Local weak hydrogen bonds induced dipole-dipole interactions in polymer for enhancing photocatalytic oxidation.

Functionalizing organic polymers is an effective strategy for enhancing their photocatalytic performance. However, this approach is currently limited by specific motifs, complex preparation methods, and an unclear electron transfer mechanism. Here, we present a meticulously designed structure of perylene diimide connected with poly (barbituric acid trimer) through self-assembled hydrogen bonding. In particular, the local chemical environment of the two components is adjusted by hydrogen bond-induced dipole-dipole interactions, leading to the emergence of a significant inherent electric field. Additionally, the formation of hydrogen bonds provides electronic pathways that facilitate charge transfer from perylene to adjacent units. Moreover, the distinctive electronic structure enhances polarity transfer and improves activation and adsorption capabilities for reactive molecules. Ultimately, B-PDI exhibits outstanding oxidation rates for benzylamine to N-benzylidene-benzylamine (10.03 mmol g-1h-1) and selectivity (>99.99 %). Our work offers a widely popular approach for enhancing the photocatalytic activity of organic semiconductor materials by constructing hydrogen bonds in heterogeneous molecules.

Local polarization redistribution in ZnmIn2S3+m for the enhancing synergetic piezo-photocatalytic overall water splitting.

Piezo-photocatalytic water (deuterium oxide) decomposition is a promising strategy for realizing renewable energy, but the manipulation of the polar center remains a big challenge. This study uses a simple low-temperature hydrothermal process to successfully manufacture ZnmIn2Sm+3 (m = 1-3) (ZnIn2S4, Zn2In2S5 and Zn3In2S6). Incorporating both experimental and theoretical analyses, the structural contraction and local polarization of the Zn-S bond in Zn2In2S5 enhance the piezoelectric response and surface charge accumulation, which facilitate charge transfer and reduce the activation energy of water. Remarkably, Zn2In2S5 exhibits excellent piezoelectric photocatalytic total water splitting performance (H2/O2: 4284.72/1967.00 µmol g-1h-1), which is 1.77 times that of photocatalytic performance. Moreover, a significant enhancement in D2O splitting performance can be obtained for the optimized Zn2In2S5. Our work offers valuable insights into the disclosure of local polarization in catalysts for enhancing piezo-photocatalytic overall water splitting.

Personalized digital simulation­assisted acetabular component implantation in revision hip arthroplasty.

The number of artificial total hip revision arthroplasties is increasing yearly in China, and >50% of these cases have acetabular defects. Accurately locating and quantifying the bone defect is one of the current challenges of this surgery. Thus, the objective of the present study was to simulate acetabular implantation with the aid of Mimics 17.0 software (Materialise NV) in patients with loosened acetabular prosthesis, to evaluate the 'ideal acetabular center' and the 'actual acetabular center' to guide the choice of prosthesis and surgical method. From January 2017 to June 2021, the present study included 10 hips from 10 patients [seven men (seven hips) and three women (three hips)]. In all patients, the Mimics software was applied to simulate the dislocation of the femoral prosthesis and acetabular prosthesis implantation before surgery; calculate the height difference between the 'ideal acetabular center' and the 'actual acetabular center' to assess the bone defect; confirm the size of the acetabular prosthesis, abduction angle, anteversion angle and bone coverage of the acetabular cup; and measure the intraoperative bleeding and postoperative follow-up Harris score of the hip joint. After statistical analysis, the present study revealed that digital simulation assistance could improve the accuracy of hip revision acetabular prosthesis implantation, reduce postoperative shortening of the affected limb, especially for surgeons with relatively little experience in hip revision surgery, and greatly reduce the occurrence of complications such as hip dislocation because of poor postoperative prosthesis position.

Therapeutic utility of human umbilical cord-derived mesenchymal stem cells-based approaches in pulmonary diseases: Recent advancements and prospects.

