Efficient photoreduction of carbon dioxide to ethanol using diatomic nitrogen-doped black phosphorus.

Successful conversion of CO2 into C2 products requires the development of new catalysts that overcome the difficulties in efficient light harvesting and CO-CO coupling. Herein, density functional theory (DFT) is used to assess the photoreduction properties of nitrogen-doped black phosphorus. The geometric structure, redox potential, first step of hydrogenation activation, CO desorption, and CO-CO coupling are systematically calculated, based on which the diatomic nitrogen-doped black phosphorus (N2@BPV) stands out. The calculated results of the CO2RR pathway demonstrate that N2@BPV has excellent selectivity and high activity for CH3CH2OH production. The results of the time-dependent ab initio nonadiabatic molecular dynamics simulation show that the diatomic N active sites of N2@BPV facilitate charge separation and inhibit electron-hole recombination. In addition, the activation mechanism of CO2 is studied. The main reason for CO2 activation is attributed to the imbalance in electron transfer that destroys the symmetry of CO2. We expect that our study will offer some theoretical guidance in CO2 conversion.

Characterization of Type I/II g-C3N4/MoS2 van der Waals Heterostructures: A New Theoretical Insight.

The charge transfer mechanism of the g-C3N4/MoS2 heterojunction is still disputed. Some regard it as a type I pathway, some regard it as a type II pathway, and still some regard it as a Z-scheme pathway. Especially, the results obtained by density functional theory (DFT) calculations are not totally in agreement. Here, we constructed four g-C3N4/MoS2 heterojunctions on the basis of the aperture alignment modes of g-C3N4 and MoS2. Their morphology and photocatalytic activity were investigated via first-principles and excited state dynamics simulations. By systemically comparing the interfacial binding energy and electronic structure (e.g., band structure, electrostatic potential, and band edge positions) of g-C3N4/MoS2 heterojunctions, we found that both type I and type II band alignment structures could be obtained. Moreover, the calculated lifetimes of interlayer photogenerated electrons and holes show that type II g-C3N4/MoS2 tends to favor a general type II pathway rather than a Z-scheme pathway. This study could provide a deep understanding of the photocatalytic mechanism of g-C3N4/MoS2 van der Waals heterostructures, which will be of great use for applications in photocatalysis.

Enhancing photocatalytic overall water-splitting performance on dual-active-sites of the Co-P@MoS2 catalysts: a DFT study.

The rational construction of photocatalysts possesses tremendous potential to solve the energy crisis and environmental pollution; however, designing a catalyst for solar-driven overall water-splitting remains a great challenge. Herein, we propose a new MoS2-based photocatalyst (Co-P@MoS2), which skillfully uses the cobalt (Co) atom to stimulate in-plane S atoms and employs the phosphorus (P) atom to stabilize the basal plane by forming the Co-P bands. Using density functional theory (DFT), it was found that oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) can occur at the P site and S2 site of the Co-P@MoS2, respectively, and the dual-active sites successfully makes a delicate balance between the adsorption and dissociation of hydrogen. Furthermore, the improved overall water-splitting performance of Co-P@MoS2 was verified by analyzing the results of the electron structure and the dynamics of photogenerated carries. It was found that the imbalance of electron transfer caused by the introduction of the Co atom was the main contributor to the catalytic activity of Co-P@MoS2. Our study broadens the idea of developing photocatalysts for the overall water-splitting.

One-step solution for angioplasty, low-profile stent delivery, and intrastent dilation using a dual-lumen angioplasty balloon microcatheter: technical advances, limitations, outcomes, and literature review.

Dual-lumen angioplasty balloon microcatheters make it possible to perform percutaneous transluminal angioplasty (PTA), low-profile stent delivery, and intrastent dilation without the microcatheter exchange technique. This technique has shown many advantages in recent years. We reviewed the techniques and applications in different intracranial vascular diseases and summarized the outcomes and indications. Gateway dual-lumen angioplasty balloon was used for PTA and kept in situ. Stent was delivered and deployed via Gateway microcatheter. Intrastent balloon dilation was performed after stent deployment. We retrospectively reviewed the clinical and imaging data, surgical procedures, technique application, and follow-up outcomes of six patients treated from 2020 to 2023. Neurological function was assessed by the modified Rankin scale (mRS). A literature review was performed using PubMed. All seven patients (4 males, 3 females; mean age, 62.6 ± 6.9 years) underwent percutaneous transluminal angioplasty and stent deployment using a balloon microcatheter. There was one middle cerebral artery (MCA) aneurysm with parent artery stenosis, two MCA dissections, and four intracranial atherosclerotic stenoses (ICASs). The mRS score was 0 in five patients and 1 in two patients. Cerebral dissection with stenosis is the best indication, and its application in stent-assisted aneurysm coiling is inappropriate. This technique is controversial in ICAS treatment.

