Electrocatalytic Hydrogen Evolution of Bent Bis(dipyrrin) Ni(II) Complexes.

Planar Ni(II) porphyrinoid complexes have been widely used in electrochemical carbon dioxide reduction reaction and oxygen reduction reaction as well as hydrogen evolution reaction (HER). However, nonplanar Ni(II) tetra-pyrrolic complexes have not been thoroughly investigated thus far. In this study, three highly bent bis(dipyrrin) Ni(II) complexes have been synthesized to investigate their structure, electronic property, and electrocatalytic HER activities. Cyclic voltammetry and thin-layer UV-visible spectroelectrochemistry studies revealed four redox processes, yielding two reduced species as the final products. The ic/ip values of phenyl- and pentafluorophenyl-bearing bis(dipyrrin) Ni(II) complexes were >30 when trifluoroacetic acid was used as the proton source, and their Faradaic efficiencies for H2 generation were >93%. Density functional theory calculations of the HERs revealed low endothermic energies of bent bis(dipyrrin) Ni(II) complexes.

Multivariable Coupled System Control Method Based on Deep Reinforcement Learning.

Due to the multi-loop coupling characteristics of multivariable systems, it is difficult for traditional control methods to achieve precise control effects. Therefore, this paper proposes a control method based on deep reinforcement learning to achieve stable and accurate control of multivariable coupling systems. Based on the proximal policy optimization algorithm (PPO), this method selects tanh as the activation function and normalizes the advantage function. At the same time, based on the characteristics of the multivariable coupling system, the reward function and controller are redesigned structures, achieving stable and precise control of the controlled system. In addition, this study used the amplitude of the control quantity output by the controller as an indicator to evaluate the controller's performance. Finally, simulation verification was conducted in MATLAB/Simulink. The experimental results show that compared with decentralized control, decoupled control and traditional PPO control, the method proposed in this article achieves better control effects.

Metal-Corrole-Based Porous Organic Polymers for Electrocatalytic Oxygen Reduction and Evolution Reactions.

Integrating molecular catalysts into designed frameworks often enables improved catalysis. Compared with porphyrin-based frameworks, metal-corrole-based frameworks have been rarely developed, although monomeric metal corroles are usually more efficient than porphyrin counterparts for the electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). We herein report on metal-corrole-based porous organic polymers (POPs) as ORR and OER electrocatalysts. M-POPs (M=Mn, Fe, Co, Cu) were synthesized by coupling metal 10-phenyl-5,15-(4-iodophenyl)corrole with tetrakis(4-ethynylphenyl)methane. Compared with metal corrole monomers, M-POPs displayed significantly enhanced catalytic activity and stability. Co-POP outperformed other M-POPs by achieving four-electron ORR with a half-wave potential of 0.87 V vs. RHE and reaching 10 mA cm-2 OER current density at 340 mV overpotential. This work is unparalleled to develop and explore metal-corrole-based POPs as electrocatalysts.

MiR-195 alleviates oxygen-glucose deprivation/reperfusion-induced cell apoptosis via inhibition of IKKα-mediated NF-κB pathway.

OBJECTIVES: Increasing evidence confirmed that miRNA plays a critical role in the occurrence and development of ischemic stroke. Here, the aim of this study was to examine the function and mechanisms of miR-195 in vascular endothelial cell apoptosis induced by oxygen-glucose deprivation (OGD). METHODS: This study intended to use OGD to simulate ischemia in vitro. The mRNA expression of miR-195, IKKα and NF-κB in human umbilical vein endothelial cells (HUVECs) were detected by RT-qPCR. The proliferation and apoptosis ability of HUVECs were evaluated using MTT assay, colony formation assay and flow cytometry, respectively. Western blot was applied to examine related protein expression. The interaction between miR-195 and IKKα was verified by dual-luciferase reporter gene assay. RESULTS: OGD significantly inhibited cell viability and induced cell apoptosis in HUVECs. Meanwhile, OGD treatment notably decreased the expression of miR-195, as well as enhanced NF-κB expression. Moreover, miR-195 directly interacted with IKKα and suppressed its expression. Mechanically, overexpression of miR-195 exhibited pro-proliferation and anti-apoptotic effect on HUVECs treated with OGD through targeting IKKα-mediated NF-κB pathway. At the molecular level, through suppressing IKKα/NF-κB pathway, miR-195 inhibited the expression of pro-apoptotic protein Bax and active caspase-3, but increased the expression of anti-apoptotic Bcl-2 in HUVECs. CONCLUSIONS: Our finding uncovers the protective effect of miR-195 on the biological behavior of HUVECs via suppression of the NF-κB pathway induced by IKKα, which may provide a new potential strategy for ischemic stroke clinical treatment.