Pulmonary diseases across all ages threaten millions of people and have emerged as one of the major public health issues worldwide. For diverse disease conditions, the currently available approaches are focused on alleviating clinical symptoms and delaying disease progression but have not shown significant therapeutic effects in patients with lung diseases. Human umbilical cord-derived mesenchymal stem cells (UC-MSCs) isolated from the human UC have the capacity for self-renewal and multilineage differentiation. Moreover, in recent years, these cells have been demonstrated to have unique advantages in the treatment of lung diseases. We searched the Public Clinical Trial Database and found 55 clinical trials involving UC-MSC therapy for pulmonary diseases, including coronavirus disease 2019, acute respiratory distress syndrome, bronchopulmonary dysplasia, chronic obstructive pulmonary disease, and pulmonary fibrosis. In this review, we summarize the characteristics of these registered clinical trials and relevant published results and explore in depth the challenges and opportunitiesfaced in clinical application. Moreover, the underlying molecular mechanisms involved in UC-MSC-based therapy for pulmonary diseases are also analyzed in depth. In brief, this comprehensive review and detailed analysis of these clinical trials can be expected to provide a scientific reference for future large-scale clinical application.

Molecular network analysis of 308 newly diagnosed HIV infection and 210 ART failure patients from rural counties in Sichuan.

BACKGROUND: Few studies on molecular epidemiology have studied people with newly diagnosed HIV infection and ART Failure Patients at the same time in rural China. With more serious HIV epidemic than in other provinces in China, Sichuan is an area suitable for this study. OBJECTIVE: To analyze the characteristics of HIV-1 molecular networks and factors related to network entry among newly diagnosed HIV infection and ART Failure Patients in three county-level cities (A, B, C) in Sichuan Province, to provide scientific basis for accurate prevention and control. METHODS: Nested PCR amplification method was used to amplify HIV-1 pol gene region of 530 blood samples, Sequencer 4.9 was used to edit, clean and splice the gene sequence, Bioedit correction, Fastree 2.1.8 and Figtree 1.4.2 to construct evolutionary tree and determine genotype. HyPhy2.2.4 and Cytoscape 3.6.1 software were used to construct molecular network. Logistic regression analysis was applied. RESULTS: 523(98.68%) pol sequences were obtained, and a total of 518 valid sequences with basic information came into the final analyses. A total of 6 genotypes were detected, namely CRF01_AE (320,61.78%), CRF07_BC (149,28.76%), B (30,5.79%), CRF08_BC (11, 2.12%), CRF55_01B (6, 1.16%) and C (2, 0.39%). 186 of 518(35.91%) sequences entered the network at a genetic distance of 0.8%, forming 42 propagation clusters. "High-risk transmitters"(connected with two and more) accounted for 21.62%. Logistic regression showed that≥50 years old (OR = 2.474) were more risky than 18-49 years old, CRF07_BC sub-type (OR = 0.174) were less risky than CRF01_AE sub-type, B sub-type (OR = 6.698) is higher risky than CRF01_AE sub-type, and District B (OR = 0.077) less risky than that of A city. CONCLUSION: The sources of HIV infection in rural Sichuan are diversified and complicated. The prevention and control of HIV infection in Sichuan Province should focus on strengthening the long-term dynamic detection of elderly population, B strain sub-type, and in City A.

Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles.

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles via a Michaelis-Arbuzov-type rearrangement is reported. A broad range of allylic alcohols and P(III)-nucleophiles (P(OR)3, ArP(OR)2, and Ar2P(OR)) are well tolerated in this reaction, and the expected dehydroxylative phosphorylation products could be synthesized with good to excellent yields under the optimal reaction conditions. The reaction can be easily scaled up at a gram-synthesis level. Furthermore, through the step-by-step control experiments, kinetic study experiments, and 31P NMR tracking experiments, we acquired insights into the reaction and proposed the possible mechanism for this transformation.

An Angular Acceleration Based Looming Detector for Moving UAVs.

