voltammograms with those obtained for the standards. Measurements based on the peak areas in the chromatograms were obtained by calculating the ratio of the peak area for a substance relative to the peak area for the standard.The HPLC-ECD system used for measuring the tyrosine and 3,4-dihydroxyphenylalanine (DOPA) levels developed by Matsuyama et al.42. The precipitated protein pellet obtained from the brain tissue after extracting biogenic amines was treated with the same procedures as described by Sasaki et al.40. The absorbance of each reacted sample was measured at a wavelength of 590 nm using a microplate reader .To normalize the levels of the biogenic amines based on the protein contents in the brain, the amounts of protein were measured using the Bradford method43. The transparent cover sheet was separated into four divisions by crosshairs and then covered by a red plastic sheet over the half of the transparent cover to provide a dark (red) area for insects in the chamber. After acclimatization for 5 min, the spontaneous locomotor activity of each bee was recorded using a digital video camera for 15 min. The number of crosses of the crosshairs was counted in the video data recording. In addition, not moving and walking individuals were counted. The duration of residing under the red plastic sheet was recorded for determination of light preference. After measuring the locomotor activity and light preferences, the latency of flight initiation was measured in a net cage (45 cm × 60 cm × 45 cm) at 28 °C, as described by Sasaki et al.43  with a transparent sheet cover at 28 °C until the behavioral experiment Fig. . The beh.43 Fig. . The cha–4, 10–3, and 10–2 M) were dissolved in 0.1 M phosphate buffer (pH 7.0) or 2 µl of 0.1 M phosphate buffer (control). Epinastine  was dissolved in 0.1 M phosphate buffer to the concentration of 10–2 M. To examine the roles of biogenic amines in the locomotion, light preference, and flight behaviors of bumble bee males, prepared solutions were injected into the abdomens of 4 day-old males using a 10-µL microsyringe with a fine needle. The duration of acclimatization was 15 min after drug injection before observing locomotor activities.Two µl of dopamine (Sigma-Aldrich) and octopamine (Sigma-Aldrich) solution (10https://cran.r-project.org/). Levels of biogenic amines were compared between groups using the Kruskal–Wallis test followed by the Steel–Dwass test for pairwise comparisons. Locomotor activities and durations of residence in the red area were also analyzed using the Kruskal–Wallis test followed by the Steel–Dwass test. Proportions of locomotor  and flight (“not flying” vs. “flying”) activities were examined using Fisher’s exact test with Bonferroni correction. Behavioral activities of males were examined using the Kruskal–Wallis test followed by the Steel test (control vs. treatments). Behavioral activities of males treated with or without epinastine were compared using the Mann–Whitney U test.All statistical analyses were performed using R software (ver. 4.1.2, Supplementary Information 1.Supplementary Information 2.


This paper describes the influence of the transannular π–π interaction in controlling the carrier transport in molecular wires by employing the STM break junction technique. Five pentaphenylene-based molecular wires that contained [2.2]paracyclophane-1,9-dienes (PCD) as the building block were prepared as model compounds. Functional substituents with different electronic properties, ranging from strong acceptors to strong donors, were attached to the top parallel aromatic ring and used as a gate. It was found that the carrier transport features of these molecular wires, such as single-molecule conductance and a charge-tunneling barrier, can be systematically controlled through the transannular π–π interaction. Single-molecule electronics (SME) is the study of electrical procedures measured or controlled on a molecular scale. Charge-transport property regulation is one of the main challenges in the field of molecular electronics, and molecular-scale tuning is the most effective way to address this. Therefore, controlling the charge transport through single-molecule wires is very important for both the understanding of mechanisms and for practical single-molecule applications ,2,3,4. Iπ–π distance and strengthen the intramolecular π–π interaction of the two aromatic rings, in contrast with the saturated bridges of [2.2]paracyclophanes [π–π interaction also leads to a distorted π-electron system and a highly strained molecular structure, which is of importance as PCD molecules can be ring-opened by ring-opening metathesis polymerization to produce poly-based conjugated polymers for the fabrication of functional devices [π–π interaction in regulating the electronic property of PCD molecules [Cyclophane chemistry has attracted much interest over the last 5 decades due to its unique geometric structure and electronic properties. It has been widely used in various aspects, such as molecular self-assembly ,22, molelophanes ,27. The  devices ,28,29. Rolecules .π–π interaction, which is a noncovalent interaction, has been rarely used as a tuning factor to control the charge-transport process in molecular electronics [π-orbital of the top phenyl ring and the vinyl groups are orthogonal to the charge-transport direction along the molecular wire  palladium, which was purchased from Aldrich. Toluene and tetrahydrofuran (THF) were dried over sodium/benzophenone and freshly distilled prior to use. Other reagents were used without further purification. Compounds 6a, 6b, 6c, 6d, 6e, and 7 , ESI† we1H nuclear magnetic resonance (1H NMR) spectra were recorded on a Bruker AV400 spectrometer . Matrix-assisted laser desorption/ionization with time-of-flight (MALDI-TOF) mass spectrometry was carried out on a Bruker Ultraflextreme MALDI-TOF/TOF spectrometer using a matrix of dithranol.A KSV  CAM 200 contact angle device was selected to detect the contact angle. An Escalab-250Xi  containing monochromatic Al Kα as a radiation source was used to study the X-ray photoelectron spectroscopy (XPS). −4 M of the target molecule. After 4 h of immersion in PCD solution, the gold substrate was then washed with THF and ethanol, dried with N2, and used immediately.First, a propane flame was used to anneal the chosen substrate, and then the SAMs of the isolated molecules were fabricated according to a previous publication. Briefly, tetrabutylammonium fluoride (TBAF) was used as the deprotecting agent with a tetrahydrofuran (THF) solution containing ca. 1 × 102. Then, the solvent holder was placed over the gold–SAM surface, and the designated amount of toluene was added during the measurement. It is estimated that about ~2000 current-distance traces are required in a typical BJ experiment.Briefly, a 0.25 mm gold wire was prepared as the gold tip by mechanical cutting. All the experiments were conducted in degassed mesitylene in order to decrease the chance of surface contamination. After that, the STM Teflon solvent holder was sonicated in acetone and dried under NI-V recording experiments were conducted at 100 mV bias voltage in toluene. There are three