Cyclization Engineering of Electron-Deficient Maleimide Unit for Nonfused Ring Electron Acceptors Enables Efficient Organic Solar Cells.

Nonfused ring electron acceptors (NFREAs) have emerged as promising materials for commercial applications in organic solar cells due to their straightforward synthesis process and cost-effectiveness. The rational design of their structural frameworks is crucial for enhancing device efficiency. In this study, we explore the use of maleimide and thiophene as key building blocks, employing cyclization engineering techniques. Additionally, cyclopentanedithiophene was chosen as the bridging unit, coupled with fluorinated terminals, to fabricate NFREAs, namely, PI-DTS and DPI-DTS. DPI-DTS demonstrated superior molecular planarity and an upshifted lowest unoccupied molecular orbital energy level. Moreover, DPI-DTS-based blend films display enhanced π-π interactions and crystallinity, alongside a predominantly face-on orientation. Consequently, DPI-DTS-based devices displayed enhanced and more balanced carrier mobility, reduced bimolecular recombination, and trap-assisted recombination, leading to improved charge transfer efficiency. Ultimately, this led to an excellent efficiency of 10.48%, with an open-circuit voltage as high as 0.914 V. These findings highlight the significant promise of aromatic imides in constructing NFREAs, and the established structure-performance relationship provides a theoretical basis for the design of high performance NFREAs.

Tuning the planarity of molecularly imprinted covalent organic frameworks for selective extraction of ochratoxin A in alcohol samples.

Here, we report a monomer planarity modulation strategy for room-temperature constructing molecularly imprinted-covalent organic frameworks (MI-COFs) for selective extraction of ochratoxin A (OTA). 2,4,6-triformylphloroglucinol (Tp) was used as basic building block, while three amino monomers with different planarity were employed as modulators to explore the effect of planarity on the selectivity of MI-COFs. The MI-TpTapa constructed from Tp and the lowest planarity of monomer Tapa gave the highest selectivity for OTA, and was further used as the adsorbent for dispersed-solid phase extraction (DSPE) of OTA in alcohol samples. Coupling MI-TpTapa based DSPE with high-performance liquid chromatography allowed the matrix-effect free determination of OTA in alcohol samples with the limit of detection of 0.023 µg kg-1 and the recoveries of 91.4-97.6%. The relative standard deviation (RSD, n = 6) of intra and inter day was <3.2%. This work provides a new way to construct MI-COFs for selective extraction of hazardous targets.

Design of Novel Functional Conductive Structures and Preparation of High-Hole-Mobility Polymer Transistors by Green Synthesis Using Acceptor-Donor-Acceptor Strategies.

The design of novel acceptor molecular structures based on classical building blocks is regarded as one of the efficient ways to explore the application of organic conjugated materials in conductivity and electronics. Here, a novel acceptor moiety, thiophene-vinyl-diketopyrrolopyrrole (TVDPP), was envisioned and prepared with a longer conjugation length and a more rigid structure than thiophene-diketopyrrolopyrrole (TDPP). The brominated TVDPP can be sequentially bonded to trimethyltin-containing benzo[c][1,2,5]thiadiazole units via Suzuki polycondensation to efficiently prepare the polymer PTVDPP-BSz, which features high molecular weight and excellent thermal stability. The polymerization process takes only 24 h and eliminates the need for chlorinated organic solvents or toxic tin-based reagents. Density functional theory (DFT) simulations and film morphology analyses verify the planarity and high crystallinity of the material, respectively, which facilitates the achievement of high carrier mobility. Conductivity measurements of the polymeric material in the organic transistor device show a hole mobility of 0.34 cm2 V-1 s-1, which illustrates its potential for functionalized semiconductor applications.

Quantification of Slip Band Distribution in Polycrystals: An Automated Fast Fourier Transform Decomposition Approach.

Plastic deformation is accumulated in slip bands in a wide variety of engineering alloys. Multiple material and loading conditions impact their distribution and degree of slip localization, but these effects are rarely quantified. To tackle this, the current work introduces a fast Fourier transform (FFT) decomposition method and applies it to a tensile-loaded polycrystalline nickel-based superalloy imaged via high-resolution digital image correlation and electron backscatter diffraction. This approach identifies active slip planes over the FFT images of individual grains and performs inverse transforms such that slip band traces with shared orientations are isolated. This technique enabled the largest quantification of slip band spacings and in-plane strains to date, with a total of 6,557 slip bands detected. The results show that the slip band spacings increase with grain size, with no evident dependence on grain orientation and Schmid factor. Slip bands are found to develop similar spacings along different octahedral planes and continue to spread over larger regions of the grain as the resolved shear stress of the active slip system increases. The FFT decomposition technique, which could be employed with multiple microscopy techniques, will allow for much-needed large-scale quantitative studies of slip localization.