A neuromechanical model for Drosophila larval crawling based on physical measurements.

BACKGROUND: Animal locomotion requires dynamic interactions between neural circuits, the body (typically muscles), and surrounding environments. While the neural circuitry of movement has been intensively studied, how these outputs are integrated with body mechanics (neuromechanics) is less clear, in part due to the lack of understanding of the biomechanical properties of animal bodies. Here, we propose an integrated neuromechanical model of movement based on physical measurements by taking Drosophila larvae as a model of soft-bodied animals. RESULTS: We first characterized the kinematics of forward crawling in Drosophila larvae at a segmental and whole-body level. We then characterized the biomechanical parameters of fly larvae, namely the contraction forces generated by neural activity, and passive elastic and viscosity of the larval body using a stress-relaxation test. We established a mathematical neuromechanical model based on the physical measurements described above, obtaining seven kinematic values characterizing crawling locomotion. By optimizing the parameters in the neural circuit, our neuromechanical model succeeded in quantitatively reproducing the kinematics of larval locomotion that were obtained experimentally. This model could reproduce the observation of optogenetic studies reported previously. The model predicted that peristaltic locomotion could be exhibited in a low-friction condition. Analysis of floating larvae provided results consistent with this prediction. Furthermore, the model predicted a significant contribution of intersegmental connections in the central nervous system, which contrasts with a previous study. This hypothesis allowed us to make a testable prediction for the variability in intersegmental connection in sister species of the genus Drosophila. CONCLUSIONS: We generated a neurochemical model based on physical measurement to provide a new foundation to study locomotion in soft-bodied animals and soft robot engineering.

First-principles calculations of 0D/2D GQDs-MoS2 mixed van der Waals heterojunctions for photocatalysis: a transition from type I to type II.

The fabrication of type II heterojunctions is an efficient strategy to facilitate charge separation in photocatalysis. Here, mixed dimensional 0D/2D van der Waals (vdW) heterostructures (graphene quantum dots (GQDs)-MoS2) for generating hydrogen from water splitting are investigated based on density functional theory (DFT). The electronic and photocatalytic properties of three heterostructures, namely, C6H6-MoS2, C24H12-MoS2 and C32H14-MoS2 are estimated by analyzing the density of states, charge density difference, work function, Bader charge, absorption spectra and band alignment. The results indicated that the built-in electric fields from GQDs to MoS2 boost charge separation. Meanwhile, all the GQDs-MoS2 exhibit strong absorption in the visible light region. Surprisingly, the transition of heterojunctions from type I to type II is realized by tuning the size of GQDs. In particular, C32H14-MoS2 with enhanced visible-light absorption and an appropriate band edge position, as a type II heterostructure, may be a promising photocatalyst for generating hydrogen from water splitting. Thus, in this work a novel type II 0D/2D nanocomposite as a photocatalyst is constructed that provides a strategy to regulate the type of heterostructure from the perspective of theoretical calculation.

Multi-residue analysis of 206 pesticides in grass forage by the one-step quick, easy, cheap, effective, rugged, and safe method combined with ultrahigh-performance liquid chromatography quadrupole orbitrap mass spectrometry.