steps, include tapping, conductance step detection, and I-V recording. For the tapping step, when the current increases to a predefined value, the tip will move to the substrate, and then it will retract until reaching a lower, pre-set current. During each retraction, the conductance step detection was applied, and we selected the measured conductance range according to a previously measured conductance histogram. The I-V recording step was performed immediately upon the application of the conductance step, and the whole procure included three sub-steps. The first was the immediate holding in position of the tip. The second was the quick (10 Hz) current–voltage curve recording (from +1.5 V to −1.5 V (or +1.8 V to −1.8 V)). The last sub-step occurred when the I-V curve detection was completed; the tip would be removed from the substrate once the current decreased to a pre-set value, and the test was started again. For the data selection, I-V curves that were incomplete or contained large switching noises were detected and removed from the statistical analysis. This procedure allowed us to obtain complete I-V curves for statistical analysis.The φ0 and the voltage division factor γ of the molecular junctions were calculated, following the work by Baldea, with the Equation [Energy offsets Equation :(1)φ0=eV3, -Cl, -H, -CH3, and -OCH3 were immobilized on the top phenyl ring, ranging from a strong electron acceptor to a strong electron donor. For the convenience of discussion, the molecular wires have been named “PCD-X”, where X represents the substituent group. Detailed characterizations of the intermediate products and the final PCD-X molecular wires were carried out by combining 1H-NMR  intermediates are expected as products during the cyclization process, namely, pseudo-gemini (eclipsed conformation of substituents on the aromatic rings) and pseudo-ortho isomers. However, only one of the possible isomers was recognized on the TLC plate and successfully purified as the main product after column chromatography, with an overall yield of around 40–50%. The clear lophanes  ESI† andlophanes  ESI† als2Cl2 solutions of both compounds. The X-ray crystal structure , which excludes the influence of isomerization on the electronic property of the prepared molecular wires. In addition, two phenyl groups in cyclophane are closely stacked with a short distance of 2.97 Å; therefore, the π electron clouds of the phenyl rings can strongly overlap, and electronic tuning can be performed more effectively. UV–Vis measurement showed that the absorption edges for the PCD-Cl, PCD-H, PCD-CH3, and PCD-OCH3 molecular wires were around ~350 nm, while a 20 nm red shift was observed for PCD-CF3, which is strong evidence that the R group on the top phenyl ring can successfully affect the pentaphenylene backbone via the effective π–π overlap. The trend agrees well with the DFT calculation results  were investigated, and the crystallographic data can be found in ESI†. Single crystals were grown through the slow diffusion of MeOH into the concentrated CHtructure  ESI† of  results  ESI†.Self-assembled monolayer (SAM) films were fabricated on a gold surface, with the reaction of the thiol–gold used to test the conductance of the single molecules, and the molecular junction was based on the reaction of two molecules’ terminal thiol groups with two gold electrodes. Successful immobilization of the molecular wires onto the gold substrates was confirmed by combining contact angle and XPS measurements of the SAMs . Namely,−6~10−4 G0 in these stretching traces, which is consistent with the first signature in a single-molecule junction. . The plateau length is commonly around 0.5–1.0 nm, and the conductance fluctuation below 10−6 G0 may be caused by the noise floor. 3, PCD-Cl, PCD-H, PCD-CH3, and PCD-OCH3 were 5.8 × 10−6 G0, 8.2 × 10−6 G0, 2.5 × 10−5 G0, 3.2 × 10−5 G0, and 8.1 × 10−5 G0, respectively. The conductance systematically changed as the substituent varied from strong acceptor (CF3) to strong donor (OCH3).The STM-based break junction technique was used to measure the single-molecule conductance ,37. WithI-V) curves were recorded for each sample. Thus, the corresponding transition voltage spectroscopy (TVS) results can be obtained. The incomplete and switching I-V curves resulting from the breakdown and instability of the molecular junctions were automatically detected but did not appear in the I-V histogram. The I-V and G-V histograms of the five substituted molecules are presented in the 2) versus 1/V curve [Keeping in mind that bias voltage range plays an important role in the charge transport of the single-molecule junction, thousands of current–voltage  decreased from 1.4 V to 0.9 V and from 1.6 V to 1.3 V when the substituent is altered from PCD-CF3 to PCD-OCH3, and this could be explained as the contact of symmetry molecule and metal-molecule. In addition, the asymmetry could also be caused by the solvent polarity [polarity .0) between the electrodes’ Fermi level and molecular orbitals are seriously affected by the applied bias V, φ0 ≡ φ0(V)|V = 0 → φ0(V), voltage division factor γ was used to offset the effect, where φ0(V) = φ0 + γeV [t,p and Vt,n for bias polarities could be utilized to evaluate the corresponding ambipolar transition voltage ; the correct energy offset φ0 and the voltage division factor γ based on the equations were established by Baldea  were deduced as being around 1.28 eV, 1.21 eV, 1.15 eV, 1.01 eV, and 0.91 eV, respectively. We can thus conclude that the transition voltage and the corresponding charge-tunneling barrier increase with substituent varying from electron donor to electron acceptor. Finally, we calculated the voltage division factor γ, and the values ranged from 0.03~0.06 (Considering that the offset energy (φφ0 + γeV ,30, In py Baldea  ESI† [41.03~0.06  ESI†, wh3 to electron donor -OCH3, while the LUMO simultaneously extends to the pentaphenylene backbone. 0 changes with the HOMO energy level of the PCD-based molecular wires. It is clear that the φ0 decreases as the HOMO energy level increases, indicating that the charge-transport mechanism in these PCD molecular wires is indeed through hole transport and can be regulated by the intramolecular π–π interaction.All of the results discussed above indicate that the top parallel phenyl ring can modulate the molecular conductance and the charge-tunneling barrier of the pentaphenylene conducting channel through the transannular π–π interaction. DFT calculations based on the RB3LYP method, with basis set of 6-31G*, were carried out to obtain insight into the energy-level alignment of these PCD molecular wires. In summary, we have successfully prepared a series of molecular wires that demonstrated how the intramolecular transannular π–π interaction affects the charge-transport property in molecular wires. Both the single-molecule conductance and current–voltage characteristics can be systematically tuned through the transannular π–π interaction. Transition voltage spectroscopy measurement and DFT calculation suggest that the effect is manifested via tuning the HOMO energy level and orbital spatial distribution of these PCD molecules.