Site-specific relaxation of peptide bond planarity induced by electrically attracted proton/deuteron observed by neutron crystallography.

In structural biology, peptide bonds, fundamental linkages between hundreds of amino acids, of which a protein molecule is composed, have been commonly treated as a plane structure just as Linus Pauling et al. proposed. In this paper, a site-specific peptide bond relaxation mechanism by deuterons whose localization has been suggested by neutron crystallography is proposed. Such deuteron was observed as an arm of neutron scattering length density protruding from the carbonyl oxygen atoms in the main chain in the omit map drawn by neutron crystallography of human lysozyme. Our comprehensive study using x-ray and neutron diffraction and 15 N chemical shifts of individual amide nitrogen atoms within the same peptide bond strongly suggests the relaxation of the electronic resonance structure because of site-specific modulation by protons/deuterons localized on the electron orbital of the carbonyl oxygen. All experimental data used in this examination were obtained at room temperature, which is preferable for enzymatic activity. Such a close interaction between the electron resonance structure of a peptide bond and the exchangeable protons/deuterons well agreed with that observed in an intermediate state in an amide hydrolytic reaction simulated by the ab-initio calculation including water molecules.

Atomistic Study of the Effect of Hydrogen on the Tendency toward Slip Planarity in Bcc Iron.

H-enhanced slip planarity is generally explained in terms of H-reducing stacking fault energy in fcc systems. Here, we showed that H-decreasing dislocation line energies can enhance the tendency toward slip planarity in bcc Fe through systematically studying the interaction between H and 1/2 <111> {110} dislocations using the EAM potential for Fe-H systems. It was found that the binding energy of H, the excess H in the atmosphere, and the interaction energy of H increased with edge components, leading to larger decrements in the line energies of the edge and increased mixed dislocations than those of a screw dislocation. The consequence of such interaction patterns is an increment in the energy change in the system when the edge and mixed dislocations are converted to screw dislocations as compared to the H-free cases. The cross-slip in bcc Fe is thus suppressed by H, increasing the tendency toward slip planarity.

Physical Mechanism of One-Photon Absorption, Two-Photon Absorption, and Electron Circular Dichroism of 1,3,5 Triazine Derivatives Based on Molecular Planarity.

We provide a method to regulate intramolecular charge transfer (ICT) through distorting fragment dipole moments based on molecular planarity and intuitively investigate the physical mechanisms of one-photon absorption (OPA), two-photon absorption (TPA), and electron circular dichroism (ECD) properties of the multichain 1,3,5 triazine derivatives o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ containing three bromobiphenyl units. As the position of the C-Br bond on the branch chain becomes farther away, the molecular planarity is weakened, with the position of charge transfer (CT) on the branch chain of bromobiphenyl changing. The excitation energy of the excited states decreases, which leads to the redshift of the OPA spectrum of 1,3,5-triazine derivatives. The decrease in molecular plane results in a change in the magnitude and direction of the molecular dipole moment on the bromobiphenyl branch chain, which weakens the intramolecular electrostatic interaction of bromobiphenyl branch chain 1,3,5-triazine derivatives and weakens the charge transfer excitation of the second step transition in TPA, leading to an increase in the enhanced absorption cross-section. Furthermore, molecular planarity can also induce and regulate chiral optical activity through changing the direction of the transition magnetic dipole moment. Our visualization method helps to reveal the physical mechanism of TPA cross-sections generated via third-order nonlinear optical materials in photoinduced CT, which is of great significance for the design of large TPA molecules.

Molecular Structure and Conformational Design of Donor-Acceptor Conjugated Polymers to Enable Predictable Optoelectronic Property.

Tuning the optoelectronic properties of donor-acceptor conjugated polymers (D-A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D-A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D-A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D-A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.

Hydrodynamic simulation of hypervelocity generation by multidimensional graded impactors: Planarity enhancement study.

