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.

Adaptive Response to Solvation in Flexible Molecules: Oligo Hydrates of 4-Hydroxy-2-butanone.

Structural changes induced by water play a pivotal role in chemistry and biology but remain challenging to predict, measure, and control at molecular level. Here we explore size-governed gas-phase water aggregation in the flexible molecule 4-hydroxy-2-butanone, modeling the conformational adaptability of flexible substrates to host water scaffolds and the preference for sequential droplet growth. The experiment was conducted using broadband rotational spectroscopy, rationalized with quantum chemical calculations. Two different isomers were observed experimentally from the di- to the pentahydrates (4-hydroxy-2-butanone-(H2O)n=2-5), including the 18O isotopologues for the di- and trihydrates. Interestingly, to accommodate water molecules effectively, the heavy atom skeleton of 4-hydroxy-2-butanone reshapes in every observed isomer and does not correspond to the stable conformer of the free monomer. All solvates initiate from the alcohol group (proton donor) but retain the carbonyl group as secondary binding point. The water scaffolds closely resemble those found in the pure water clusters, balancing between the capability of 4-hydroxy-2-butanone for steering the orientation and position of the water molecules and the ability of water to modulate the monomer's conformation. The present work thus provides an accurate molecular description on how torsionally flexible molecules dynamically adapt to water along progressing solvation.

Competition between O-H and S-H Intermolecular Interactions in Conformationally Complex Systems: The 2-Phenylethanethiol and 2-Phenylethanol Dimers.

Noncovalent interactions involving sulfur centers play a relevant role in biological and chemical environments. Yet, detailed molecular descriptions are scarce and limited to very simple model systems. Here we explore the formation of the elusive S-H···S hydrogen bond and the competition between S-H···O and O-H···S interactions in pure and mixed dimers of the conformationally flexible molecules 2-phenylethanethiol (PET) and 2-phenylethanol (PEAL), using the isolated and size-controlled environment of a jet expansion. The structure of both PET-PET and PET-PEAL dimers was unraveled through a comprehensive methodology that combined rotationally resolved microwave spectroscopy, mass-resolved isomer-specific infrared laser spectroscopy, and quantum chemical calculations. This synergic experimental-computational approach offered unique insights into the potential energy surface, conformational equilibria, molecular structure, and intermolecular interactions of the dimers. The results show a preferential order for establishing hydrogen bonds following the sequence S-H···S < S-H···O ≲ O-H···S < O-H···O, despite the hydrogen bond only accounting for a fraction of the total interaction energy.

A Rotational Study of 2-tert-Butylphenol and Its 1 : 1 Argon Complex.

The chirped-pulse Fourier Transform microwave spectrum of 2-tert-butylphenol, an industrial intermediate for the production of antioxidants, has been investigated in the 2-8 GHz frequency range. The spectral analysis has allowed obtaining precise structural information on the most stable conformer and its complex with argon. The conformation of the monomer reveals that the hydroxyl group is coplanar with the ring but points in the opposite direction to the tert-butyl group, reducing steric interactions. In the tert-butyl group one methyl group is coplanar and the other two are symmetrically staggered respect to the ring. The complex shows the rare gas sitting above the aromatic ring. Interestingly, neither the monomer nor the complex exhibit large-amplitude hydroxyl torsion motions, previously observed in 2,6-disubstituted phenols such as 2,6-di-tert-butylphenol or propofol. The experimental results are supported by computational calculations, validating the molecular structure. Additionally, symmetry-adapted perturbation theory has allowed determining the van der Waals intermolecular interaction energy of the complex.

Non-radical activation of low additive periodate by carbon-doped boron nitride for acetaminophen degradation: Significance of high-potential metastable intermediates.