Codex Alimentarius and WOAH. Applied in four stages of progressive development, the objective of the tool is to provide a qualitative and systematic assessment of the risks of AMR from animal production systems, to animal and human health, and to identify gaps in cross cutting factors in AMR management. The tool consists of three instruments: (i) a survey to collect data for a situation analysis of AMR risks; (ii) a methodological procedure for the analysis of the information obtained; (iii) instructions for the preparation of a national roadmap for the containment of AMR at a national level. Based on the results from the information analysis, a roadmap is prepared by guiding and prioritizing the needs and sectoral actions for the containment of AMR under an intersectoral, multidisciplinary and collaborative approach, and according to country priorities and resources. The tool helps to determine, visualize and prioritize the risk factors and challenges that contribute to AMR from the animal production sector and that need to be addressed to manage AMR.In response to the need to manage Antimicrobial Resistance (AMR), countries have produced National Action Plans (NAPs), which require detailed information of the AMR situation in all sectors. Considering the limited information that is publicly available for an analysis of the AMR situation in animal production, the FAO Regional Office for Latin America and the Caribbean (FAO RLC) developed the “FAO tool for a situation analysis of AMR risks in the food and agriculture sectors.” The objective of this paper is to present the methodology developed for a qualitative evaluation of the risk factors of AMR toward animal and human health, based on terrestrial and aquatic production systems and their associated national public and private mitigation measures. The tool was developed reflecting the AMR epidemiological model and the guidelines to conduct a risk analysis of AMR from the  Antimicrobials are critical elements in the food and agriculture sector, contributing to sustainable terrestrial and aquatic animal production systems. Although Antimicrobial Resistance (AMR) is known to be part of a natural selection for bacterial agents , 2, the AMR has prompted a global health crisis which knows no geographical, political or economic barriers. Scientific evidence shows that with the emergence of bacteria now resistant to substances to which they were once susceptible, infections are increasingly difficult to treat. Thus, AMR constitutes a serious threat to human and animal health. From an economic standpoint, the World Bank reports that by 2050 AMR could cause a decrease in the world's gross domestic product (GDP) of 1.1–3.8 percent per annum. During the same timeframe, health costs could also increase between USD 0.33 trillion and over USD 1 trillion per year. Livestock is especially exposed to AMR impacts, by 2050 a loss of 11 percent of livestock production is expected in low-income countries . In the Recognizing the importance and impact of AMR, and in response to the Global Action Plan for AMR , countriOne of the first steps for the implementation of a NAP demands that responsible health authorities have information detailing the AMR situation, thus enabling them to design, implement and manage appropriate strategies for each country .The use of antimicrobials in animal production, human health and agriculture is one of the most important elements in the generation of AMR. The epidemiological interdependence between humans, animals and the environment highlights the importance of addressing the risk factors that contribute to the introduction and exposure of AMR from animal production .The exploration of the risk pathways associated with AMR in the food chain in the Latin American and Caribbean region revealed a significant lack of information that would enable a systematic quantitative/semi-quantitative assessment . One appCodex Alimentarius, is a scientifically based process consisting of the following steps: (i) hazard identification; (ii) hazard characterization; (iii) exposure assessment; and (iv) risk characterization  developed the “FAO tool for a situation analysis of AMR risks in the food and agriculture sectors” . This tool was developed under the One Health approach, essential for the containment of AMR, to provide a qualitative and organized assessment of AMR risks from animal production systems.Given that the countries did not have specific AMR data (epidemiology/microbiology) for the food and agriculture sector at that time, this tool aims to be a first approach on the general aspects of AMR, taking into account the risks and the mitigation measures  without considering any specific characteristics of a particular agent.The objective of this paper is to present the methodology developed by FAO for a qualitative evaluation of the risks of AMR to animal and human health . The evaThis tool was initially developed with antibiotics as the main antimicrobial of concern in animal production. It allows the evaluation of all types of antimicrobials, but prior to its application, questions should be revised to reflect the specific antimicrobial to be assessed.Codex Alimentarius  identifying information related to AMR in the animal production chain; (ii) designing the information collection and analysis process; and (iii) validating the tool.The FAO RLC team assembled an exhaustive review of literature from international organizations, country studies and scientific papers related to AMR and AMU in food animal production systems. With this information, FAO RLC team identified the epidemiological routes of AMR from the use in animal production to animal health, human health and the environment. Identifying the epidemiological routes of AMR contributes to the design, application and evaluation of successful mitigation measures .The generation and dissemination of any infectious agent in an animal production system depends on multiple factors such as the conditions in which the animals are kept, feeding, biosecurity measures, and the use of preventive elements such as vaccination, among others. Despite the measures applied, the risk of existence of these agents persists. Therefore, resources such as antimicrobials are used to tackle or prevent the diseases caused by infectious agents, practices that influence the generation of AMR. The risk of AMR spread from animal production to the animals themselves is related to direct contact between the animals, waste disposal and the contamination of the environment (including water sources). For humans, these exposure routes are depicted as transmission through environmental pollution, contaminated food, and direct contact with animals and products from the productive system .However, the generation and dissemination of AMR is also influenced by other cross cutting factors. These include regulatory policies, the effectiveness of sanitary programmes associated with antimicrobial use (AMU) in animal production, and the existence and exchange of information regarding AMR in animal and human health. Equally important are the data for the implementation and monitoring of strategies, the use of alternatives to antimicrobials, the collaboration mechanisms under One Health, and research .The necessary data was identified from the literature review. The data to be collected, included factors from the AMR epidemiological model , public A survey was designed to gather information and initiate and/or strengthen intersectoral work by the participation of national technical teams from both the public and private sectors. The survey is led by the Animal Health Authority (as FAO counterpart) for the collection of information. The survey comes with a list of instructions, including the list of stakeholders that should participate during the collection of information .Codex Alimentarius  to animal and human health.The tool consists of three main instruments applied in four stages of progressive development with the support of the FAO team :A survey for data collection to generate a situation analysis of AMR risks, including instructions for its application, indicating the stakeholders considered for each of the components;A methodological procedure for the analysis of the information obtained through the survey, andInstructions for the development of a national roadmap for the containment of AMR.In general, Stage 1 is allotted a period of 2 weeks. Stage 2 takes 2 months on average. Stage 3 is finalized in 1 month.The purpose of the survey is to obtain information to evaluate: (i) risk factors toward animal and human health  related to the introduction and exposure of AMR from animal production; (ii) existence and effectiveness of public/private programs and regulatory elements, as well as private mitigation measures, which contribute to the control of AMR risk factors; and (iii) gaps in cross cutting factors that enable system sustainability.The survey has 322 questions organized into four components  the qualitative assessment of AMR risks from animal production and their effects on animal and human health; and (ii) an evaluation of gaps of the system sustainability factors.This assessment is based on the hazard, risks of introduction, risks of exposure, and mitigation measures associated with each of the introduction and exposure risks 1. The riEach risk subfactor and mitigation measure is evaluated as per criteria developed by the FAO team and validated by international experts from Latin America through an expert elicitation process , 5. The The risk assessment process is carried out independently for animal and human health, and for each animal production system evaluated, distinguishing between intensive production and family farming.The analysis of sustainability factors consists of identifying gaps in the system using the criteria developed by the FAO team and validated by international experts from Latin America through an expert elicitation process. The factors analyzed are Surveillance of the use of antibiotics, AMR surveillance, Institutional governance of One Health and the agri-food sector, Communication, awareness and training, and Research and innovation. These are comprised of 7, 18, 36, 23, and 2 subfactors, respectively , environment and the human health sector. These include technical staff, decision makers and policymakers on AMR.Based on the analysis of the information collected from the survey, the roadmap is prepared by guiding and prioritizing national needs and sectoral actions for the containment of AMR. Actions are outlined according to the characteristics of the productive, health and institutional systems of each country, and in line with the National Action Plan on AMR, the Global Action Plan on Antimicrobial Resistance , and theThe roadmap guides decision-making based on evidence and mitigation measures according to country technical, legal and economic feasibility (the tool includes instructions for roadmap application to facilitate the process). Consequently, the country has an agreed instrument for the construction, strengthening and monitoring of the national strategy for the containment of AMR in the food and agriculture sector.The steps to formulating a roadmap are:- Step 1. Awareness and prioritization of risks and gaps. Country stakeholders prioritize the risks and gaps recognized through the qualitative risk assessment and gap identification. The prioritization of risks should be carried out together with other relevant actors from the public and/or private sectors.