Hypervelocity impact in the universe can be generated by a three-stage gas gun. Achieving the desirable planarity of the flyer enlarges the experimentally effective area of the flyer under the hypervelocity condition. The multidimensional graded density impactor (MDGDI) enhances the planarity of the flyer. In this investigation, a one-dimensional Lagrange elastoplastic hydrodynamic method and a Euler grid finite difference method were used to examine the relationship between the structure of graded density impactors (GDIs) and the planarity of flyers. MDGDIs lead to a deviation of the stress wave produced by the one-dimensional graded density impactor (1DGDI), which offsets the stress disturbance effect, changes the velocity at each particle, and enhances the planarity of flyers. The proportion of flat areas of the flyer increases from 52.70% to 95.71% by adopting MDGDIs. The proportion of flat areas is linear with the wave impedance of the high-impedance layer for 1DGDIs and the wave impedance near the barrel of the high-impedance layer for MDGDIs. This investigation guides the design of GDIs and expands the application of gas gun technology in the field of hypervelocity impact.

Large Steric Hindrance Enhanced Molecular Planarity for Low-Cost Non-Fused Electron Acceptors.

Designing efficient non-fused ring electron acceptors is of great importance in decreasing the material cost of organic photovoltaic cells (OPVs). It is a challenge to construct a planar molecular skeleton in non-fused molecules as there are many torsions between adjacent units. Here, we design two non-fused electron acceptors based on bithieno[3,2-b]thiophene units as core structures and study the impact of steric hindrance of substituents on molecular planarity. We use 2,4,6-triisopropylphenyl and 4-hexylphenyl groups to prepare ATTP-1 and ATTP-2, respectively. Our results suggest that the enhanced steric hindrance is beneficial for obtaining a more planar molecular configuration, which significantly increases the optical absorption and charge transport properties. The power conversion efficiency (PCE) of PBDB-TF:ATTP-1 combination (11.3%) is superior to that of PBDB-TF:ATTP-2 combination (3.7%). In addition, an impressive PCE of 10.7% is recorded in ATTP-1-based devices when a low-cost polythiophene donor PDCBT is used, which is an outstanding value in OPVs fabricated by non-fused donor/acceptor combinations. Our work demonstrates that modulation of the steric hindrance effect is of great significance to control the molecular planarity and thus obtain excellent photovoltaic performance of low-cost non-fused electron acceptors.

Increasing Molecular Planarity through Donor/Side-Chain Engineering for Improved NIR-IIa Fluorescence Imaging and NIR-II Photothermal Therapy under 1064†nm.

Developing conjugated small molecules (CSM) with intense NIR-II (1000-1700 nm) absorption for phototheranostic is highly desirable but remains a tremendous challenge due to a lack of reliable design guidelines. This study reports a high-performance NIR-II CSM for phototheranostic by tailoring molecular planarity. A series of CSM show bathochromic absorption extended to the NIR-II region upon the increasing thiophene number, but an excessive number of thiophene results in decreased NIR-IIa (1300-1400 nm) brightness and photothermal effects. Further introduction of terminal nonconjugated alkyl chain can enhance NIR-II absorption coefficient, NIR-IIa brightness, and photothermal effects. Mechanism studies ascribe this overall enhancement to molecular planarity stemming from the collective contribution of donor/side-chain engineering. This finding directs the design of NIR-II CSM by rational manipulating molecular planarity to perform 1064 nm mediated phototheranostic at high efficiency.

Impact of end-group modifications and planarity on BDP-based non-fullerene acceptors for high-performance organic solar cells by using DFT approach.

With the aim to enhance the photovoltaic properties of organic solar cells (OSCs), seven new non-fullerene acceptors (K1-K7) have been designed by end-group modifications of benzo[2,1-b:3,4-b']bis(4H-dithieno[3,2-b:2',3'-d]pyrrole) (BDP)-based small molecule "MH" (which is taken as our reference R) using computational techniques. To investigate their various optoelectronic parameters, DFT studies were applied using the B3LYP functional at 6-31G (d, p) basis set. The measurement of molecular planarity parameter (MPP) and span of deviation from plane (SDP) confirmed the planar geometries of these structures resulting in enhanced conjugation. Frontier molecular orbital (FMO) and density of states (DOS) analyses confirmed shorter band gaps of K1-K7 as compared to R, which promotes charge transfer in them. Optical properties demonstrated that these compounds have absorption range from 692 to 711 nm, quite better than the 684 nm of reference R. Molecular electrostatic potential (MEP) and Mulliken' charge distribution analysis also revealed the presence of epic charge separation in these structures. K1-K7 showed enhanced LHE values as compared to R putting emphasis on their better abilities to produce charge carrier by absorption of light. Reorganization energies showed that all newly designed compound could have better rate of charge carrier mobility (except K4) than R. Calculations of open-circuit voltage (Voc) and fill factor (FF) revealed its highest values for K3 and K4. Among newly designed molecules, K3 showed betterment in all its investigated parameters, making it a strong candidate to get enhanced power conversion efficiencies of OSCs.