Metal-free environmental-friendly and cost-effective catalysts for periodate (PI) activation are crucial to popularize their application for micropollutant removal in water. Herein, we report that carbon-doped boron nitride (C-BN) can efficiently activate PI to degrade acetaminophen under very low oxidant doses (40 µM) and over a relatively wide pH range (3-9). As expected, the significant reduction in periodate addition is likely to be due to the higher chemical utilization efficiency achieved by a non-radical oxidation pathway. This involved two main mechanisms, the electron transfer process mediated by the high-potential metastable C-BN-900-PI* complex and singlet oxygen. In this case, the CO groups and defects on the C-BN surface were identified as key active sites for PI activation. Notably, the prepared C-BN-900 had good cycling performance and the degradation efficiency is recovered after simple annealing. The existence of HCO3- and HA significantly inhibited the reaction, whereas Cl-, SO42-, and NO3- had little effect on the degradation of ACE. Overall, this study provides a new alternative method to regulate the non-radical pathway of boron nitride/periodate system.

Rotational Spectroscopy and Conformational Flexibility of 2-Phenylethanethiol: The Dominant S-H⋠⋠⋠π Intramolecular Hydrogen Bond.

We present a rotational-computational investigation of the aromatic mercaptan 2-phenylethanethiol, addressing its potential energy surface, conformational equilibrium, internal dynamics and intramolecular interactions. The experiment used broadband chirped-pulse Fourier transform microwave spectroscopy in a supersonic jet expansion, recording the rotational spectrum in the 2-8 GHz frequency region. Two different conformers were detected in the spectrum. The most intense transitions correspond to a skew (gauche-gauche) conformation, identified as the global minimum. The spectra of ten different isotopologues were assigned for this species, leading to accurate effective and substitution structures. The weaker spectrum presents small tunnelling doublings caused by the torsional motion of the thiol group, which are only compatible with an antiperiplanar skeleton and a gauche thiol. The larger stability of the global minimum is attributed to an intramolecular S-H⋅⋅⋅π weak hydrogen bond. A comparison of the intramolecular interactions in the title molecule and 2-phenylethanol, similarly stabilized by a O-H⋅⋅⋅π hydrogen bond, shows the different strength of these interactions. Density functional (B3LYP-D3, B2PLYP-D3) and ab initio (MP2) calculations were conducted for the molecule.

The Structure of 2,6-Di-tert-butylphenol-Argon by Rotational Spectroscopy.

The molecular structure of a van der Waals-bonded complex involving 2,6-di-tert-butylphenol and a single argon atom has been determined through rotational spectroscopy. The experimentally derived structural parameters were compared to the outcomes of quantum chemical calculations that can accurately account for dispersive interactions in the cluster. The findings revealed a π-bound configuration for the complex, with the argon atom engaging the aromatic ring. The microwave spectrum reveals both fine and hyperfine tunneling components. The main spectral doubling is evident as two distinct clusters of lines, with an approximate separation of 179 MHz, attributed to the torsional motion associated with the hydroxyl group. Additionally, each component of this doublet further splits into three components, each with separations measuring less than 1 MHz. Investigation into intramolecular dynamics using a one-dimensional flexible model suggests that the main tunneling phenomenon originates from equivalent positions of the hydroxyl group. A double-minimum potential function with a barrier of 1000 (100) cm-1 effectively describes this extensive amplitude motion. However, the three-fold fine structure, potentially linked to internal motions within the tert-butyl group, requires additional scrutiny for a comprehensive understanding.

Clinical outcomes of indwelling needle-delivered urokinase thrombolysis in the treatment of thrombosed arteriovenous grafts.