- Step 2. Identification of solutions for prioritized risks and gaps. For each solution, the internal or external factors  are defined, along with the actors that could facilitate or restrict the application and/or effectiveness of the proposed solutions.- Step 3. Analysis and proposal for the management of stakeholders. This step consists of the identification and characterization of the interest groups related to the containment of AMR . The role of each stakeholder within the roadmap is also identified.- Step 4. Development of the roadmap. The identified actions or solutions are ranked. Each action or solution is characterized in relation to its verifiable product, the person or unit responsible, start and end dates, the resources involved, and other necessary requirements.Many international agencies have developed guides, databases and tools to support countries in the management of AMR –31. HoweThe constant support of the FAO team during the application of the tool facilitates its implementation across different settings, addressing the challenges related to the collection of information. To date, the FAO situation analysis tool has been applied in ten countries in Latin America and the Caribbean, and two countries in Africa. The results show the feasibility of carrying out a qualitative assessment of the risks of AMR from food animal production to animal and human health.The FAO situation analysis tool is designed to be applied in any country, regardless of its economic classification, thereby offsetting the centralization of information from high-income countries .Risk assessment is often regarded as a complex process due to the amount of information it requires. The application through this tool in two geographical regions shows the existence of information (whether aggregated or not) and the capacity to obtain relevant information in the countries to develop a risk assessment.The methodology has a global and highly specific approach to AMR risk management. From the global point of view, the risk factors applicable to risk assessment and associated mitigation measures are identified , along with fundamental aspects of the system's sustainability. At the same time, the specificity of the tool enables the evaluation of those risk factors with the associated mitigation measures, and sustainability elements that are generally not characterized, both challenges are rendered invisible in the daily tasks of animal production. Examples of this include the insufficient use of records in the application of good production practices, the lack of regulations developed which pertain to the use of antibiotics in food for animal consumption and environmental management practices. Regarding the evaluation of the mitigation measures (regulatory or public/private programs), the specificity of the tool allows the country not only to evaluate the existence of the regulation, but also the effectiveness of the application of this measure .The structure of the FAO situation analysis tool allows the country to look at the epidemiological and system sustainability factors that influence AMR and highlights the importance of taking a systematic approach to address One Health challenges.The application of the FAO situation analysis tool enables the identification of the weakest factors to address the containment of AMR. In some cases, such as in the consumption of food of animal origin, the consumption of food of animal origin contaminated with bacteria, and the direct contact with animals or animal products, the high percentage of risks may be caused by the lack of data in the countries , 9. One Related to system sustainability factors, important gaps were observed in the surveillance of the use of antibiotics, AMR surveillance and risk communication.The FAO situation analysis tool shows the differences between animal production systems in the countries. For example, broiler chickens, laying hens, pigs and crustaceans show higher risks , 9. FiguThe consumption of food of animal origin contaminated with bacteria, and direct contact with animals and animal products are significant exposure risk factors for human health, especially in broiler chickens, pigs and cattle.The identification of the weakest factors and the differences between animal production systems allow countries to prioritize their risks and gaps, facilitating the formulation of a roadmap to address the containment of AMR.The independent evaluation of intensive production and family farming allows to identify specific risks for each of these productive systems, and highlights the importance of the participation of all productive sectors in AMR management. The need for specific characterization and the availability of differential policies, programs and/or regulations developed and implemented in an effective way for this sector is evident in family farming.The FAO situation analysis tool is designed to be applied to seven animal production systems. The country has the possibility of applying the tool in some or all seven, or it can propose new animal production systems. Moreover, the independent evaluation between intensive animal production systems and family farming also allows the country to opt for evaluation in both areas.The tool has shown that the containment of AMR not only requires specific measures but can also be managed indirectly. The latter includes adequate sanitary management; the application of good animal production practices; the implementation of biosecurity and animal welfare measures; good practices in the production and handling of food for animal consumption; adequate hygiene practices during the processing of foods of animal origin, among others.The journey from information gathering to roadmap formulation contributes to participatory instances between the different actors involved in the animal production chain. This enhances the understanding and awareness of the risks derived from AMR, increases the participatory and collaborative intersectoral work in the public and private sectors, and emphasizes shared responsibility in containing AMR. At the same time, it also increases the participation of the agri-food sector in the National Intersectoral Committee on AMR.Countries address multiple health topics in the agri-food sector simultaneously. The FAO situation analysis tool facilitates the establishment of priorities for the AMR challenges identified within the animal production sector, and allows high-level decision makers to visualize those challenges, enhancing the importance of AMR within the political agenda of the food sector. On the other hand, the results reveal country strengths regarding the construction of general and specific policies and strategies for the containment of AMR.As AMR is a topic of global concern, the development of public policies for AMR management could be necessary for some countries, and the adequate technical, legal, economic, and political inputs are fundamental elements for policy success. One outcome of the tool's application was a document that provides technical and legal elements for the construction and implementation of a national public policy for AMR, with an emphasis on animal production . This doDespite the results obtained, the tool is subject to constant evaluation and refinement.The tool is particularly dependent on intersectoral participation to reflect the animal production chain and the impact of AMR risks on animal and human health. Although the tool seeks to be implemented under an intersectoral approach and suggests its importance, it was not created with the evaluation of that approach in mind. The challenge of addressing AMR from the One Health approach, requiring strong commitment and intersectoral participation, is a recent effort that may suffer delays due to the organizational structure of the National Official Services and the relationship between public institutions and with the private sector, respectively. However, the gradual strengthening of the One Health approach should facilitate tool application.This version of the tool requires the support of the FAO team in each stage of its application. In the future, the tool will undergo sufficient refinement to be applied in the self-assessment format. This will give countries the autonomy to undertake its periodical application without FAO intervention.Some of the information requested may exist in a disaggregated form, be difficult to access or not exist at all, skewing the results toward greater risks. However, the results from the tool's application in the country represent the current situation, which may change over time. Final risk results may be greater or lesser, depending on the data available .For the purposes of the tool, the methodology for the information analysis was developed under a regional context. However, the evaluation criteria could be adjusted according to the specific needs of each country with the input of national experts.Finally, as with any tool, the results will depend on the quality of the data provided.The FAO situation analysis tool helps to determine and visualize the risk factors involved in the process of AMR introduction and exposure from animal production. The tool allows the identification and collection of information from the different sectors of animal production. The analysis highlights, lists and prioritizes the challenges to be addressed for the management of AMR at the technical level, but also at the level of authorities and decision makers, based on country priorities and resources. In the public sector, it strengthens the relationship between the areas or institutions of national services, together with the private sector, academia, and other actors. For the private sector, the tool demonstrates the importance of the problem and reinforces sectoral participation in the search for joint solutions with the public sector under the One Health approach.The original contributions presented in the study are included in the article/All authors listed have made a substantial, direct, and intellectual contribution to the work and approved it for publication.