Target-swiped DNA lock for electrochemical sensing of miRNAs based on DNAzyme-assisted primer-generation amplification.

As an extremely important post-transcriptional regulator, miRNAs are involved in a variety of crucial biological processes, and the abnormal expressions of miRNAs are closely related to a variety of diseases. In this work, for the first time, we designed a nucleic acid lock nanostructure for specific detection of miRNA-21, which changes the self-structure to "active conformation" by binding the target, in order to generate triggers to initiate the subsequent reaction. Emphatically, this flexible nucleic acid lock is capable of self-cleaving without the assistance of external component, overcoming the disadvantages of the complex design and requiring protease assistance in traditional nanostructure. Moreover, the combination of DNAzyme and RCA technology not only greatly improves the efficiency of signal amplification but also enables primer generation to simultaneous cascade RCA amplification. Additionally, the electrochemical detection technology based on silver nanoclusters overcomes the shortcomings of traditional detection methods such as low sensitivity and complex operation. The detection limit achieved was 9.3 aM with a wide dynamic response ranging from 10 aM to 100 pM (at the DPV peak of - 0.5 V), which is comparable to most of the reported studies. Therefore, our work provided an ultra-sensitive way for the detection of miRNAs using nanostructures and revealed an effective means for disease theranostics and cancer diagnosis. In this work, for the first time, we designed a nucleic acid lock nanostructure based on its self-structural transformation for the specific detection of miRNA. And the combination of DNAzyme and cascade RCA reaction greatly improved the signal amplification efficiency.

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two-Electron and Four-Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers.

Achieving a selective 2 e- or 4 e- oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso-phenyls each bearing a bulky ortho-amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers αßαß and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2 ), respectively, but ααßß and αααß show poor selectivity with n=2.89-3.10. Isomer αßαß catalyzes 2 e- ORR by preventing a bimolecular O2 activation path, while αααα improves 4 e- ORR selectivity by improving O2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K-edge near-edge X-ray absorption fine structure. This work represents an unparalleled example to improve 2 e- and 4 e- ORR by tuning only steric effects without changing molecular and electronic structures.

A high-performance functional phthalonitrile resin with a low melting point and a low dielectric constant.

A monomer of fluorinated phthalonitrile, namely 4,4'-bis(p-perfluoro-phenol-(bis(p-phenol)propane-2,2-diyl)-p-oxy-diphthalonitrile) (PBDP), was synthesized by the nucleophilic substitution reaction of bisphenol A, decafluorobiphenyl and 4-nitrophthalonitrile. The structure of the monomer was characterized by nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The results indicated that the PBDP monomer was synthesized successfully. The monomer was cured in the presence of 4-(aminophenoxy)phthalonitrile (APPH) and the curing behaviour was investigated by differential scanning calorimetry (DSC), suggesting a low melting point of 96 °C and an excellent processing window (96-262 °C). Thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) showed that the fluorinated phthalonitrile resin possessed outstanding thermal and thermo-oxidative stabilities as well as good mechanical properties. The glass transition temperature was >400 °C and the 5% thermal degradation temperature was 501 °C. When the frequency was 50 MHz, the dielectric constant and dielectric loss of the polymer were 2.84 and 0.007, respectively. The PBDP resin has ultra-low water absorption of 0.77% and 1.4%, when exposed to an aqueous environment for 50 days at 24 °C and for 24 h at 100 °C, respectively. The prepared PBDP resin with outstanding thermal stability and low dielectric constant is an ideal candidate for aerospace industries, and microelectronic and other electronic packaging materials.

Enhanced Thermal Conductivity of Polyimide Composites Filled with Modified h-BN and Nanodiamond Hybrid Filler.

A new thermally conductive and electrically insulative polyimide were prepared by filling different amounts of hexagonal boron nitride (h-BN) particles, and the thermal conductivity of Polyimide (PI) composites were improved with the increasing h-BN content. Based on this, two methods were applied to improve thermal conductivity furtherly at limited filler loading in this paper. One is modifying the h-BN to improve interface interaction, another is fabricating a nano-micro hybrid filler with 2-D h-BN and 0-D nano-scale nanodiamond (ND) to build more effective conductive network. Both surface modification and hybrid system have a positive effect on thermal conductivity. The composites introducing 40 wt% hybrid filler (the weight ratio of ND/modified BN was 1/10) showed the highest thermal conductivity, being up to 0.98 W/(m K) (5.2 times that of PI). In addition, the composites exhibits excellent electrical insulation, thermal stability properties etc.

