Bilayer Adsorption of Porphyrin Molecules Substituted with Carboxylic Acid atop the NN4A Network Revealed by STM and DFT.

Bottom-up technology is a bridge connecting a two-dimensional (2D) monolayer structure with a three-dimensional (3D) bulk structure. From 2D to 3D, it helps us to understand the driving force of an organization process to control the molecular arrangement in the 3D phase. Here, we aimed at the fabrication of multilayer nanostructures on solid substrates. Bis(3,5-diacidic)diazobenzene (NN4A) was chosen as one molecule because of its photosensitive azo group and carboxylic group possessing hydrogen bonding effect, while porphyrin molecules composed of different numbers and positions of carboxylic acid groups were used as the other component. It was found that the porphyrin molecules could adopt different adsorption configurations because of the influence of carboxylic groups, leading to different subsequent coassemblies on the solid surface. The NN4A/porphyrin systems underwent structural transformation when NN4A molecules were adsorbed on the highly oriented pyrolytic graphite surface with predeposited porphyrin. This work displayed an efficient method on the construction of multilayer nanostructures in the molecular surface engineering and provided a new way to construct 3D structures based on the molecular design.

Surface Separation and in Situ Structural Regulation of Photosensitive Oligomer in a Flexible Template.

Surface-selective adsorption and separation are very important for the application of surface functional materials. In this study, a photosensitive diazo-macrocycle has been synthesized by the solvent method with a very low yield, which can adsorb onto the substrate surface modified with a template molecule. By using this flexible template on the graphite surface, a simple separation strategy for the macrocyclic molecule with specific shape and size from reaction mixtures was developed. Additionally, one of the two azo units in this trapped photosensitive macrocycle could convert from trans to cis conformation under UV irradiation due to the steric effect. Our results provide a new way to construct functional nanodevices using a surface flexible template as the separation and regulation medium.

Unravelling the Self-Assembly of Diketopyrrolopyrrole-Based Photovoltaic Molecules.

The nanostructure of bulk heterojunction in an organic solar cell dominating the electron transport process plays an important role in improving the device efficiency. However, there is still a great need for further understanding the local nanostructures from the viewpoint of molecular design because of the complex alignment in the solid film. In this work, four kinds of photovoltaic materials containing a diketopyrrolopyrrole (DPP) unit combined with other different building blocks were selected and their self-assembled structures on a solid surface were studied by scanning tunneling microscopy technique in combination with theory calculations. The results reveal these DPP-based photovoltaic molecules self-assembled into different nanostructures, which strongly depend on the chemical structure, in particular the backbones and alkyl side chains. The planarities of backbones are affected both by molecule-substrate interaction and steric hindrance induced by the substituted thiophene or benzo[ b]thiophene units on DPP and porphyrin building blocks. The substituted branched alkyl side chains are out of the plane, which are influenced by the alignments of molecular backbones. In addition, the solution concentration also shows a large effect on the self-assembled nanostructures. This systematic research on the self-assembled structures of DPP-based semiconductors on a surface would provide guidance for designing materials and controlling the morphology of a donor/acceptor heterojunction system.

Self-assemblies of TTF derivatives programmed by alkyl chains and functional groups.

Tetrathiafulvalenes (TTFs) are a class of important functional materials whose intermolecular interaction, which will contribute to constructing a supramolecular structure, still needs further understanding. In this study, the self-assembly behavior and structure of a series of TTFs bearing different alkyl chains and substituents were investigated by scanning tunneling microscopy (STM) in combination with density functional theory (DFT) calculations. Contrary to previous reports, herein, a series of benzoic acid-functionalized TTFs (CnTTFCOOH) and pyridine-functionalized TTFs (CnTTFN) with different lengths of alkyl chains have been substituted on the sulfur atom, where n is equal to 8, 10, 14, or 16. Due to the weak intra- and intermolecular interactions, CnTTFN (n = 8 and 10) molecules cannot be observed during STM scanning. For other cases, various self-assembled monolayers with different nanostructures were observed depending on different substituents. The results reveal that the alkyl chains and functional groups on the TTF skeleton synergistically affect the molecular self-assembly process, which results from the synergism of van der Waals, hydrogen bonding, and SS interactions. These results not only help to explain the relationship between structures and properties, but also help to design better molecular structures for various fields.

On-Surface Synthesis of Self-Assembled Monolayers of Benzothiazole Derivatives Studied by STM and XPS.