White wine’s oxidative stability after several years of bottle aging is synonymous to its organoleptic quality. In order to gain control over the cascade of chemical reactions that are implicated in that phenomenon, fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS)-based metabolomics and sensory evaluation were combined for the analysis of a vertical series of white wines from different vineyard plots. Data mining using supervised cluster analysis allowed the extraction of known and unknown sulfur- and nitrogen-containing molecular features, with oxidative stability molecular markers presenting an increased number of S and O atoms in their formulas. In their majority, S-containing molecular features possessed between 4 to ~12 O atoms, indicating the relatively higher importance of sulfonation reactions as opposed to dimerization reactions. Molecular networking, based on sulfonation reaction transformations, evidences the importance of hitherto unknown and/or minor sulfur dioxide binders  on wine’s oxidative stability. During bottle aging, wine is exposed to relatively low quantities of oxygen that are nevertheless sufficient to influence the outcomes of their shelf-life period. In particular, reactive oxygen species (ROS), formed by the reduction of molecular oxygen, modulate the extent of different reactions involving volatile and nonvolatile components, resulting in the formation and/or degradation of a number of powerful aroma compounds, with major consequences on the process of aromas’ oxidative evolution . At thisAbove all, these results emphasized the dependency of the oxygenation process on the wine’s compositions, where different wines could exhibit different reactivity towards oxygen, thus stressing the need for analytical approaches that can provide comprehensive pictures of subtle mechanistic variations among series of samples. In that respect, non-targeted mass spectrometry-based metabolomics have recently shown great potential in describing the evolution of chemical spaces involved in enological practices ,5,6,7, b2 concentration added to must at pressing or to wine at bottling [Sulfur- and nitrogen-containing compounds constitute the antioxidant molecular capital of white wines in the bottle and determine their aging potential ,15. Thesbottling ,21. Thesbottling .All these studies highlighted the extent to which the chemistry that could be involved in wine’s oxidative stability during bottle aging is still unknown. The main scope of the present study was to examine the importance of key chemical reactions such as sulfonation in wine’s oxidative stability during bottle aging. In particular, in this work, we aimed to compare the metabolic profile of white wines, sealed with a natural cork, sensory evaluated as oxidized or good (not oxidized) after several years of bottle aging under cellar conditions. To obtain a high level of variability, the experimental design included wines from the same winery from two vintages and five vineyard plots. An investigation of known and unknown sulfonation reaction products was performed by means of in silico deconjugation.r > 0.8) for each cluster. G-related molecular markers were dominated by sulfur-containing molecules (CHOS and CHONS) with contributions to the total intensity of assigned molecular formulas of up to 55% and 39%, respectively. On the other hand, O-related molecular markers were characterized by a significantly higher contribution of CHON formulas with 31% of the total intensity of assigned molecular formulas (28% for G) and lower contributions of sulfur-containing formulas, in particular CHOS (27% and 28% for CHOS and CHONS respectively). This result is in accordance with recent published data reporting the consumption of CHOS and the formation of CHON and CHONS compounds after controlled electrochemical simulation of oxidative reactions in white wine [Unsupervised PCA was initially conducted to obtain an overview of FT-ICR-MS data from wines exhibiting oxidative (O) or not (G) sensory characters. As shown in ite wine . Annotatite wine . However3H) and nitration (-NO3H) reactions, resulting good markers (The van Krevelen diagrams (H/C versus O/C) were generally used to identify the structural properties of molecular markers in FT-ICR-MS research, as only the molecular formula was given. Upon comparing the ratios of H/C and O/C for CHOS- and CHONS-containing compounds, products on the right-hand side of the van Krevelen diagram with higher O/C ratios, G samples allowed the highest number of oxygen atoms to support sulfonation  were referred to mass differences specific to nucleophilic addition reactions of some chemical families, including known phenols, sulfites (HSO3−), carbonyls, and amino acids—peptide compounds with unknowns in G-related molecular markers. In the presented compositional network, edges are colored according to the chemical families mentioned above. The clustering of G markers shows clearly that CHONS-containing compounds resulted from the sulfonation reaction essentially of amino acids and peptides, while CHOS-containing compounds are the reaction products of essentially polyphenol and carbonyl sulfonation reactions. Among connected masses, 172 were connected by targeted grape- and oak wood-derived polyphenols, 504 were connected to carbonyls, 310 were connected to sulfites, and 145 were connected to amino acid and peptides. In all targeted groups of chemical families, some of the selected masses exhibited very high connectivity (>10), thus suggesting its key role in wine’s oxidative stability during bottle aging. In detail, among targeted polyphenols, globally non-carboxyl monophenols, tyrosol, and hydroxytyrosol (formed during yeast fermentation from tyrosine), followed by main grape-derived phenolic acids  showed higher connectivity than flavanols (catechin and epicatechin).In order to give more insights into the chemical mechanisms implicated in wine’s oxidative stability during bottle aging, an alternative approach exploiting the exact mass information provided by FT-ICR-MS through the building of compositional networks was applied in the present study. Compositional networks enable mass coverage beyond classical annotations and thus the identification of unknowns. Exact mass from FT-ICR-MS data thus provides the chemical basis on which we can construct sample-related metabolic pathways in a data-driven network-based approach. By displaying data points as nodes that conditionally become connected (edges) to each other, networks have been proven ideal for efficient modeling and visualization of multivariate data . The tot3−), which possibly react with wine-relevant nucleophiles, mainly polyphenols, amino acids, sugars, keto acids, and other unknown compounds. The reactivity/behavior of HSO3− changes according to the metabolic environment, which changes constantly during aging. The few known sulfite binders are just the tip of the iceberg, and their presence can only partially explain the variability related to the binding strength of sulfites on different wines [Sulfonation reactions occur under wine’s acidic conditions from the very beginning of winemaking until/during bottle aging. In wine matrices (pH = 3.0–4.0), sulfites are present in the form of bisulfite ions  between measured and exact theoretical masses were calculated to support the compound identification. A total of 6 compounds corresponding to 164 nodes from the network were putatively identified as known analogues of polyphenols, carbonyls, and amino acids—peptide compounds with a very good error (Δppm < 1). Indeed, the unidentified masses at MS-grade