[Features of vectorcardiograms in patients with hypertension complicated by chronic heart failure with reduced left ventricle ejection fraction].

AIM: To explore the features of vectorcardiograms (VCG) of patients with essential hypertension complicated by chronic heart failure with reduced left ventricular ejection fraction (CHFrLVEF). MATERIALS AND METHODS: We analyzed VCGs of 70 hypertensive patients with CHFrLVEF and 275 hypertensive patients without clinical signs of CHF and with LVEF50%. We assessed the presence of rhythm and conduction disturbances, and the parameters of the synthesized VCG, i.e., module of the maximum QRS vector, planarity index of the spatial QRS loop (P/S), and spatial angle between the integral QRS and T vectors (sQRS-Ta). RESULTS: In hypertensive patients with CHF, certain conditions were detected more often as compared with hypertensive patients without CHF, i.e., atrial fibrillation (AF) in 52.9% vs 5.1%; p0.0001, and left bundle branch block (LBBB) in 38.6% vs 0.4%; p0.0001. The module of the maximum QRS vector and sQRS-Ta were significantly greater and P/S was significantly less in VCGs of patients with CHF. ROC-analysis showed that the presence of AF and LBBB just as VCG parameters assessed in this study provide clear discrimination between hypertensive patients with or without CHF both in the group as a whole and in the subgroups (1) without LBBB, (2) with sinus rhythm, and (3) with AF. sQRS-Ta was the most informative parameter (threshold 137, sensitivity 91%, specificity 92%). The P/S indicator at the optimal threshold value 0.92 was characterized by lower specificity (68%) with rather high sensitivity (79%). CONCLUSION: AF, LBBB, increased module of the maximum QRS vector and sQRS-Ta, and decreased P/S index are present in hypertensive patients with CHFrLVEF as compared with patients without CHF.

Extending Goldberg's method to parametrize and control the geometry of Goldberg polyhedra.

Goldberg polyhedra have been widely studied across multiple fields, as their distinctive pattern can lead to many useful applications. Their topology can be determined using Goldberg's method through generating topologically equivalent structures, named cages. However, the geometry of Goldberg polyhedra remains underexplored. This study extends Goldberg's framework to a new method that can systematically determine the topology and effectively control the geometry of Goldberg polyhedra based on the initial shapes of cages. In detail, we first parametrize the cage's geometry under specified topology and polyhedral symmetry; then, we manipulate the predefined independent variables through optimization to achieve the user-defined geometric properties. The benchmark problem of finding equilateral Goldberg polyhedra is solved to demonstrate the effectiveness of the proposed method. Using this method, we have successfully achieved nearly exact spherical Goldberg polyhedra, with all vertices on a sphere and all faces being planar under extremely low numerical errors. Such results serve as strong numerical evidence for the existence of this new type of Goldberg polyhedra. Furthermore, we iteratively perform k-means clustering and optimization to significantly reduce the number of different edge lengths to benefit the cost reduction for architectural and engineering applications.

Improving the solubility and antileukemia activity of Wnt/ß-catenin signaling inhibitors by disrupting molecular planarity.

Leukemia cells depend on the Wnt/ß-catenin signaling pathway for their growth. Pyrvinium, a known Wnt signaling inhibitor, has demonstrated promising efficacy in the treatment of the aggressive blast phase chronic myeloid leukemia (BP-CML). We previously developed potent inhibitors 1-2 for the Wnt/ß-catenin signaling pathway. However, the further application of these compounds as anti-leukemia agents is limited by their modest anti-leukemia activity in cells and poor aqueous solubility, due to the high molecular planarity of the chemical scaffold. Here, we reported our efforts in the synthesis and in vitro evaluation of 18 new compounds (4a-r) that have been designed to disrupt the molecular planarity of the chemical scaffold. Several compounds of the series showed significantly improved anti-leukemia activity and aqueous solubility. As a highlight, compounds 4c not only maintained excellent inhibitory potency (IC50 = 1.3 nM) for Wnt signaling but also demonstrated good anti-leukemia potency (IC50 = 0.9 µM) in the CML K562 cells. Moreover, compound 4c had an aqueous solubility of 5.9 µg/mL, which is over 50-fold enhanced compared to its parents 1-2.

Molecular Engineering of Star-Shaped Indoline Hole Transport Materials: The Influence of Planarity on the Hole Extraction and Transport Processes.