On-surface synthesis has gradually become a prevalent approach to constructing two-dimensional functional monolayers on various substrates. In the present work, the synthesis of self-assembled monolayers (SAMs) of benzothiazole derivatives was conducted at the liquid/solid interface for the first time. Two kinds of nanostructures were achieved on the highly oriented pyrolytic graphite (HOPG) surface via the condensation reaction between aromatic aldehyde derivatives and 2-aminothiophenol (ATP). The formation of thiazole-based self-assemblies was revealed by scanning tunneling microscopy (STM) and further confirmed by X-ray photoelectron spectroscopy (XPS). The successful synthesis of the benzothiazole derivatives not only extends the scope of on-surface reactions but also can be applied in designing multifunctional SAMs at the interface.

Two-dimensional (2D) self-assembly of oligo(phenylene-ethynylene) molecules and their triangular platinum(ii) diimine complexes studied using STM.

In this investigation, the two-dimensional (2D) self-assembly nanostructures of a series of cyclic oligo(phenylene-ethynylene) (OPE) molecules (L1, L2-6 and L2-12) at the 1-phenyloctane/highly oriented pyrolytic graphite (HOPG) interface were thoroughly studied using scanning tunneling microscopy (STM). Comparative STM studies with their triangular Pt(ii) diimine complexes (C1, C2-6 and C2-12) were also carried out. Based on careful measurements on single molecule level STM images and density functional theory (DFT) calculations, the formation mechanisms of the nanoarrays formed were revealed.

STM analysis of surface-adsorbed conjugated oligo(p-phenylene-ethynylene) (OPE) nanostructures.

The nanostructures of a series of conjugated oligo(p-phenylene-ethynylene)s (OPE) adsorbed on a surface were thoroughly studied using scanning tunneling microscopy (STM). These oligomers have different backbone lengths and side chains. As a result, various nanostructures displaying periodic linear patterns at a single molecule level were obtained. Based on careful measurements on the STM images in combination with density functional theory (DFT) calculations, it could be found that the vertical and parallel distances between neighboring oligomers were responsible for the specific arrangement of the backbone and side chains. The results showed that these molecular designs strongly affect their self-assembled structure, which is important to clarify the structure-property relationship in the nanoscience field.

Study of the Edge-on Self-Assembly of Axially Substituted Silicon(IV) Phthalocyanine Derivatives in a Template on the HOPG Surface.

Molecular conformation is an important issue related to the self-assembly architecture and property. The self-assembly of silicon(IV) phthalocyanines covalently linked to the 5-N-cytidine or 4-carboxyphenoxy moiety at the axial positions, namely, SiPc(NC)2 and SiPc(CP)2, respectively, has been studied by means of scanning tunneling microscopy (STM) at the solid-liquid interface. The intermolecular axial hydrogen bonding in combination with the stabilizing role of the TCDB template brings about supramolecular self-assembled structures of silicon(IV) phthalocyanines in an edge-on orientation. Two pyridine compounds, 4,4'-bipyridine (BPY) and 1,2-di(4-pyridyl)ethylene (DPE), can tune the supramolecular structure, leading to interestingly axial self-assemblies of SiPc(CP)2 with BPY and DPE in an edge-on manner by hydrogen bonding. The results indicate that the axial substituents and the axial ligands can regulate and precisely control the conformation and arrangement of the phthalocyanine moiety on the graphite surface.

Orthogonal Supramolecular Polymer Formation on Highly Oriented Pyrolytic Graphite (HOPG) Surfaces Characterized by Scanning Probe Microscopy.

Formation of an orthogonal supramolecular polymer on a highly oriented pyrolytic graphite (HOPG) surface was demonstrated for the first time by means of scanning probe microscopy (SPM). Atomic force microscopy (AFM) was employed to characterize the variation of both the thickness and the topography of the film formed from (1) monomer 1, (2) monomer 1/Zn(2+), and (3) monomer 1/Zn(2+)/cross-linker 2, respectively. Scanning tunneling microscopy (STM) was used to monitor the self-assembly behavior of monomer 1 itself, as well as 1/Zn(2+) ions binary system on graphite surface, further testifying for the formation of linear polymer via coordination interaction at the single molecule level. These results, given by the strong surface characterization tool of SPM, confirm the formation of the orthogonal polymer on the surface of graphite, which has great significance in regard to fabricating a complex superstructure on surfaces.

Solvent-induced variable conformation of bis(terpyridine) derivatives during supramolecular self-assembly at liquid/HOPG interfaces.