BACKGROUND: To investigate the clinical outcomes of indwelling needle-delivered local urokinase thrombolysis, a cost-saving thrombolytic approach, in the treatment of thrombosed arteriovenous grafts (AVGs). METHODS: The clinical data of 71 patients with a first episode of thrombosed AVG were analyzed. Among them, 49 patients underwent urokinase thrombolysis and percutaneous transluminal angioplasty (PTA), and 22 patients underwent thrombectomy and PTA. The operation success rate, operation time, perioperative and postoperative complications, primary patency, and secondary patency were compared. RESULTS: Clinical success was achieved in all 71 PTAs. After thrombolysis, 29 patients achieved complete lysis, and 20 patients achieved partial lysis. All patients achieved thrombus clearance after PTA. The operating room usage time was 37.48 ± 5.33 min for the complete thrombolysis group and 41.70 ± 6.16 min for the incomplete thrombolysis group, and these values were not significantly different (p = 0.853). The operating room usage time of the thrombectomy group was 124.73 ± 5.08 min, which was significantly longer than that of the other groups (p < 0.001). The log-rank test indicated no significant difference in the 90-, 180-, and 360-day primary patency and corresponding secondary patency (all p > 0.05). The Cox regression showed that no significant difference was noted in the changing rate of primary or secondary patency among the groups (all p > 0.05). No major complications occurred in any of the groups, and the difference in the complication incidence was not significant (p = 0.336). CONCLUSIONS: Indwelling needle-delivered urokinase thrombolysis is an acceptable method for the treatment of thrombosed AVGs. Compared with thrombectomy and PTA, thrombolysis and PTA can significantly shorten the time to use the operating room without reducing primary and secondary patency or increasing complications.

Surface Engineering over Metal-Organic Framework Nanoarray to Realize Boosted and Sustained Urea Oxidation.

Facilitating C─N bond cleavage and promoting *COO desorption are essential yet challenging in urea oxidation reactions (UORs). Herein a novel interfacial coordination assembly protocol is established to modify the Co-phytate coordination complex on the Ni-based metal-organic framework (MOF) nanosheet array (CC/Ni-BDC@Co-PA) toward boosted and sustained UOR electrocatalysis. Comprehensive experimental and theoretical investigations unveil that surface Co-PA modification over Ni-BDC can manipulate the electronic state of Ni sites, and in situ evolved charge-redistributed surface can promote urea adsorption and the subsequent C─N bond cleavage. Impressively, Co-PA functionalization can impart a negatively charged catalyst surface with improved aerophobicity, not only weakening *COO adsorption and promoting CO2 departure, but also repelling CO3 2- approaching to deactivate Ni species, eventually alleviating CO2 poisoning and enhancing operational durability. Beyond that, improved hydrophilic and aerophobic characteristics would also contribute to better mass transfer kinetics. Consequently, CC/Ni-BDC@Co-PA exhibits prominent UOR performance with an ultralow potential of 1.300 V versus RHE to attain 10 mA cm-2 , a small Tafel slope of 45 mV dec-1 , and strong durability, comparable to the best Ni-based electrocatalysts documented thus far. This work affords a novel paradigm to construct MOF-based materials for promoted and sustained UOR catalysis through elegant surface engineering based on a metal-PA complex.

Equilibrium structures of selenium compounds: The torsionally flexible molecule of selenophenol.

The equilibrium structure of selenophenol has been investigated using rotational spectroscopy and high-level quantum mechanical calculations, offering electronic and structural insight into the scarcely studied selenium compounds. The jet-cooled broadband microwave spectrum was measured in the 2-8 GHz cm-wave region using broadband (chirped-pulse) fast-passage techniques. Additional measurements up to 18 GHz used narrow-band impulse excitation. Spectral signatures were obtained for six isotopic species of selenium (80Se, 78Se, 76Se, 82Se, 77Se, and 74Se), together with different monosubstituted 13C species. The (unsplit) rotational transitions associated with the non-inverting µa-dipole selection rules could be partially reproduced with a semirigid rotor model. However, the internal rotation barrier of the selenol group splits the vibrational ground state into two subtorsional levels, doubling the dipole-inverting µb transitions. The simulation of the double-minimum internal rotation gives a very low barrier height (B3PW91: 42 cm-1), much smaller than for thiophenol (277 cm-1). A monodimensional Hamiltonian then predicts a huge vibrational separation of 72.2 GHz, justifying the non-observation of µb transitions in our frequency range. The experimental rotational parameters were compared with different MP2 and density functional theory calculations. The equilibrium structure was determined using several high-level ab initio calculations. A final Born-Oppenheimer (reBO) structure was obtained at the coupled-cluster CCSD(T)_ae/cc-wCVTZ level of theory, including small corrections for the wCVTZ → wCVQZ basis set enlargement calculated at the MP2 level. The mass-dependent method with predicates was used to produce an alternative rm(2) structure. The comparison between the two methods confirms the high accuracy of the reBO structure and offers information on other chalcogen-containing molecules.