Visual perception equips unmanned aerial vehicles (UAVs) with increasingly comprehensive and instant environmental perception, rendering it a crucial technology in intelligent UAV obstacle avoidance. However, the rapid movements of UAVs cause significant changes in the field of view, affecting the algorithms' ability to extract the visual features of collisions accurately. As a result, algorithms suffer from a high rate of false alarms and a delay in warning time. During the study of visual field angle curves of different orders, it was found that the peak times of the curves of higher-order information on the angular size of looming objects are linearly related to the time to collision (TTC) and occur before collisions. This discovery implies that encoding higher-order information on the angular size could resolve the issue of response lag. Furthermore, the fact that the image of a looming object adjusts to meet several looming visual cues compared to the background interference implies that integrating various field-of-view characteristics will likely enhance the model's resistance to motion interference. Therefore, this paper presents a concise A-LGMD model for detecting looming objects. The model is based on image angular acceleration and addresses problems related to imprecise feature extraction and insufficient time series modeling to enhance the model's ability to rapidly and precisely detect looming objects during the rapid self-motion of UAVs. The model draws inspiration from the lobula giant movement detector (LGMD), which shows high sensitivity to acceleration information. In the proposed model, higher-order information on the angular size is abstracted by the network and fused with multiple visual field angle characteristics to promote the selective response to looming objects. Experiments carried out on synthetic and real-world datasets reveal that the model can efficiently detect the angular acceleration of an image, filter out insignificant background motion, and provide early warnings. These findings indicate that the model could have significant potential in embedded collision detection systems of micro or small UAVs.

Trivalent Organostibines: Sb,N Ligands in Double N-Arylation of Primary Amines toward Functionalized Carbazoles.

A Sb,N ligand (L-Sb) for Pd-catalyzed double N-arylation of primary amines was developed. This trivalent ligand L-Sb, containing a 5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine skeleton and stable under air and moisture, could be synthesized facilely on a gram scale from chlorostibine (1) and cyclopentylmagnesium bromide. L-Sb showed excellent catalytic performance in Pd2(dba)3-catalyzed double N-arylation of 2,2'-dibromo-1,1'-biphenyl (2) with primary amines (3), affording functionalized carbazoles in good yields. This Pd2(dba)3/L-Sb-catalyzed double N-arylation, the first example of the application of trivalent organostibines as a ligand in N-arylation, featured the following advantages: small catalyst loading, wide functional group tolerance, good yields, and ease of gram-scale synthesis.

Nickel-Catalyzed C(sp3)-Sb Coupling of Chlorostibines with Unactivated Alkyl Chlorides and In Vitro Anticancer Activity of Products.

In this study, we present a nickel-catalyzed reductive C(sp3)-Sb coupling of unactivated alkyl chlorides with chlorostibines. This approach is highly versatile, tolerating various functional groups such as acetal, alkene, nitrile, amine, ester, silyl ether, thioether, and various heterocyclic compounds. Notably, the late-stage modification of bioactive molecules and the satisfactory anticancer activity against cancerous MDA-MB-231 also demonstrate the potential application.

[Comparison of early clinical effects between direct superior approach and posterolateral approach in hemiarthroplasty of femoral neck fracture in the elderly].

OBJECTIVE: To compare and analyze the early clinical effect of direct superior approach(DSA) and posterior lateral approach (PLA) in hemiarthroplasty for elderly patients with femoral neck fracture. METHODS: The clinical data of 72 elderly patients with femoral neck fracture who underwent hemiarthroplasty from January 2020 to December 2021 were retrospectively analyzed. Among them, 36 patients were operated through minimally invasive DSA including 10 males and 26 females with an average age of (82.82±4.05) years old; the other 36 patients underwent traditional PLA including 14 males and 22 females with an average age of (82.79±3.21) years old. The perioperative related indexes and Harris scores during follow-up between two groups were compared. RESULTS: Comparison of operation time between two groups, (79.41±17.39) min of DSA group was shorter than(98.45±26.58) min of PLA group;incision length (8.33±2.69) cm was shorter than (11.18±1.33) cm of PLA group;intraoperative blood loss (138.46±71.58) ml was less than (173.51±87.17) ml of PLA group, initial landing time (3.04±0.95) d was earlier than (4.52±1.10) d of PLA group, hospitalization time (8.70±1.89) d was shorter than (10.67±2.35) d of PLA group(P<0.05). There was no statistical difference in Harris score between two groups before operation(P>0.05), but Harris score in DSA group was higher than that of PLA group at 1 month after operation(P<0.05), but at 12 months after operation, the difference was not statistically significant between two groups(P>0.05). CONCLUSION: Compared with PLA, DSA is superior in clinical indexes such as operation time, intraoperative blood loss, incision length, first landing time, length of hospitalization and Harris score in the first month after operation in hemi hip replacement, and has comparative advantages in promoting early postoperative rehabilitation of elderly patients with femoral neck.