Functionalization of Nanodiamond with Four Kinds of Expoxies.

In this work, a simple and effective method for the covalent functionalization of nanodiamond (ND) with four epoxies has been developed. After homogenization by mixed acids and thionyl chlorides, the surface of ND was modified with triethylenetetramine (TETA) to possess amine groups, which were used as active points to react with epoxy by ring opening reaction. Four different epoxies used are bifunctional diglycidyl ether of bisphenol-A (DGEBA), trifunctional triglycidyl p-amino phenol (TGAP), tetrafunctional tetraglycidyldiamino diphenylmethane (TGDDM) and bisphenol-A novolac epoxy resin (BAEPN). FT-IR spectra revealed that the epoxy was covalently attached to the ND (ND-g-epoxy). In addition, functionalized ND particles were characterized with WAXD and UV-Vis spectra to confirm the result. The weight gains as a result of the epoxy-functionalized ND were determined by TGA analysis. The ND-g-epoxy particles were better dispersed in common organic solvents and the average diameters were characterized. The better dispersion and of the modified ND were identified from the SEM images.

Preparation of Polyimide/MWCNT Nanocomposites via Solid State Shearing Pulverization (S3P) Processing.

Polyimide/multiwall carbon nanotube (PI/MWCNT) nanocomposite films with homogeneous MWCNTs dispersion were prepared via a solid state shearing pulverization (S3P) approach. Polyimide precursor, viz., poly(amic acid) (PAA), was synthesized from 4,4'-oxydianiline (ODA) and pyromellitic dianhydride (PMDA). Then, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) was mixed with the PAA powder and acid functionalized MWCNTs (acid-MWCNTs) by solid state shearing pulverization (S3P) approach. Finally, PI/MWCNT nanocomposite films were prepared by thermal imidization at elevated temperatures. Using such an approach not only the MWCNTs are well-dispersed but also the mechanical and thermal properties of PI are improved. The tensile strength of PI was enhanced by 74% and the elongation at break decreased to 10.35% with 5.0 wt% acid- MWCNT loading. And the glass transition temperature of PI was increased to 341 degrees C from 303 degrees C because of the strong interfacial bonding between PI and acid-MWCNTs. The solid state shearing pulverization (S3P) approach developed in this study provides a novel method to prepare various polymer composites with desired particle dispersion.

Nonadiabatic molecular dynamics with subsystem density functional theory: application to crystalline pentacene.

In this work, we report the development and assessment of the nonadiabatic molecular dynamics approach with the electronic structure calculations based on the linearly scaling subsystem density functional method. The approach is implemented in an open-source embedded Quantum Espresso/Libra software specially designed for nonadiabatic dynamics simulations in extended systems. As proof of the applicability of this method to large condensed-matter systems, we examine the dynamics of nonradiative relaxation of excess excitation energy in pentacene crystals with the simulation supercells containing more than 600 atoms. We find that increased structural disorder observed in larger supercell models induces larger nonadiabatic couplings of electronic states and accelerates the relaxation dynamics of excited states. We conduct a comparative analysis of several quantum-classical trajectory surface hopping schemes, including two new methods proposed in this work (revised decoherence-induced surface hopping and instantaneous decoherence at frustrated hops). Most of the tested schemes suggest fast energy relaxation occurring with the timescales in the 0.7-2.0 ps range, but they significantly overestimate the ground state recovery rates. Only the modified simplified decay of mixing approach yields a notably slower relaxation timescales of 8-14 ps, with a significantly inhibited ground state recovery.

Relationship between paravertebral muscle degeneration and spinal-pelvic sagittal parameters in patients with lumbar disc herniation.