As the key properties of perovskite solar cells (PSCs), the hole extraction and transport capabilities of the hole transport material (HTM) affect the photovoltaic performance of PSCs to a considerable extent, while both capabilities can be adjusted by molecular planarity. Therefore, in this work, the molecular planarity of the HTM is systematically optimized to regulate the hole extraction and transport capabilities. Along with the improvement in planarity, the HTM's HOMO level is increased, leading to the enhancement of hole extraction capability. Meanwhile, the hole transport capability can also be improved due to the intensification of molecular stacking during the film formation. As a result, the planar HTM achieves a relatively high efficiency of 18.48 %, which is higher than that of spiro-OMeTAD. Accordingly, the molecular planarity presents an important impact on the photovoltaic performance of PSCs, providing us with a promising strategy for further optimization of efficient HTMs.

Linear Relationships Among the Hand and Clubhead Motion Characteristics in Golf Driving in Skilled Male Golfers.

The purpose of this study was to investigate the linear relationships among the hand/clubhead motion characteristics in golf driving in skilled male golfers (n = 66; handicap ≤ 3). The hand motion plane (HMP) and functional swing plane (FSP) angles, the HMP-FSP angle gaps, the planarity characteristics of the off-plane motion of the clubhead, and the attack angles were computed from the drives captured by an optical motion capture system. The HMP angles were identified as the key variables, as the HMP and FSP angles were intercorrelated, but the plane angle gaps, the planarity bias, and the attack angles showed correlations to the HMP angles primarily. Three main swing pattern clusters were identified. The parallel HMP-FSP alignment pattern with a small direction gap was associated with neutral planarity and planar swing pattern. The inward alignment pattern with a large inward direction gap was characterized by flat planes, follow-through-centric planarity, spiral swing pattern, and inward/downward impact. The outward alignment pattern with a large outward direction gap was associated with steep planes, downswing-centric planarity, reverse spiral swing, and outward/upward impact. The findings suggest that practical drills targeting the hand motion pattern can be effective in holistically reprogramming the swing pattern.

Simple, reliable, and universal metrics of molecular planarity.

Planarity is a very important structural character of molecules, which is closely related to many molecular properties. Unfortunately, there is currently no simple, universal, and robust way to measure molecular planarity. In order to fill this evident gap, we propose two metrics of molecular planarity, namely molecular planarity parameter (MPP) and span of deviation from plane (SDP), to quantitatively characterize planarity of molecules. MPP reflects the overall degree of deviation of the structure from a plane, while SDP represents the span of the structural deviation relative to the fitting plane; respectively, they are complementary to each other. The examples in this article demonstrate that these metrics have strong rationality and practicality. They can not only be used to investigate the planarity of the entire molecule, but also measure the planarity of local structures, and they can even be employed to study variation of molecular planarity during a dynamic process. In addition, we also propose a new representation, namely coloring atoms according to their signed deviation distance to the fitting plane. This kind of map allows researchers to intuitively and quickly recognize position of the atoms in the system relative to the fitting plane. It can be seen from the examples that this representation is very useful in graphically exhibiting molecular planarity. The methods proposed in this work have been implemented in our open-source analysis code Multiwfn, which can be freely obtained via http://sobereva.com/multiwfn . The use is very simple and rich file formats are supported as input file.

2,3-Di-hydro-1H-cyclo-penta-[b]naphthalene-4,9-dione.

The title compound, C13H10O2, crystallizes with two almost planar mol-ecules in the asymmetric unit. In the crystal, slipped π-π stacking inter-actions help to establish the packing with the shortest centroid-centroid separation being 3.8195 (18) Å.

Geometrical and electro-static determinants of protein-protein interactions.

Protein-protein interactions (PPI) are pivotal to the numerous processes in the cell. Therefore, it is of interest to document the analysis of these interactions in terms of binding sites, topology of the interacting structures and physiochemical properties of interacting interfaces and the of forces interactions. The interaction interface of obligatory protein-protein complexes differs from that of the transient interactions. We have created a large database of protein-protein interactions containing over100 thousand interfaces. The structural redundancy was eliminated to obtain a non-redundant database of over 2,265 interaction interfaces. Therefore, it is of interest to document the analysis of these interactions in terms of binding sites, topology of the interacting structures and physiochemical properties of interacting interfaces and the offorces interactions. The residue interaction propensity and all of the rest of the parametric scores converged to a statistical indistinguishable common sub-range and followed the similar distribution trends for all three classes of sequence-based classifications PPInS. This indicates that the principles of molecular recognition are dependent on the preciseness of the fit in the interaction interfaces. Thus, it reinforces the importance of geometrical and electrostatic complementarity as the main determinants for PPIs.