3D Hierarchical-Architectured Nanoarray Electrode for Boosted and Sustained Urea Electro-Oxidation.

Exploring active and durable Ni-based materials with optimized electronic and architectural engineering to promote the urea oxidation reaction (UOR) is pivotal for the urea-related technologies. Herein a 3D self-supported hierarchical-architectured nanoarray electrode (CC/MnNi@NC) is proposed in which 1D N-doped carbon nanotubes (N-CNTs) with 0D MnNi nanoparticles (NPs) encapsulation are intertwined into 2D nanosheet aligned on the carbon cloth for prominently boosted and sustained UOR electrocatalysis. From combined experimental and theoretical investigations, Mn-alloying can regulate Ni electronic state with downshift of the d-band center, facilitating active Ni3+ species generation and prompting the rate-determining step (*COO intermediate desorption). Meanwhile, the micro/nano-hierarchical nanoarray configuration with N-CNTs encapsulating MnNi NPs can not only endow strong operational durability against metal corrosion/agglomeration and enrich the density of active sites, but also accelerate electron transfer, and more intriguingly, promote mass transfer as a result of desirable superhydrophilic and quasi-superaerophobic characteristics. Therefore, with such elegant integration of 0D, 1D and 2D motifs into 3D micro/nano-hierarchical architecture, the resulting CC/MnNi@NC can deliver admirable UOR performance, favorably comparable to the best-performing UOR electrocatalysts reported thus far. This work opens a fresh prospect in developing advanced electrocatalysts via electronic manipulation coupled with architectural engineering for various energy conversion technologies.

Probing the n → π* carbonyl-carbonyl interactions in the formaldehyde-trifluoroacetone dimer by rotational spectroscopy.

The non-covalent bonding features of carbonyl-carbonyl interactions have been investigated in the dimer of formaldehyde and trifluoroacetone using high resolution rotational spectroscopy combined with quantum chemical calculations. The observation of all possible isotopic substitutions for the heavy atoms in the complex enabled the determination of the accurate structure, characterized by the antiparallel arrangement of the two C=O bonds. The two moieties are connected through a dominant n → π* interaction enhanced by one weak C-H⋯O hydrogen bond, as revealed by supporting natural bond orbital analysis and symmetry-adapted perturbation theory analysis. Further computational investigations on 17 related adducts stabilized by carbonyl-carbonyl n → π* interactions show how the interaction strength is regulated by the incorporation of either electron-donating or withdrawing functional groups.

The effect of silicon groups on the physicochemical property and bioactivity of L-phenylalanine derived poly(amide-imide).

Poly(amide-imide) (PAI), serving as a synthetic polymer, has been widely used in industry for excellent mechanical properties, chemical resistance and high thermal stability. However, lack of suitable cell niche and biological activity limited the further application of PAI in biomedical engineering. Herein, silicon modified L-phenylalanine derived poly(amide-imide) (PAIS) was synthesized by introducing silica to L-phenylalanine derived PAI to improve physicochemical and biological performances. The influence of silicon amount on physicochemical, immune, and angiogenic performances of PAIS were systemically studied. The results show that PAIS exerts excellent hydrophilic, mechanical, biological activity. PAIS shows no effects on the number of macrophages, but can regulate macrophage polarization and angiogenesis in a dose-dependent manner. This study advanced our understanding of silicon modification in PAI can modulate cell responses via initiating silicon concentration regulation. The acquired knowledge will provide a new strategy to design and optimize biomedical PAI in the future.

Sulfur-arene interactions: the S⋯π and S-H⋯π interactions in the dimers of benzofuran⋯sulfur dioxide and benzofuran⋯hydrogen sulfide.