Lumbar disc herniation (LDH) is a clinically common degenerative disease of the spine, and spinal-pelvic sagittal balance and paravertebral muscle degeneration have been a research focus in recent years. To explore the relationship between the degeneration of paravertebral muscle and the changes in the spinal-pelvic sagittal parameters in LDH patients, 105 LDH patients (experimental group) and 63 healthy volunteers (control group) hospitalized in Ordos Central Hospital from January 2020 and January 2023 were included as study subjects. All the patients underwent lumbar magnetic resonance imaging and spinal X-ray using uniform criteria. The correlation between the paravertebral muscle and sagittal-pelvic sagittal parameters of the patients with LDH was obtained from two imaging examinations, and the data were organized and grouped to explore the correlation between these parameters. No significant difference in general data existed between the groups (P > 0.05). In the L4/5 LDH patients group, the ratio of fat infiltration (FIR) in the healthy side [multifidus (MF) and erector spinae (ES)] was negatively correlated with the lumbar lordosis (LL) (r = -0.461, r = -0.486, P < 0.05). The relative cross-sectional area (RCSA) of the bilateral MF was positively correlated with the pelvic tilt (r = 0.549, r = 0.515, P < 0.05). The bilateral ES RCSA was negatively correlated with the sagittal vertical axis (r = -0.579, r = -0.621, P < 0.05). A positive correlation existed between the RCSA and thoracic kyphosis in the healthy side ES (r = 0.614, P < 0.05). In the L5/S1 LDH patients group, a negative correlation existed between the FIR and LL in the healthy side ES (r = -0.579, P < 0.05). Thus, the paravertebral muscle parameters were correlated with the spinal-pelvic sagittal parameters in the patients with LDH.

[Professor ZHANG Wei-hua's clinical experience in chronic somatic pain treated with zhidong needling techniques].

The paper summarizes professor ZHANG Wei-hua's clinical experience for the treatment of chronic somatic pain with zhidong needling techniques. In terms of the characteristics of chronic somatic pain, professor ZHANG has integrated zhidong needling with acupuncture kinetic therapy. The satisfactory therapeutic effects are obtained by selecting the painful points and regions as the treatment sites and the specific techniques of zhidong needling depending on the size of affected area, the depth of illness, the size and shape of the cord-like muscle, etc. Five techniques of zhidong needling are used accordingly with twirling, pulling, lifting and thrusting, surrounding needling methods involved, as well as with the manipulation speed, direction and frequency considered.

[ZHANG Wei-hua's clinical experience of Zhenjing Anshen method in treatment of insomnia].

The paper summarizes professor ZHANG Wei-hua's clinical experience in treatment of insomnia with Zhenjing Anshen (calming-down the spirit) method. It is believed that insomnia results from the unstable spirit in pathogenesis of TCM. The basic therapeutic principle is regulating the spirit, in which, stabilizing the primary spirit and tranquilizing the heart spirit are emphasized. Main acupoints are Baihui (GV 20), Sishencong (EX-HN 1) and Yintang (GV 24+) to stabilize the primary spirit, located on the head; and Shenmen (HT 7) located on the wrist to calm-down the heart spirit, as well as Sanyinjiao (SP 6) and Yongquan (KI 1) in the lower extremities to benefit yin and balance yang, and then to house the spirit eventually. The needles are inserted in different depths and to various directions. The external application of herbal plaster is combined at Yongquan (KI 1) and the supplementary acupoints are selected in terms of syndrome differentiation. This therapy is simple in acupoint selection and very effective in treatment of insomnia.

Artificial intelligence in cancer pathology: Challenge to meet increasing demands of precision medicine.

Clinical efforts on precision medicine are driving the need for accurate diagnostic, new prognostic and novel drug predictive assays to inform patient selection and stratification for disease treatment. Accumulating evidence suggests that a combination of cancer pathology and artificial intelligence (AI) can meet this requirement. In the present review, the past, present and emerging integrations of AI into cancer pathology were comprehensively reviewed, which were divided into four main groups to highlight the roles of AI­integrated cancer pathology in precision medicine. Furthermore, the unsolved problems and future challenges in AI­integrated cancer pathology were also discussed. It was found that, although AI­integrated cancer pathology could enable the amalgamation of complex morphological phenotypes with the multi­omics datasets that drove precision medicine, synergies of cancer pathology with other medical tools could be more promising for the clinic when making an accurate and rapid decision in personalized treatments for patients. It was hypothesized by the authors that exploring the potential advantages of the multimodal integration of cancer pathology, imaging­omics, protein­omics and other­omics, as well as clinical data to decide upon appropriate management and improve patient outcomes may be the most challenging issue of cancer precision medicine in the future.

Super-tough polylactic acid (PLA)/poly(butylene succinate) (PBS) materials prepared through reactive blending with epoxy-functionalized PMMA-GMA copolymer.