methanol was obtained from Fisher Scientific  and ultrapure water (18.2 MΩ·cm) was obtained from a Milli-Q system .The experimental design included 20 chardonnay wines from five different vineyard plots located in Burgundy—North East France, from vintages of 2004 and 2005, produced according to standard winemaking procedures  and aged in oak wood barrels for nine months at the same winery. Wines were bottled after finning using natural cork and aged in cellar conditions. They were all analyzed in June 2015.A panel of six trained judges performed sensory analyses of the wines. All panelists had extensive experience in wine tasting and participated regularly in sensory panels with chardonnay wines. All of the assessments were performed at room temperature (18 ± 1 °C) in individual booths under daylight lighting. Fifty milliliters of wine were poured in standard ISO 3591 XL5-type tasting glasses with glass covers identified by three-digit random codes and assessed within 15 min of pouring. Each wine was submitted to the panelists just after the bottle was opened. They were asked to evaluate the presence or absence of oxidation flavors .m/z and 1000 m/z mass range in 2 MW FIDs and summed over 300 scans. All samples were analyzed randomly. The MS was first calibrated using arginine ion clusters (57 nmol/mL in methanol). Next, raw spectra were further internally calibrated using a reference list including known wine markers and ubiquitous fatty acids to achieve the best possible mass accuracy and precision among the samples [Analyses were realized using a Bruker SolariX Ion Cyclotron Resonance Fourier Transform Mass Spectrometer (FT-ICR-MS)  equipped with a 12 Tesla superconducting magnet  and an APOLO II ESI source  in negative ion mode. Samples were diluted at 1/20 into methanol and injected at flow rate of 120 µL/h into the electrospray. The broadband spectra were acquired between 147 p < 0.05), by a posteriori Duncan test. Differences between groups were considered significant when p < 0.05. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) were obtained with Perseus software  [m/z peaks) were filtered according to S/N higher than 10 and an absolute intensity above 2 × 106. Features alignment was made with the Matrix Generator software  with a mass accuracy window of 1 ppm and filtered to keep features present in 90% of samples. Elementary formula assignment of features was realized with in-house software NetCalc 2015  [Evaluation of statistical significance was conducted by one-way analysis of variance (ANOVA) followed, if significant (Germany) . The cluuenchen) . A visuauenchen) .In the present study, (-)ESI FT-ICR-MS-based metabolomics were combined with sensory analysis to characterize the chemical diversity of compounds related to white wine’s oxidative stability during bottle aging. Molecular markers of wine’s oxidative stability were first described by a specific CHONS chemical space in accordance with already published results indicating the increase in this specific molecular fingerprint during aging. Our findings based on the comparison of the ratios of H/C and O/C for CHOS- and CHONS-containing compounds evidenced that, in their majority, S-containing molecular features possessing O4∼12 number appeared to be related to the good state of aged wines, indicating the importance of sulfonation reactions instead of dimerization reactions on wine’s oxidative stability during aging. Moreover, molecular networking provided a more complete overview of the sulfonation molecular targets during wine aging. Indeed, based on sulfonation reaction transformations, we could report the importance of hitherto unknown and/or minor sulfur dioxide binders on wine’s oxidative stability.


Epitaxial growth, often termed “epitaxy”, is one of the most essential techniques underpinning semiconductor electronics, because crystallinities of the materials seriously dominate operation efficiencies of the electronic devices such as power gain/consumption, response speed, heat loss, and so on. In contrast to already well-established epitaxial growth methodologies for inorganic  semiconductors, studies on inter-molecular  epitaxy for organic semiconductors is still in the initial stage. In the present review paper, we briefly summarize recent works on the epitaxial inter-molecular junctions built on organic semiconductor single-crystal surfaces, particularly on single crystals of pentacene and rubrene. Experimental methodologies applicable for the determination of crystal structures of such organic single-crystal-based molecular junctions are also illustrated. Molecular beam epitaxy (MBE) is an established technique to produce high-quality crystalline thin films of conventional semiconductor materials and has been widely adopted from a lab scale to industrial processes [Semiconductor technologies have been developed at a synchronized pace with an advance in methodologies for the fabrication of semiconductor solids toward rocesses . In the rocesses .Regarding organic optoelectronics such as organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs), the performance of the devices is dominated not only by the molecular solids themselves but also by embedded interfaces between two molecular species of contrasting electronic characters, i.e., donors and acceptors, in other words, p-type and n-type organic semiconductors. In fact, the presence of donor–acceptor interfaces is essential as “p–n junctions” for practical OLED and OPV devices ,4, and uSingle-crystal surfaces can be used to construct well-defined model interfaces between organic semiconductors for the pursuit of molecular-scale understanding of the inter-molecular contacts. However, experimental studies to fabricate and characterize inter-molecular interfaces on molecular single-crystal surfaces were quite limited except for several pioneering works by Sassella et al. ,11 and YThis article is devoted to reviewing the recent works for the formation of well-ordered epitaxial molecular junctions by an MBE-like framework on organic semiconductor single-crystal substrates, particularly on single crystals of pentacene and rubrene, and to instruct experimental methodologies and know-hows for accurate determination of the crystallographic structures of the inter-molecular junctions using “third-generation” synchrotron radiation light source . In the next section, the essences of the experimental methods for the fabrication of the molecular single-crystal substrates and surface X-ray diffraction techniques on the molecular single-crystal samples are described. Epitaxial growth manners of three molecular species of different structural characteristics on the single crystal of pentacene are reviewed in Single-crystal samples of fine quality and high purity are preconditions for successful MBE. There are several methods for the fabrication of molecular single-crystal samples ,26. To sGrazing incidence X-ray diffraction (GIXD), often cited as grazing incidence wide-angle X-ray scattering (GIWAXS), is a technique to analyze crystal structures of thin films. In comparison to electron diffraction techniques such as low-energy electron diffraction (LEED) and reflection high-energy electron diffraction (RHEED), GIXD is a more applicable technique for “fragile” materials to electron beam irradiation and thus has been utilized in molecular or polymer semiconductors ,33 and rz with respect to the surface. A sudden drop of the reflectance at θz = 0.14° corresponds to the total-reflection critical angle of the Si wafer for the X-ray, while a small dip at θz = 0.105° can be attributed to that of the