Non-covalent interactions between sulfur centers and aromatic rings play important roles in biological chemistry. We examined here the sulfur-arene interactions between the fused aromatic heterocycle benzofuran and two prototype sulfur divalent triatomics (sulfur dioxide and hydrogen sulfide). The weakly-bound adducts were generated in a supersonic jet expansion and characterized with broadband (chirped-pulsed) time-domain microwave spectroscopy. The rotational spectrum confirmed the detection of a single isomer for both heterodimers, consistent with the computational predictions for the global minima. The benzofuran⋯sulfur dioxide dimer exhibits a stacked structure with sulfur closer to benzofuran, while in benzofuran⋯hydrogen sulfide the two S-H bonds are oriented towards the bicycle. These binding topologies are similar to the corresponding benzene adducts, but offer increased interaction energies. The stabilizing interactions are described as S⋯π or S-H⋯π, respectively, using a combination of density-functional theory calculations (dispersion corrected B3LYP and B2PLYP), natural bond orbital theory, energy decomposition and electronic density analysis methods. The two heterodimers present a larger dispersion component, but nearly balanced by electrostatic contributions.

NXNL2 Promotes Colon Cancer Proliferation and Metastasis by Regulating AKT Pathway.

This study aimed to explore the role of nucleoredoxin-like 2 (NXNL2) in colon cancer (CC). The GEPIA and UALCAN databases were analyzed to explore genes involved in the prognosis of CC patients. DLD1 cells were treated with the DNA methylation inhibitor 5-azacitidine to validate the above findings. The methyltransferase DNMT (DNA methylation) was further knocked down by shRNA, then the expression of NXNL2 was assessed by qPCR. The role of NXNL2 on cell proliferation and metastasis was examined using corresponding assays. NXNL2 was found to exhibit the greatest impact on the prognosis of CC patients. High NXNL2 correlated with poor survival outcomes of CC. The expression of NXNL2 was regulated by DNA methylation. NXNL2 promoted CC cell proliferation and metastasis. Also, NXNL2 promoted the AKT pathway activity. In conclusion, NXNL2 could affect the cancer cell proliferation and metastasis, and has a poor survival prognosis in CC.

Cost and Life Cycle Emissions of Ethanol Produced with an Oxyfuel Boiler and Carbon Capture and Storage.

Decarbonization of transportation fuels represents one of the most vexing challenges for climate change mitigation. Biofuels derived from corn starch have offered modest life cycle greenhouse gas (GHG) emissions reductions over fossil fuels. Here we show that capture and storage of CO2 emissions from corn ethanol fermentation achieves ∼58% reduction in the GHG intensity (CI) of ethanol at a levelized cost of 52 $/tCO2e abated. The integration of an oxyfuel boiler enables further CO2 capture at modest cost. This system yields a 75% reduction in CI to 15 gCO2e/MJ at a minimum ethanol selling price (MESP) of $2.24/gallon ($0.59/L), a $0.31/gallon ($0.08/L) increase relative to the baseline no intervention case. The levelized cost of carbon abatement is 84 $/tCO2e. Sensitivity analysis reveals that carbon-neutral or even carbon-negative ethanol can be achieved when oxyfuel carbon capture is stacked with low-CI alternatives to grid power and fossil natural gas. Conservatively, fermentation and oxyfuel CCS can reduce the CI of conventional ethanol by a net 44-50 gCO2/MJ. Full implementation of interventions explored in the sensitivity analysis would reduce CI by net 79-85 gCO2/MJ. Integrated oxyfuel and fermentation CCS is shown to be cost-effective under existing U.S. policy, offering near-term abatement opportunities.

Three non-bonding interaction topologies of the thiazole-formaldehyde complex observed by rotational spectroscopy.