A novel method for detecting pesticide multi-residue in grass forage (alfalfa and oat) was established based on the one-step automatic extraction and purification technology of quick, easy, cheap, effective, rugged, and safe combined with ultrahigh-performance liquid chromatography quadrupole Orbitrap high-resolution mass spectrometry. The crushed sample was extracted with acetonitrile with 1% acetate, followed by a cleanup step with a primary-secondary amine, octadecylsilane, and graphitized carbon black. The extraction and purification were carried out using the one-step automatic pretreatment equipment. The target pesticides were acquired in positive ion electrospray ionization mode and full scan/data dependent secondary scan mode. The calibration curve shows good linearity over the corresponding concentration range, with the coefficient of determination greater than 0.99. The screening detection limits were 0.5-50 µg/kg, and the limit of quantification for the 206 pesticides was set at 1-50 µg/kg. At the spiking levels of one, two, and 10 times of limit of quantification, more than 95% of pesticides had recovery between 70-120%, with a relative standard deviation ≤20%. The method was proved to be simple, rapid, high-sensitivity, and could be routinely used for the high throughput screening and quantitative analysis of pesticide residues in alfalfa and oat.

Reducing the particles generated by flushing institutional toilets.

Airborne particles play a significant role in the transmission of SARS-CoV-2, the virus that causes COVID-19. A previous study reported that institutional flush-O-meter (FOM) toilets can generate 3-12 times as many droplets as other toilets by splashing (large droplets) and bubble bursting (fine droplets). In this study, an aerosol suppression lid was evaluated to measure the reduction of particles by size using three metrics; number, surface area, and mass concentrations. To quantify toilet flush aerosol over time, detailed particle size distributions (from 0.016-19.81 µm across 152 size bins) were measured from a FOM toilet in a controlled-environment test chamber, without ventilation, with and without use of the suppression lid. Prior to each flushing trial, the toilet bowl water was seeded with 480 mL fluorescein at 10 mg/mL. A high-speed camera was used to record the large droplet movements after flushing. An ultraviolet-visible spectrophotometer was used to analyze the wipe samples to evaluate the contamination on the lid. The particle number, surface area, and mass concentrations without a lid were elevated compared to a lid in the first 90 sec. Overall, the lid reduced 48% of total number concentration, 76% of total surface area concentration, and 66% of total mass concentration, respectively. Depending on the particle size, the number concentration reduction percentage ranged from 48-100% for particles larger than 0.1 µm. Large droplets created by splashing were captured by the high-speed camera. Similar studies can be used for future particle aerodynamic studies. The fluorescein droplets deposited on the lid back sections, which were closer to the FOM accounted for 82% of the total fluorescein. Based on two-way ANOVA analysis, there were significant differences among both the experimental flushes (p = 0.0185) and the sections on the lid (p = 0.0146). Future work should explore the aerosolization produced by flushing and the performance of the lid in real restroom environments, where feces and urine exist in the bowl water and the indoor ventilation system is in operation.

Interfacial Properties of ZnO Nanowire-Enhanced Carbon Fiber Composites: A Molecular Dynamics Simulation Study.

The interfacial properties of ZnO nanowire (NW)/carbon fiber-reinforced epoxy composites are investigated using molecular dynamics (MD) simulations. An atomistic representative volume element (RVE) is developed in which a single ZnO NW is aligned on carbon fiber and embedded in the cross-linked epoxy. Effects of ZnO NWs on the fiber-matrix adhesion are studied by evaluating the fiber and the enhanced matrix interaction. The traction-separation behavior in both sliding mode (shear separation) and opening mode (normal separation) is evaluated. The cohesive parameters, including the peak traction and adhesion energy, are calculated in each mode. Different numbers of cross-linked epoxy units in the system are studied and validated. The interfacial properties of the hybrid system are compared with the simulated bare RVE containing fiber and epoxy. MD results showed that the interfacial strength is increased from 485 MPa to 1066 MPa with the ZnO NWs. The adhesion energy in both opening and sliding modes is significantly improved by growing ZnO NWs on the carbon fibers. In addition, the hybrid system shows more rate-independent behavior compared with the bare system in the opening mode.

Theoretical insight into the photophysical properties of long-lifetime Ir(iii) and Rh(iii) complexes for two-photon photodynamic therapy.