organic molecular film. For the sake of emphasizing the signal from the molecular thin films of typically several-tens nm-thick out of that from Si, an X-ray glancing angle that is shallower than the total-reflection critical angle of Si but is greater than that of organic thin films, for instance, 0.12°, is generally adopted for the GIXD measurements. The highly directional character of SR enables such precise control of the X-ray beam path. A typical experimental setup for the two-dimensional grazing incidence X-ray diffraction (2D-GIXD) technique is shown in 3 equipped with doubled Soller slits and an X-ray attenuator is generally used as a “zero-dimensional (0D)” X-ray detector. An analyzer crystal  and Si(111)) is additionally inserted in between the two slits for high-resolution grazing incidence X-ray diffraction (HR-GIXD) measurements using intense and highly aligned X-ray from undulator beamlines. It should be noted that the reciprocal lattice vector perpendicular to the surface is in principle not accessible by GIXD. Instead, the crystal structures in the surface normal direction have to be measured by θ–2θ scans which are in the same manner as standard X-ray diffraction (XRD) measurements along the surface normal direction. Such out-of-plane XRD measurements are capable of using an identical machine setup to GIXD  are presented in For the most results reviewed in this article, the GIXD experiments were performed at BL19B2 or BL46XU of SPring-8, Japan, unless otherwise noted. The X-ray energy and glancing angle were set at 12.4 keV and 0.12° from the surface plane, respectively. A 2D X-ray detector (PILATUS300K) was located at ca. 175 mm from the ϕ rotation center of the sample for the 2D-GIXD measurements. On the single-crystalline and/or epitaxial thin-film samples, 2D-GIXD patterns were collected by rotating ϕ by 360° for the identification of the in-plane crystallographic orientation of the sample. This is a kind of tomography that (in principle) enables full mapping of the interface diffraction patterns in the three-dimensional reciprocal space for single-crystalline samples. As an example, two constant-22H14: a = 0.593 nm, b = 0.756 nm, c = 1.565 nm, α = 98.6°, β = 93.3°, γ = 89.8°) [a = 0.6079 nm, b = 0.7893 nm, c = 1.478 nm, α = 83.20°, β = 79.92°, γ = 94.40°) [a = 0.6266 nm, b = 0.7775 nm, c = 1.453 nm, α = 76.475°, β = 87.682°, γ = 84.684°) [2V−1s−1 for its vapor-deposited thin films with uniaxially oriented polycrystallites in the thin-film phase [2V−1s−1 at 225 K [Pentacene C22H14: a, a typi= 89.8°) , bulk ph 94.40°) , and sin84.684°) . This malm phase . Furtherat 225 K ,47,48,49at 225 K ,51.60 fullerene  substrate at room temperature (RT) measured in vacuo (in situ) [60 assembled into table-like islands of very flat tops with mono-molecular steps, uniform heights, and straight rims commonly pointing to specific directions, suggesting good crystallinity. Out-of-plane XRD data exhibited clear peaks assignable to (111) and (222) reflections of C60 in its fcc phase as shown in 60-derived peak was accompanied by so-called Laue oscillation on both sides, which was already visible for the 5 nm-thick C60 thin films (60 formed (111)-oriented crystallite with a uniform out-of-plane coherent size on the PnSC surface. It is worth noting that AFM and XRD results on the samples after being taken out of the vacuum have confirmed that exposure to the ambient atmosphere and light did not induce any apparent structural change of this molecular heterojunction. All X-ray diffraction data presented hereafter were obtained from ex-situ measurements in the ambient conditions.in situ) . On the in films e. These 60 on PnSC was analyzed in detail by GIXD. 2D-GIXD images of a PnSC sample covered with a 20 nm-thick C60 film deposited at room temperature are shown in 60 q = ~, as shown in 60 made physisorption on the PnSC surface to maintain its bulk crystal structure, and any chemical reactions such as photooxidation of C60 [60 and pentacene [xyq, zq)~ in other directions ~ are plotted as a function of ϕ in 60 60 on the PnSC surface. These ϕ-dependencies are visualized in a polar plot for zq~0 nm−1  and the (001) surface of PnSC was concluded as shown in 60 molecules align in a direction (125.45 ± 0.3)° counterclockwise to the a-axis of PnSC, which corresponds to the [a-axis). A lattice point of the C60 (111) surface roughly overlaps with the PnSC 60 molecules aligned to the PnSC [60 crystallites were never detected. Another factor to be taken into consideration is the surface diffusion of ad-molecules on the surface, which takes place before the initial nucleation of the crystallites. Cantrell and Clancy predicted based on their molecular dynamics simulation results that the [60 diffusion on the PnSC (001) surface [By setting the sample orientation at ϕ where the PnSC  crystal . The int than 6% d. It is  instead e, any di surface . This su60 60 [60 deposited on a PnSC substrate at 300 K was 0.0466° as shown in 60 was estimated to be (125 ± 7) nm. Since this size is in very good agreement with the average grain size (123 nm) of C60/PnSC obtained by AFM  [60, pentacene and PFP tend to exhibit interdiffusion at their heterojunction due to the resemblance of their molecular structures [60, despite the striking difference in molecular and crystallographic symmetries each other, as briefly introduced below.Perfluoropentacene C22F14, a is know, 22H14) . Contrasructures ,68,69. H60/PnSC, and were determined by AFM and GIXD [a = 1.511 nm, b = 0.4490 nm, c = 1.1149 nm, α = γ = 90°, β = 91.567° [60 on PnSC.The structures of PFP adlayers on PnSC substrates were prepared in the same manner as the case of Cand GIXD . AFM imam0. On the other hand, valence bands of PnSC had also been measured by ARPES to reveal a moderate hole effective mass (approx. 3.5 m0) [An important characteristic of this epitaxial PFP/PnSC p–n junction is that the electronic band dispersion was demonstrated experimentally for both sides . The ene 3.5 m0) ,51. Thes14H8N4, Aza-substituted aromatic molecules have been of growing interest as a class of n-type small molecular semiconductors (acceptors) in recent years ,72,73,74zq~8.45 nm−1, which corresponds to the 020-reflection of the known bulk crystal structure of TANC . In addThe electronic structures of the epitaxial TANC/PnSC heterojunction were also studied by photoelectron spectroscopy (PES). Unlike the case of PFP grown on PnSC, a sharp profile of the TANC HOMO-derived PES peak suggested a small energy dispersion width. The energy offset between the HOMO levels across this epitaxial heterojunction was derived to be 1.75 eV. The LUMO level of TANC was supposed to be just above the Fermi level, which corroborated the favorable character of TANC as good n-type material and the topical heterojunction can actually be used as a p–n junction of crystalline organic semiconductors.60 on single-crystal rubrene as investigated by AFM, 2D-GIXD, and HR-GIXD.In this subsection, we summarize reports on the crystal structures and qualities of interfaces of C42H28: a = 2.69 nm, b = 0.718 nm, c = 1.44 nm [Rubrene C42H28: a is a re 1.44 nm , and the 1.44 nm . In othe60 has also been studied for a wide-variety of optoelectronic device applications [61-butyric acid methyl ester (PCBM), a derivative of C60, and the single-crystal rubrene especially in the low energy region [60 on polycrystalline rubrene thin films that photogeneration of the charge carriers can be enhanced by “band-like” delocalization of the excitonic states at the highly crystallized interfaces [60 on individual rubrene crystallites, detailed crystal structures