Variable supramolecular structures constructed by bis-(2,2':6',2''-terpyridine)-4'-oxyhexadecane (BT-O-C16) on a highly oriented pyrolytic graphite (HOPG) surface were investigated by scanning tunneling microscopy (STM). Seven different solvents (1-phenyloctane, n-tetradecane, n-dodecane, n-decane, n-octane, 1-heptanoic acid, and 1-octanoic acid) were utilized to affect the self-assembling structures of BT-O-C16 at liquid/HOPG interfaces. High-resolution STM analyses revealed that various nanostructures were formed by the change of molecular conformation, which are actually driven by the cooperative interaction effect under different environments. Therefore, the solvent-induced cooperative influence on the molecular self-assembly is important for constructing supramolecular nanostructures.

Control of Multi-Fluorination Number and Position in D-π-A Type Polymers and Their Impact on High-Voltage Organic Photovoltaics.

Exploring the structure-performance relationship of high-voltage organic solar cells (OSCs) is significant for pushing material design and promoting photovoltaic performance. Herein, we chose a D-π-A type polymer composed of 4,8-bis(thiophene-2-yl)-benzo[1,2-b:4,5-b']dithiophene (BDT-T) and benzotriazole (BTA) units as the benchmark to investigate the effect of the fluorination number and position of the polymers on the device performance of the high-voltage OSCs, with a benzotriazole-based small molecule (BTA3) as the acceptor. F00, F20, and F40 are the polymers with progressively increasing F atoms on the D units, while F02, F22, and F42 are the polymers with further attachment of F atoms to the BTA units based on the above three polymers. Fluorination positively affects the molecular planarity, dipole moment, and molecular aggregations. Our results show that VOC increases with the number of fluorine atoms, and fluorination on the D units has a greater effect on VOC than on the A unit. F42 with six fluorine atom substitutions achieves the highest VOC (1.23 V). When four F atoms are located on the D units, the short-circuit current (JSC) and fill factor (FF) plummet, and before that, they remain almost constant. The drop in JSC and FF in F40- and F42-based devices may be attributed to inefficient charge transfer and severe charge recombination. The F22:BTA3 system achieves the highest power conversion efficiency of 9.5% with a VOC of 1.20 V due to the excellent balance between the photovoltaic parameters. Our study provides insights for the future application of fluorination strategies in molecular design for high-voltage organic photovoltaics.

The Development of Quinoxaline-Based Electron Acceptors for High Performance Organic Solar Cells.

In the recent advances of organic solar cells (OSCs), quinoxaline (Qx)-based nonfullerene acceptors (QxNFAs) have attracted lots of attention and enabled the recorded power conversion efficiency approaching 20%. As an excellent electron-withdrawing unit, Qx possesses advantages of many modifiable sites, wide absorption range, low reorganization energy, and so on. To develop promising QxNFAs to further enhance the photovoltaic performance of OSCs, it is necessary to systematically summarize the QxNFAs reported so far. In this review, all the focused QxNFAs are classified into five categories as following: SM-Qx, YQx, fused-YQx, giant-YQx, and polymer-Qx according to the molecular skeletons. The molecular design concepts, relationships between the molecular structure and optoelectronic properties, intrinsic mechanisms of device performance are discussed in detail. At the end, the advantages of this kind of materials are summed up, the molecular develop direction is prospected, the challenges faced by QxNFAs are given, and constructive solutions to the existing problems are advised. Overall, this review presents unique viewpoints to conquer the challenge of QxNFAs and thus boost OSCs development further toward commercial applications.

Effect of Number and Position of Chlorine Atoms on the Photovoltaic Performance of Asymmetric Nonfullerene Acceptors.

It has been well proved that the introduction of halogen can effectively modify the optoelectronic properties of classic symmetric nonfullerene acceptors (NFAs). However, the relevant studies for asymmetric NFAs are limited, especially the effect of halogen substitution number and position on the photovoltaic performance is not clear. In this work, four asymmetric NFAs with A-D-A1-A2 structure are developed by tuning the number and position of chlorine atoms on the 1,1-dicyanomethylene-3-indanone end groups, namely, A303, A304, A305, and A306. The related NFAs show progressively deeper energy levels and red-shifted absorption spectra as the degree of chlorination increases. The PM6:A306-constructed organic solar cells (OSCs) give a champion power conversion efficiency (PCE) of 13.03%. This is mainly ascribed to the most efficient exciton dissociation and collection, suppressed charge recombination, and optimal morphology. Moreover, by alternating the substitution position, the PM6:A305-based device yielded a higher PCE of 12.53% than that of PM6:A304 (12.05%). This work offers fresh insights into establishing excellent asymmetric NFAs for OSCs.