Two-photon photodynamic therapy (TP-PDT) plays crucial roles in curing tumors because it involves deep penetration of drugs into the tissue and has minimal damage to the surrounding cells. Our theoretical study was aimed at providing fresh insights into photosensitizers, such as [Ir(N^C)2(N^N)]+ (N^C = 2-phenylpyridine, N^N = bis-benzimidazole) and [Rh(N^C)2(N^N)]+, to treat cancer via the TP-PDT route. To better understand the properties of the complexes [Ir(N^C)2(N^N)]+ and [Rh(N^C)2(N^N)]+, the one-photon and two-photon absorption electronic spectra, energy gap (ΔES-T), strength of two-photon absorption cross-section (δ), spin-orbit matrix element (S1|HSO|Tj), and phosphorescence lifetimes (τ) were calculated by DFT and TD-DFT. The calculation results suggested that both complexes met the criteria (i.e. an efficient ISC process, enough energy to produce 1O2 and phototherapeutic window of the absorption wavelength) of photosensitizers; importantly, the designed complex [Rh(N^C)2(N^N)]+ had better performance than [Ir(N^C)2(N^N)]+, especially in the long-lived triplet excited state. It is expected that our research can make quite a few contributions to the development of photosensitizers and establish some guidelines for experiments based on TP-PDT.

Discovery of N-aryl-N'-pyrimidin-4-yl ureas as irreversible L858R/T790M mutant selective epidermal growth factor receptor inhibitors.

A novel series of N-aryl-N'-pyrimidin-4-yl ureas has been optimized to afford potent and selective inhibitors of the EGFR L858R/T790M. The most representative compound 28 showed high activity against EGFR L858R/T790M kinase (IC50 = 4 nM) and 22-fold selectivity against wild type EGFR. Moreover, compound 28 potently inhibited EGFR L858R/T790M phosphorylation (IC50 = 41 nM) and cellular proliferation (IC50 = 37 nM) in the H1975 cell line, while being significantly less toxic to A431 cells. Further, compound 28 exhibited a great selectivity in a mini-panel of kinases.

Theoretical study on photophysical properties of three high water solubility polypyridyl complexes for two-photon photodynamic therapy.

Two-photon photodynamic therapy (TP-PDT) is a very promising treatment that has drawn much attention in recent years due to its ability to penetrate deeper into tissues and minimize the damage to normal cells. Here, the properties of three highly water soluble Ru(ii) and Zn(ii) polypyridyl complexes as photosensitizers (PSs) were examined, including the one-photon and two-photon absorption (OPA and TPA) spectra, singlet-triplet energy gap (ΔH-L), TPA cross-section and spin-orbit coupling constant via Density Function Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT). Their potential therapeutic use as photosensitizers in TP-PDT is proposed, where the reasoning is as follows: first, they possess strong absorption in the therapeutic window; second, the vertical excitation energy is greater than 0.98 eV, which can generate a singlet oxygen species and the remarkable coupling between the S1 and T1 states. Moreover, the spin-orbit matrix elements are greater than 0.24 cm-1 for Ru-bpy and Zn-tpy, indicating that the intersystem spin crossing processes are efficient. It is expected that these complexes will be applied to PSs in TP-PDT, and we hope this research can serve as a guideline for the development of efficient two-photon PSs.

A Computational Way To Achieve More Effective Candidates for Photodynamic Therapy.

The purpose of the work described herein is to design highly efficient photosensitizers (PS) for photodynamic therapy (PDT) in theory. A series of expanded Zn porphyrins have been studied as light-activated PS. Their main photophysical properties are systematically calculated by using density functional theory and its time-dependent extension. The mechanisms of PDT are discussed. All the considered candidates exhibit intense absorption in the therapeutic window (600-800 nm), efficient intersystem crossing, and sufficient energy for singlet molecular oxygen production. Accordingly, the designed Zn pentaphyrins and sapphyrins would be proposed as potential PS for PDT. Moreover, the therapeutic effects of Zn pentaphyrins and sapphyrins are better than those of the referenced Zn iso-pentaphyrin. It is expected that the results could provide a new way to design and develop PS for PDT application.

Dynamic evolution of a vesicle formed by comb-like block copolymer-tethered nanoparticles: a dissipative particle dynamics simulation study.