of their heterojunction were hidden behind the polycrystalline nature of the rubrene substrates.The combination of rubrene and Cications ,94,95,96y region . While tterfaces . Althoug60 crystallites aligning on the rubrene single-crystal (100) surface studied by reflection high-energy electron diffraction (RHEED), AFM, and GIWAXS [60 films of greater single-crystalline domains. The out-of-plane XRD profiles indicated that C60 grew in the (111)-orientation on RubSCs. RHEED patterns suggested the epitaxial growth of C60 on RubSC, and indeed GIWAXS results exhibiting the C60-derived diffraction spots at specific azimuthal orientations also confirmed this notion. However, dissimilar to the aforementioned C60/PnSC case, the C60 60 (111) surface. This means that C60 grew in two different growth orientations on the RubSC surface. These results were also found almost at the same time by GIXD works conducted by Tsuruta and coworkers [60 60 thin films on a RubSC sample deposited at 300 K. The C60 Mitsuta et al. reported the epitaxial growth of Cd GIWAXS . They sy-crystal  surface 60 60 [6060 was evaluated to be about 125 nm independent of the domain orientation on the RubSC surface. This implies that adsorbed C60 molecules diffuse equally along crystallographically equivalent [Orientations of these two types of crystalline domains were accurately determined through HR-GIXD measurements using a Ge (111) analyzer crystal . The azi60 varied depending on the temperature of the RubSC substrates during the growth as shown in 60/PnSC case, C60 on RubSC exhibited a steeper increase in the mean crystallite size as the growth temperature was elevated. Hence, the crystallite size of C60 was larger than that of on-PnSC in the high-temperature region above room temperature, and actually, highly crystalline domains with a mean size up to 250 nm were obtained on RubSC. On the other hand, in the low-temperature region, the in-plane crystallite size shrunk more rapidly and it may converge to zero at a finite temperature above 0 K. At present, the reasons for this discrepancy in the growth temperature dependence of the mean crystallite size between the C60/RubSC and C60/PnSC heterojunctions. One plausible factor to be considered should be packing densities at the surfaces. Ends of molecular backbones that are prone to congregate densely are directly exposed to the top surface of PnSC (001), whereas the tetracene backbones of rubrene molecules are buried beneath the phenyl side groups pointing to the surface. Actually, the density of benzene rings per unit surface area is about 6% smaller for RubSC (3.869 nm−1) in comparison to that for PnSC (4.123 nm−1). This variation in the surface molecular packing may affect the surface diffusion of the C60 molecules via the difference in vigor of molecular vibration at the substrate surfaces.The in-plane mean crystallite size of C60 on PnSC is not realistic. One may recall orthodox doctrines for the epitaxial growth that minimization of a lattice-mismatch of an ad-grown material to a substrate crystal is a primary precondition for achieving a crystalline interface. Indeed, homoepitaxy, which in principle enables zero lattice-mismatch conditions between ad-layers and substrates, has succeeded in the fabrication of highly crystallized overlayers on metals and inorganic semiconductor materials [Even though the aforementioned heteroepitaxial systems have demonstrated considerably good crystallinities at the molecular interfaces, some constraints in their crystal qualities are implied at the same time; e.g., judging from the growth temperature dependence represented as aterials ,102,103.aterials . Rubreneaterials ,106, andaterials ,108,109.aterials .t 100 nm c. These hickness . Whereashickness ) of the 3 up to its ratio of 100 ppm [2V−1s−1) and significant dopant ionization rate (higher than 10%). Actually, the induction of holes at the valence band maximum was detected by high-sensitivity photoelectron yield spectroscopy (PYS) measurements. The combination of the accurate control of the ppm-level doping with the homoepitaxial growth of the single-crystalline organic semiconductors may lead to a new concept for an as-desired p/n switchover of high-mobility molecular semiconductors via the Fermi level tuning in the band gaps [AFM and GIXD results have confirmed that this excellent crystalline quality of the homoepitaxial rubrene was not substantially disturbed by doping of an inorganic acceptor material FeCl 100 ppm . The buland gaps ,109.In the previous subsection, it was introduced that homoepitaxial growth enables the formation of highly crystallized organic semiconductors with excellent coherent sizes of at least one order of magnitude greater than those of the heteroepitaxial molecular junctions. This concept can be adopted for the realization of single-crystalline organic semiconductor p–n homojunctions via bulk doping , just liAre there any good tricks to satisfy both the excellent crystallinity of homoepitaxial organic semiconductor thin films and an abrupt electronic energy level offset at hetero-molecular contacts? Inorganic semiconductors have been developed by finding solutions for this problem: that is, looking for favorable combinations of target materials with crystalline substrates with minimized lattice mismatches. In this context, di(trifluoromethyl)dimethylrubrene fmRub, a, a deriAn out-of-plane XRD profile of a RubSC sample covered with fmRub by 50 nm showed a spiky peak attributed to the fraction d. This izq ones of each. The fmRub-derived spots appeared only at specific azimuthal angles indicating the epitaxial growth of fmRub on RubSC. Actually, the azimuthal dependence of the GIXD profiles (b-axis perfectly parallel to the c-axis of RubSC. Based on the lattice constants derived from the GIXD peak positions, an inter-lattice relationship between fmRub and RubSC was derived to be profiles b reveale60 grown on RubSCs at RT was no narrower than 0.04° [It is noteworthy that this quasi-homoepitaxial molecular junction actually exhibited an improved crystallinity in comparison to the aforementioned heteroepitaxial cases. For instance, HR-GIXD 2θ scans revealed a fmRub an 0.04° . A microan 0.04° , which m60, PFP, and TANC, were revealed to grow in their own bulk crystal structures aligning each specific axis commonly to the PnSC [60, rubrene itself, and fmRub molecules, respectively. In particular, it was proposed that the quasi-homoepitaxial hetero-molecular junctions may be promising for the concomitance of superior crystal qualities, which potentially fulfills a requirement for the band transport and abrupt electronic energy levels without any depletion regions for the organic semiconductor p–n junctions. These systems are prominent examples of the van der Waals epitaxy driven by weak inter-molecular couplings instead of covalent or ionic bonding, and the interface structures are formed on delicate balances between both weak admolecule–admolecule and admolecule–substrate interactions.In this paper, recent works on epitaxial molecular junctions formed on two kinds of organic semiconductor single-crystal surfaces were reviewed. On the PnSC (Toward applications of the well-ordered epitaxial molecular p–n junctions to emerging electronic devices such as organic lasers ,115 and On the other hand, one of many benefits of organic semiconductor applications to their inorganic counterparts is their processability through low-cost and resource-saving manufacturing from their solutions. Indeed, single-crystalline organic semiconductor thin films have been reported to form in macroscopic scales ,148. Alt