Ruthenium-Catalyzed 1,6-Hydroalkylation of para-Quinone Methides with Ketones via the in Situ Activation of C(sp3)-H Bonds.

A simple and efficient method for the ruthenium-catalyzed 1,6-hydroalkylation of para-quinone methides (p-QMs) with ketones via the in situ activation of C(sp3)-H bonds has been disclosed. Without the need for preactivation of the substrates and oxidant, a broad range of p-QMs and ketones are well tolerated, producing the expected 1,6-hydroalkylation products with moderate to good yields. Step-by-step control experiments and DFT calculation were conducted systematically to gain insights for the plausible reaction mechanism. This finding may have potential application in the selective diarylmethylation of ketones at the α-C position in organic synthesis.

CCA repair or ECA ligation-Which middle cerebral artery occlusion is better in the reperfusion mouse model?

A reliable animal model is essential for ischemic stroke research. The implications of the external carotid artery (ECA) transection or common carotid artery (CCA) ligation have been described. Thus, a modified animal model, the CCA-repair model, has been established, and studies have shown that the CCA-repair model has potential advantages over the CCA-ligation model. However, whether the CCA-repair model is superior to the ECA-ligation model remains unclear. Sixty male C57BL/6 mice were randomly assigned to establish the CCA-repair (n = 34) or ECA-ligation (n = 26) models. Cerebral blood flow before middle cerebral artery occlusion (MCAO), immediately after MCAO and reperfusion were monitored and the operation duration, postoperative body weight, and food intake within 7 days, and the number of intraoperative and postoperative deaths within 7 days were recorded in the two models. Modified neurological severity scores and Bederson (0-5) scores were used to evaluate postoperative neurological function deficits on Days 1/3/5/7. 2,3,5-Triphenyltetrazolium chloride staining was used to quantify lesion volume on Day 7 after the operation. We found the establishment of the CCA-repair model required a longer total operation duration (p = 0.0175), especially the operation duration of reperfusion (p < 0.0001). However, there was no significant difference in body weight and food intake development, lesion volume and intragroup variability, neurological function deficits, mortality, and survival probability between the two groups. The CCA-repair model has no significant advantage over the ECA-ligation model. The ECA-ligation model is still a better choice for focal cerebral ischemia.

High-risk human papillomavirus distribution in different cytological classification women.

High-risk human papillomavirus (HR-HPV) infection is a major cause of infection-related cancer worldwide. 3101 HR-HPV-positive females were retrospectively analyzed and grouped using the cervical cytological screening (ThinPrep cytological test, TCT) evaluations combined with colposcopy. The HPV16 infection rate is the highest in all groups. HPV16 was the most frequent in each group, with significant differences between the four groups (χ2 = 23.41, P = 0.0001). The distribution of HPV16 and HPV33 correlated with the pathologic stage in each group. The mixed infection rate of mRNA testing differs significantly between groups (P < 0.01, χ2 = 17.44, P = 0.002). HR-HPV infection duration of less than six months accounted for 87.65%, 6 and 12 months of persistent infection (28.28%), and more than one year of continuous infection accounted for only 16.48%. The top three HPV types in a group with a duration of more than 12 months were HPV52 (3.03%), HPV16 (2.55%), and HPV39 (1.58%). The least clearance types were HPV39 (63.48%), 56 (69.54%), and 52 (71.44%) more than 12 months. This study revealed the region's primary pathogenic subtypes on different cervical lesions and provided the basis for diagnosing and treating HPV infection.

Regulating local molecular polarization of triazine-PDI based polymer for high-efficient photocatalytic coupling of benzylamine.