Vesicles are well-sealed capsules that can store or transport substances. Their dynamic evolution mechanisms are important to fulfill specific functions. In the present study, dissipative particle dynamics (DPD) simulation was employed to study the formation, fusion, and fission pathways of vesicles. Our results show that comb-like block copolymer-tethered nanoparticles can self-assemble into stable vesicles, which may be a good candidate for drug entrapment and controlled release of drug. The spontaneous fusion of this type of vesicles has been studied, whose mechanism is different from that of the vesicles formed from comb-like block copolymers. However, the fission mechanisms of the two types of vesicles are similar. To summarize, the introduction of nanoparticles alters the fusion mechanism, but causes no difference in the fission pathway of vesicles. The reason may be attributed to the nature of nanoparticles. The fusion and fission processes always experience the congregation of nanoparticles. The large and rigid nanoparticles inevitably result in changes of surface tension of the vesicle that is a key factor influencing the membrane dynamics.

Activin A-induced increase in LOX activity in human granulosa-lutein cells is mediated by CTGF.

Lysyl oxidase (LOX) is the key enzyme involved in the crosslinking of collagen and elastin that is essential for the formation of extracellular matrix (ECM). LOX-mediated ECM remodeling plays a critical role in follicle development, oocyte maturation and corpus luteum formation. To date, the regulation of LOX in human ovary has never been elucidated. Activin A and its functional receptors are highly expressed in ovarian follicles from an early developmental stage. They locally regulate follicle progression. The aim of this study was to investigate the effects of activin A on the expression of LOX and its extracellular enzyme activity in primary and immortalized human granulosa-lutein cells obtained from patients undergoing an in vitro fertilization procedure. We demonstrated that activin A significantly upregulated the expression of connective tissue growth factor (CTGF) and LOX via an activin/TGF-ß type I receptor mediated-signaling pathway. Using a target depletion small interfering RNA knockdown approach, we further confirmed that the upregulation of CTGF expression resulted in an activin-A-induced increases in LOX expression and activity. These findings may provide insight into the mechanisms by which intrafollicular growth factors regulate the expression of LOX for ECM formation and tissue remodeling in the human ovary.

Sprouty4 mediates amphiregulin-induced down-regulation of E-cadherin and cell invasion in human ovarian cancer cells.

Sprouty (SPRY) proteins are well-characterized factors that inhibit receptor tyrosine kinase (RTK)-mediated activation of cellular signaling pathways. The down-regulation of SPRY4 expression has been reported in human ovarian cancer. However, the specific roles and mechanisms by which SPRY4 affects ovarian cancer progression are completely unknown. Amphiregulin (AREG) binds exclusively to the epidermal growth factor receptor (EGFR) and has been considered to be a dominant autocrine/paracrine EGFR ligand in ovarian cancer. In the present study, we first examined the effects of AREG on SPRY4 expression and the possible underlying molecular mechanisms involved in this process in two human ovarian cancer cell lines. Our results demonstrated that treatment with AREG up-regulated SPRY4 expression by activating the ERK1/2 signaling pathway. In addition, we showed that small interfering RNA (siRNA)-mediated knockdown of SPRY4 attenuated the AREG-induced down-regulation of E-cadherin by inhibiting the expression of SNAIL but not SLUG. In contrast, overexpression of SPRY4 enhanced AREG-induced down-regulation of E-cadherin by increasing the expression of SNAIL. Moreover, SPRY4 knockdown attenuated AREG-induced cell migration and invasion. Overexpression of SPRY4 enhanced AREG-induced cell invasion. This study reveals that SPRY4 is involved in EGFR-mediated human ovarian cancer progression.

Follicle-stimulating hormone polypeptide modified nanoparticle drug delivery system in the treatment of lymphatic metastasis during ovarian carcinoma therapy.

OBJECTIVE: Traditional chemotherapy drugs have an obvious drawback of nonspecific biodistribution in treating ovarian cancer. Follicle-stimulating hormone receptor (FSHR), a G-protein coupled receptor which is mainly expressed in reproductive system, is an important drug target in developing novel therapeutics. METHODS: Using a polypeptide of follicle-stimulating hormone (named as FSHP), a conjugated nanoparticle, FSHP-NP was developed to target FSHR in lymphatic metastasis of ovarian cancer. FSHP-NP was tested for recognition specificity and uptake efficiency on FSHR-expressing cells. A paclitaxel (PTX)-loaded FSHP-NP (FSHP-NP-PTX) was further developed and its anti-tumor effect was determined in vivo and in vitro. RESULTS: Taking NuTu-19 cells as an example, FSHP-NP-PTX displayed significantly stronger anti-cell proliferative and anti-tumor effects in a dose- and time-dependent manner when compared with free PTX or naked PTX-loaded nanoparticles (NP-PTX) in vitro. In vivo examinations showed that the size and weight of the lymph nodes were reduced in the FSHP-NP-PTX group. CONCLUSION: FSHR as a novel therapeutic target in ovarian cancer and delivery of PTX via conjugated nanoparticle (FSHP-NP) might represent a new therapeutic approach in ovarian cancer.