Tell me your position: Distantly supervised biomedical entity relation extraction using entity position marker.

A significant amount of textual data has been produced in the biomedical area recently as a result of the advancement of biomedical technologies. Large-scale biomedical data can be automatically obtained with the help of distant supervision. However, the noisy data brought by distant supervision methods makes relation extraction tasks more difficult. Previous work has focused more on how to restore mislabeled relationships, but little attention has been paid to the importance of labeled entity locations for relationship extraction tasks. In this paper, we present a "four-stage" model based on BioBERT and Multi-Instance Learning by using entity position markers. Firstly, the sentence is marked with position. Secondly, BioBERT, a biomedical pre-trained language model, is used in the final sentence feature vector representation not only with the global position marker but also with the start and end marker of both the head and tail entity. Thirdly, the aggregation of sentence vectors in the bag is used as the vector feature of the bag by three aggregation methods, and the performance of different sentence feature vectors combined with different bag encoding methods is discussed. At last, relation classification is performed at the bag level. According to experimental results, the presented model significantly outperforms all baseline models and contributes to noise reduction. In addition, different bag encoding methods need to match corresponding sentence encoding representation to achieve the best performance.

Tailoring organic heterojunction interfaces in bilayer polymer photovoltaic devices.

In an ideal model, a p-n junction is formed by two stacked slabs of semiconductors. Although the construction of actual devices is generally more complex, we show that such a simple method can in fact be applied to the formation of organic heterojunctions. Two films of the organic semiconductors poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) can be connected by a simple film-transfer method without disturbing their flat surfaces. Each film can further be modified with a surface-segregated monolayer to tune the strength and direction of the surface dipole moment. Using this method, we fabricated bilayer organic photovoltaic devices with interfacial dipole moments that were selected to align the energy levels at the heterojunction. The open-circuit voltages of the P3HT/PCBM devices could be tuned over a wide range between 0.3 and 0.95 V, indicating that, even if the same combination of bulk materials is used, the interfacial properties drastically alter the performance of organic photovoltaic devices.

Interfacial modification of organic photovoltaic devices by molecular self-organization.

This feature article focuses on the relationship between the interfacial structures constructed by molecular self-organization and the properties of organic photovoltaic devices. The use of self-assembled monolayers (SAMs) is reviewed for metal and metal oxide/organic interfaces, while surface-segregated monolayers (SSMs) are introduced as a new method for the modification of organic/organic interfaces. Research up to now has clearly demonstrated the effectiveness of the control of energy levels and other properties at the interfaces to enhance photovoltaic performance. The possibility of more precise control of the interfacial structures is also discussed.

Synthesis and characterizations of regioregular poly(3-alkylthiophene) with alternating dodecyl/1H,1H,2H,2H-perfluorooctyl side chains.

A regioregular poly[4'-dodecyl-3-(1H,1H,2H,2H-perfluorooctyl)-2,2'-bithiophene] (P3DDFT) with alternating alkyl and semifluoroalkyl side chains were synthesized. Short ethylene spacer between perfluorohexyl part and thiophene did not largely affect the absorption and emission properties of the polythiophene backbone in comparison with poly(3-dodecylthiophene) (P3DDT). P3DDFT showed a larger onset of the oxidation potential (+0.17 V) observed by cyclic voltamogram due to the electron withdrawing effect of the fluoroalkyl part. Thermal analysis and X-ray diffraction patterns indicated that P3DDFT in the solid state forms a semicrystalline lamellar structure that is similar to that of P3DDT. Ultraviolet photoemission spectroscopy was also used to investigate their electron structure in the films. Comparison of hole mobilities in the films suggested that P3DDFT could have a less ordered packing structure compared to P3DDT both in the bulk and at the dielectric interface.

Early Diagnosis of Brain Injury in Premature Infants Based on Amplitude-Integrated EEG Scoring System.