Designing a robust built-in electric field (BF) is a charming strategy for enhancing the separation and transportation of charges via introducing large π-conjugated molecules. However, it has flexible or semiflexible geometries, which significantly disorder the crystalline and deteriorated the built-in electric field. Here, a straightforward tactic for creating a cyano-functionalized smaller D (benzene) - A (triazine) units in PDI- triazine based polymer (PDIMB) to enhance intrinsic molecule dipole has been proposed. The density functional theory (DFT) calculation revealed that the modification of smaller D-A groups destroyed the π-localization of charges, which enhanced the molecular dipole and the BF for promoting the exciton dissociation and charge transfer. Moreover, it not only exposed number of active sites, but also enhanced the interfacial molecular interacting. Therefore, PDIMB-2 exhibits high activity (24.5 mmol g-1 h-1) and selectivity (>99%) for the photooxidation of benzylamine to N-benzylidenebenzylamine under mild conditions. Our work offers a potential and simple synthetic option for enhancing the built-in electric field of polymer.

Recent Progress on Nitrogen-Rich Energetic Materials Based on Tetrazole Skeleton.

Development of nitrogen-rich energetic materials has gained much attention because of their remarkable properties including large nitrogen content and energy density, good thermal stability, low sensitivity, good energetic performance, environmental friendliness and so on. Tetrazole has the highest nitrogen and highest energy contents among the stable azoles. The incorporation of diverse explosophoric groups or substituents into the tetrazole skeleton is beneficial to obtain high-nitrogen energetic materials having excellent energetic performance and suitable sensitivity. In this review, the development of high-nitrogen energetic materials based on tetrazole skeleton is highlighted. Initially, the property and utilization of nitrogen-rich energetic materials are presented. After showing the advantage of the tetrazole skeleton, the high-nitrogen energetic materials based on tetrazole are classified and introduced in detail. Based on different types of energetic materials (EMs), the synthesis and properties of nitrogen-rich energetic materials based on mono-, di-, tri- and tetra-tetrazole are summarized in detail.

Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles.

A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis-Arbuzov rearrangement for the synthesis of ß-ketophosphine oxides, ß-ketophosphinates, and ß-ketophosphonates is reported. The present reaction could be conducted effectively without the use of a ligand and a base. Various kinds of aryl acrylic acids and P(III)-nucleophiles are tolerated in the transformation, generating the desired ß-keto-organophosphorus compounds as a valuable class of phosphorus-containing intermediates with good to excellent yields. In addition, the possible mechanism and kinetic studies for the reaction have been explored by step-by-step control experiments and competitive experiments, and the results proved that this transformation may follow second-order chemical kinetics as well as involve a radical process.

Uniform Lithium Plating for Dendrite-Free Lithium Metal Batteries: Role of Dipolar Channels in Poly(vinylidene fluoride) and PbZrxTi1-xO3 Interface.

Conventional polymer/ceramic composite solid-state electrolytes (CPEs) have limitations in inhibiting lithium dendrite growth and fail to meet the contradictory requirements of anodes and cathodes. Herein, an asymmetrical poly(vinylidene fluoride) (PVDF)-PbZrxTi1-xO3 (PZT) CPE was prepared. The CPE incorporates high dielectric PZT nanoparticles, which enrich a dense thin layer on the anode side, making their dipole ends strongly electronegative. This attracts lithium ions (Li+) at the PVDF-PZT interface to transport through dipolar channels and promotes the dissociation of lithium salts into free Li+. Consequently, the CPE enables homogeneous lithium plating and suppresses dendrite growth. Meanwhile, the PVDF-enriched region at the cathode side ensures intermediate contact with positive active materials. Therefore, Li/PVDF-PZT CPE/Li symmetrical cells exhibit a stable cycling performance exceeding 1900 h at 0.1 mA cm-2 at 25 °C, outperforming Li/PVDF solid-state electrolyte/Li cells that fail after 120 h. The LiNi0.8Co0.1Mo0.1O2/PVDF-PZT CPE/Li cells show low interfacial impedances and maintain stable cycling performance for 500 cycles with a capacity retention of 86.2% at 0.5 C and 25 °C. This study introduces a strategy utilizing dielectric ceramics to construct dipolar channels, providing a uniform Li+ transport mechanism and inhibiting dendrite growth.