Halogen bond: its role beyond drug-target binding affinity for drug discovery and development.

Halogen bond has attracted a great deal of attention in the past years for hit-to-lead-to-candidate optimization aiming at improving drug-target binding affinity. In general, heavy organohalogens (i.e., organochlorines, organobromines, and organoiodines) are capable of forming halogen bonds while organofluorines are not. In order to explore the possible roles that halogen bonds could play beyond improving binding affinity, we performed a detailed database survey and quantum chemistry calculation with close attention paid to (1) the change of the ratio of heavy organohalogens to organofluorines along the drug discovery and development process and (2) the halogen bonds between organohalogens and nonbiopolymers or nontarget biopolymers. Our database survey revealed that (1) an obviously increasing trend of the ratio of heavy organohalogens to organofluorines was observed along the drug discovery and development process, illustrating that more organofluorines are worn and eliminated than heavy organohalogens during the process, suggesting that heavy halogens with the capability of forming halogen bonds should have priority for lead optimization; and (2) more than 16% of the halogen bonds in PDB are formed between organohalogens and water, and nearly 20% of the halogen bonds are formed with the proteins that are involved in the ADME/T process. Our QM/MM calculations validated the contribution of the halogen bond to the binding between organohalogens and plasma transport proteins. Thus, halogen bonds could play roles not only in improving drug-target binding affinity but also in tuning ADME/T property. Therefore, we suggest that albeit halogenation is a valuable approach for improving ligand bioactivity, more attention should be paid in the future to the application of the halogen bond for ligand ADME/T property optimization.

Structures and electronic properties of transition metal-containing ionic liquids: insights from ion pairs.

Transition metal-containing ionic liquids (TM-ILs) have attracted a great deal of attention in recent years, due to their unique physical and chemical properties. In this work, several representative TM-ILs, such as the cations consisting of silver(I) center coordinated by two n-alkylimidazole ligands ([(C(n)(im))Ag(mim)](+)) and the anions involving mercury(II) (HgCl3(-)), zinc(II) (ZnCl3(-)), and rhenium(VII) (ReO4(-)), were investigated using density functional theory calculations. First, the structural and energetic properties of the ion pairs for these TM-ILs have been examined in detail and compared with properties for conventional ILs. It was found that the interactions between the cations and anions, including hydrogen bonds and electrostatic interactions, in TM-ILs become weaker in strength than those in traditional ILs. In particular, the calculated geometric and energetic features compare fairly well with the experimental results, such as melting points and X-ray crystal structures of these TM-ILs. Then, the structures and energetics of ion-pair dimers for three ILs containing HgCl3(-), ZnCl3(-), and ReO4(-) were also explored, to gain a deeper understanding of the properties of TM-ILs. Finally, a survey of the Cambridge Structural Database (CSD) was undertaken to provide some crystallographic implications of TM-ILs.

Multi-algorithm and multi-model based drug target prediction and web server.

AIM: To develop a reliable computational approach for predicting potential drug targets based merely on protein sequence. METHODS: With drug target and non-target datasets prepared and 3 classification algorithms (Support Vector Machine, Neural Network and Decision Tree), a multi-algorithm and multi-model based strategy was employed for constructing models to predict potential drug targets. RESULTS: Twenty one prediction models for each of the 3 algorithms were successfully developed. Our evaluation results showed that ∼30% of human proteins were potential drug targets, and ∼40% of putative targets for the drugs undergoing phase II clinical trials were probably non-targets. A public web server named D3TPredictor (http://www.d3pharma.com/d3tpredictor) was constructed to provide easy access. CONCLUSION: Reliable and robust drug target prediction based on protein sequences is achieved using the multi-algorithm and multi-model strategy.