Analyzing and discussing the relationship between brain injury in preterm infants and related risk factors can provide evidence for perinatal prevention and early intervention of brain injury in preterm infants, thereby improving the quality of life of preterm infants. This paper selects term preterm infants diagnosed with preterm infant asphyxia in the NICU of a university's First Affiliated Hospital from January 2018 to February 2019 as the research object. In addition, healthy term infants born at the same time in the obstetric department of this hospital are selected as the control group. Both groups of premature infants were monitored for brain function within 6 hours after birth. The aEEG results range from background activity (continuous normal voltage, discontinuous normal voltage, burst suppression, continuous low voltage, and plateau) and sleep-wake cycle (no sleep-wake cycle, immature, and mature sleep-wake cycle) to epileptic activity (single seizures, recurrent seizures, and status epilepticus), three aspects to judge. Statistical analysis uses SPSS 17.0 software. Amplitude-integrated EEG is a simplified form of continuous EEG recording. The trace of the trace represents the voltage change signal of the entire EEG background activity, which can reflect the EEG amplitude, frequency, burst-inhibition, and other pieces of information. aEEG can reflect the degree of HIE lesions in premature infants and the long-term prognosis. It is easy to operate and effective in diagnosis and can be continuously monitored. It is worthy of clinical popularization. There is a good correlation between the expression of EEG and biomarkers. Combining multiple methods can diagnose HIE earlier and evaluate the prognosis.

Fabrication of High VOC Organic Solar Cells with a Non-Halogenated Solvent and the Effect of Substituted Groups for "Same-A-Strategy" Material Combinations.

We report a class of high-voltage organic solar cells (OSCs) processed by the environmentally friendly solvent tetrahydrofuran (THF), where four benzotriazole (BTA)-based p-type polymers (PE31, PE32, PE33, and J52-Cl) and a BTA-based small molecule BTA5 are applied as p-type and n-type materials, respectively, according to "Same-A-Strategy" (SAS). The single-junction OSCs based on all four material blends exhibit a high open-circuit voltage (VOC) above 1.10 V. We systematically study the impact of the three different substituents (-OCH3, -F, -Cl) on the BTA unit of the polymer donors. Interestingly, PE31 containing the unsubstituted BTA unit shows the efficient hole transfer and more balanced charge mobilities, thus leading to the highest power conversion efficiency (PCE) of 10.08% with a VOC of 1.11 V and a JSC of 13.68 mA cm-2. Due to the upshifted highest electron-occupied molecular orbital (HOMO) level and the weak crystallinity of the methoxy-substituted polymer PE32, the resulting device shows the lowest PCE of 7.40% with a slightly decreased VOC of 1.10 V. In addition, after the chlorination and fluorination, the HOMO levels of the donor materials PE33 and J52-Cl are gradually downshifted, contributing to increased VOC values of 1.16 and 1.21 V, respectively. Our results prove that an unsubstituted p-type polymer can also afford high voltage and promising performance via non-halogenated solvent processing, which is of great significance for simplifying the synthesis steps and realizing the commercialization of OSCs.

Tricyclic or Pentacyclic D Units: Design of D-π-A-Type Copolymers for High VOC Organic Photovoltaic Cells.

Although there are several electron-donating (D) units, only the classic benzo[1,2-b:4,5-b']dithiophenes (BDT) unit was utilized to develop D-π-A-type copolymers for high-voltage organic photovoltaic (OPV) cells. Hence, in this work, we chose two tricyclic D units, BDT and benzo[1,2-b:4,5-b']difurans (BDF), together with one pentacyclic ring, dithieno[2,3-d;2',3'-d']benzo[1,2-b;4,5-b']dithiophenes (DTBDT), to comprehensively study the effect of different D units on the optoelectronic properties and photovoltaic performance. By copolymerized with the benzo[1,2,3]triazole (BTA) electron-accepting unit, the final copolymers J52-Cl, F11, and PE52 were combined with a nonfullerene acceptor (NFA) F-BTA3 according to the "Same-A-Strategy." As we preconceived, all the three single-junction OPV cells can obtain high open-circuit voltage (VOC) over 1.10 V. Although the tricyclic D unit of BDF exhibits a slightly lower VOC of 1.12 V because of its mildly larger energy loss of 0.698 eV, its higher carrier mobilities and exciton dissociation efficiency strikingly boost the short-circuit current (JSC) and fill factor, which contribute to a comparable PCE of 10.04% with J52-Cl (10.10%). However, the DTBDT-based polymer PE52 shows the worst performance with a PCE of 6.78% and a VOC of 1.14 V, owing to the higher bimolecular recombination and disordered molecular stacking. Our results indicate that tricyclic D units should be a better choice for constructing D-π-A-type polymers for high-voltage photovoltaic materials than the pentacyclic analogues.