Introducing Bidirectional Axial Coordination into BiVO4 @Metal Phthalocyanine Core-Shell Photoanodes for Efficient Water Oxidation.

Core-shell photoanodes have shown great potential for photoelectrochemical (PEC) water oxidation. However, the construction of a high-quality interface between the core and shell, as well as a highly catalytic surface, remains a challenge. Herein, guided by computation, we present a BiVO4 photoanode coated with ZnCoFe polyphthalocyanine using pyrazine as a coordination agent. The bidirectional axial coordination of pyrazine plays a dual role by facilitating intimate interfacial contact between BiVO4 and ZnCoFe polyphthalocyanine, as well as regulating the electron density and spin configuration of metal sites in ZnCoFe phthalocyanine, thereby promoting the potential-limiting step of *OOH desorption. The resulting photoanode displayed a high photocurrent density of 5.7±0.1 mA cm-2 at 1.23 VRHE . This study introduces a new approach for constructing core-shell photoanodes, and uncovers the key role of pyrazine axial coordination in modulating the catalytic activity of metal phthalocyanine.

Surface Oxygen Species in Metal Oxide Photoanodes for Solar Energy Conversion.

Converting and storing solar energy directly as chemical energy through photoelectrochemical devices are promising strategies to replace fossil fuels. Metal oxides are commonly used as photoanode materials, but they still encounter challenges such as limited light absorption, inefficient charge separation, sluggish surface reactions, and insufficient stability. The regulation of surface oxygen species on metal oxide photoanodes has emerged as a critical strategy to modulate molecular and charge dynamics at the reaction interface. However, the precise role of surface oxygen species in metal oxide photoanodes remains ambiguous. The review focuses on elucidating the formation and regulation mechanisms of various surface oxygen species in metal oxides, their advantages and disadvantages in photoelectrochemical reactions, and the characterization methods employed to investigate them. Additionally, the article discusses emerging opportunities and potential hurdles in the regulation of surface oxygen species. By shedding light on the significance of surface oxygen species, this review aims to advance our understanding of their impact on metal oxide photoanodes, paving the way for the design of more efficient and stable photoelectrochemical devices.

Individualized 3D-printed navigation template-assisted tension band wiring for olecranon fractures.

PURPOSE: 3D printing techniques guide precision medicine and show great development potential in clinical applications. The purpose of this study was to compare the clinical outcomes of 3D-printed navigation templates versus free-hand in tension band wiring (TBW) procedures for olecranon fractures. METHODS: Patients who underwent TBW due to Mayo type II olecranon fractures between January 2019 and December 2021 in our hospital were prospectively enrolled in the study. The patients were divided into the 3D printed navigation template guiding TBW group (3D printed group) and the free-hand TBW group (free-hand group). The primary endpoint of this study was the success rate of the bicortical placement of Kirschner wires (K-wires). Times of intraoperative fluoroscopy, operation times, complications, VAS scores, and Mayo Elbow Performance Scores (MEPS) were analyzed as the secondary outcomes measure. RESULTS: The success rate of the bicortical placement of K-wires was 85.7% in the 3D Printed group was significantly higher than the free-hand group (60%). There were fewer times of intraoperative fluoroscopy in the 3D Printed group (1.43 ± 0.51) than that in the free-hand group (2.60 ± 1.00) with statistical significance (P < 0.05). At the date of the last follow-up, four patients suffer from pain and skin injury at the K-wires insertion site in the 3D Printed group and 14 patients in the free-hand group, a significant difference between the two groups (P < 0.05). No statistically significant differences were found in operation time, VAS scores, and MEPS between the two groups. CONCLUSIONS: The individualized 3D-printed navigation template-assisted TBW demonstrated good accuracy and resulted in reduced times of intraoperative fluoroscopy and complication compared to the free-hand TBW for olecranon fractures.