High-performance biosourced polylactic acid (PLA)/poly(butylene succinate) (PBS) blends with small amounts of compatibilizer, epoxy-functionalized methyl methacrylate-co-glycidyl methacrylate copolymer (PMMA-GMA), were fabricated by melt compounding. The properties of the modified PLA/PMMA-GMA, PBS/PMMA-GMA, and PLS(PLA/PBS)/PMMA-GMA blends were investigated systematically. DSC combined with X-ray diffraction revealed a low-order semi-crystalline structure for all samples. SEM and DMA showed that the compatibility between PLA and PBS was improved after addition of PMMA-GMA. Rheological behavior of blends showed that the addition of PMMA-GMA resulted in a significant improvement in the viscoelasticity. FT-IR spectra confirmed that the interfacial compatibilization between PLA and PBS phases was improved due to the reaction of epoxy groups with terminal groups of PLA and PBS. Finally, the toughness and notched impact strength of the PLA materials were increased significantly. The elongation at break and notched impact strength of PLS/PMMA-GMA was about 55.7 and 6.2 times than neat PLA after incorporation of 7 wt% PMMA-GMA, respectively.

DNA tetrahedron-besieged primer and DNAzyme-activated programmatic RCA for low-background electrochemical detection of ochratoxin A.

Ochratoxin A (OTA) is the most toxic class of ochratoxins and has become a major threat to the environment, humans and animals. Therefore, research on the methods for its detection is also more urgent. Herein, we propose a low-background electrochemical biosensor based on a DNA tetrahedron-besieged primer and a DNAzyme-activated programmatic rolling circle amplification (RCA) that can be ultimately utilized for OTA detection in wine samples. Low-background detection can be achieved using the besieged primer via sequenced assembly of DNA tetrahedral nanostructures so that non-specific extensions of primer can be avoided. The target OTA-mediated DNAzyme activation initiates the programmatic RCA. Additionally, the catalytic property of silver nanoclusters (AgNCs) is integrated with the electrochemical assay to achieve high sensitivity for OTA detection. Benefiting from the aforementioned processes, a low-background, and highly sensitive electrochemical biosensor has been successfully constructed. This design is capable of detecting OTA at concentrations from 1 pg/mL to 10 ng/mL, and its lowest concentration limit is 0.773 pg/mL. Simultaneously, its validation in the detection of actual samples reveals that the proposed electrochemical biosensor has a lot of potential in food safety and environmental detection.

Corrigendum: The effect of temperature on dengue virus transmission by Aedes mosquitoes.

[This corrects the article DOI: 10.3389/fcimb.2023.1242173.].

The effect of temperature on dengue virus transmission by Aedes mosquitoes.

Dengue is prevalent in tropical and subtropical regions. As an arbovirus disease, it is mainly transmitted by Aedes aegypti and Aedes albopictus. According to the previous studies, temperature is closely related to the survival of Aedes mosquitoes, the proliferation of dengue virus (DENV) and the vector competence of Aedes to transmit DENV. This review describes the correlations between temperature and dengue epidemics, and explores the potential reasons including the distribution and development of Aedes mosquitoes, the structure of DENV, and the vector competence of Aedes mosquitoes. In addition, the immune and metabolic mechanism are discussed on how temperature affects the vector competence of Aedes mosquitoes to transmit DENV.

An autonomous synthetic DNA machine for ultrasensitive detection of Salmonella typhimurium based on bidirectional primers exchange reaction cascades.

Statistics show that food poisoning caused by Salmonella typhimurium (S. Typhimurium) often tops the list of bacterial food poisoning types in countries around the world. However, detecting traces of S. Typhimurium in real samples remains challenging. In recent years, primer exchange reaction (PER), a new isothermal amplification strategy, has rapidly attracted the attention of researchers in the field of biosensing. In this work, We developed a nanostructure called DNA arch bridge (DAB) and combined the DAB with cascade PER technology to construct a novel bidirectional PER (B-PER) for ultra-sensitive detection of pathogenic bacteria as a novel fluorescent biosensor. This strategy relies on the B-PER reaction mediated by binding of the target and adaptor, which occurs with the assistance of Klenow Fragment (KF) (3'-5'exo) polymerase and produces a good deal of G-quadruplex sequences that generate a fluorescent signal by embedding fluorescent dyes. Under the best conditions, the biosensor achieves ultrasensitive detection of S. Typhimurium, and the detection limit of the strategy is 9.3 cfu mL-1 over the linear detection scope of 101-105 cfu mL-1. The method has the merits of facile operation, rapid response, and high sensitivity. Furthermore, the biosensor is expected to achieve ultrasensitive detection of various small molecules through recognizing different target and primer sequences. Therefore, our proposed strategy provides an efficient, stable, universal, and practical sensing platform for pathogen and other small molecules detection.