When an aldehyde molecule interacts with a nitrogen atom inserted in an aromatic ring, they form a number of non-bonding topologies. We measured the rotational spectra of three different isomers of the thiazole-formaldehyde adduct. In all of them, formaldehyde interacts specifically with thiazole through an n → π* interaction (along the Bürgi-Dunitz trajectory) and a C-H⋯O (acting as a proton acceptor) weak hydrogen bond, or through C-H⋯N (acting as a proton donor) and C-H⋯O (acting as a proton acceptor) weak hydrogen bonds. The spectra of isotopic substituted species were also measured to draw the molecular structures. Two n → π* stabilized isomers show a vertical structure in which the two molecular planes are perpendicular to each other, and the hydrogen bonded isomers feature a co-planar architecture. The competition between these non-bonding interactions was unveiled from experiments and theoretical calculations.

Unconventional Phase Synergies with Doping Engineering Over Ni Electrocatalyst Featuring Regulated Electronic State for Accelerated Urea Oxidation.

Exploring high-performing Ni-based electrocatalysts for the urea oxidation reaction (UOR) is crucial for developing urea-related energy technologies yet remains a daunting challenge. In this study, a synergistic anomalous hcp phase and heteroatom doping engineering over metallic Ni are found to enhance the UOR. A metal-organic framework-mediated approach is proposed to construct Ni nanoparticles (NPs) with designated crystal phase embedded in N-doped carbon (fcc-Ni/NC and hcp-Ni/NC). Significant crystal phase-dependent catalytic activity for the UOR is observed; hcp-Ni/NC, featuring unusual hcp phase, outperforms fcc-Ni/NC with conventional fcc phase. Moreover, incorporating foreign Mn species in hcp-Ni/NC can further dramatically promote UOR, making it among the best UOR catalysts reported to date. From experimental results and DFT calculations, the specific nanoarchitecture, involving an anomalous hcp phase together with Mn doping engineering, endows hcp-MnNi/NC with abundant exposed active sites, facile charge transfer, and more significantly, optimized electronic state, giving rise to enriched Ni3+ active species and oxygen vacancies on the catalyst surface during electrocatalysis. These features collectively contribute to the enhanced UOR activity. This work highlights a potent design strategy to develop advanced catalysts with regulated electronic state through synergistic crystal phase and doping engineering.

An Investigation of Employees' Intention to Comply with Information Security System-A Mixed Approach Based on Regression Analysis and fsQCA.

Employee security compliance behavior has become an important safeguard to protect the security of corporate information assets. Focusing on human factors, this paper discusses how to regulate and guide employees' compliance with information security systems through effective methods. Based on protection motivation theory (PMT), a model of employees' intention to comply with the information security system was constructed. A questionnaire survey was adopted to obtain 224 valid data points, and SPSS 26.0 was applied to verify the hypotheses underlying the research model. Then, based on the results of a regression analysis, fuzzy set qualitative comparative analysis (fsQCA) was used to explore the conditional configurations that affect employees' intention to comply with the information security system from a holistic perspective. The empirical results demonstrated that perceived severity, perceived vulnerability, response efficacy, and self-efficacy all positively influenced the employees' intention to comply with the information security system; while rewards and response costs had a negative effect. Threat appraisal had a greater effect on employees' intention to comply with the information security system compared to response appraisal. The fsQCA results showed that individual antecedent conditions are not necessary to influence employees' intention to comply with an information security system. Seven pathways exist that influence an employees' intention to comply with an information security system, with reward, self-efficacy, and response cost being the core conditions having the highest probability of occurring in each configuration of pathways, and with perceived severity and self-efficacy appearing in the core conditions of configurations with an original coverage greater than 40%. Theoretically, this study discusses the influence of the elements of PMT on employees' intention to comply with an information security system, reveals the mechanism of influence of the combination of the influencing factors on the outcome variables, and identifies the core factors and auxiliary factors in the condition configurations, providing a new broader perspective for the study of information security compliance behavior and providing some theoretical support for strengthening enterprise security management. Practically, targeted suggestions are proposed based on the research results, to increase the intention of enterprise employees to comply with information security systems, thereby improving the effectiveness of enterprise information security management and the degree of information security in enterprises.