Kinetically Controlled Structural Modulation of the Self-Assembled Silver Nanoclusters.

Metal nanoclusters (NCs) with atomic precision are growing into a fascinating class of building blocks for supramolecular chemistry. What makes it more interesting is the enhanced optical properties of the ordered structures, including aggregation-induced emission (AIE). However, algorithm dictating the self-assembly of metal NCs in multicomponent environment remains largely unknown, and effective means to manipulate the self-assembly is still lacking, especially under kinetic control. Herein, nanofibers which contain sub-1 nm nanowires and exhibit circularly polarized phosphorescence (CPP) are obtained from crystallization-induced self-assembly (CISA) of water-soluble, negatively charged silver NCs (Ag9 -NCs) in the presence of glutamic acid (Glu). By the introduction of a positively-charged additive (choline chloride, CC), the structure of the nanowires is modulated and the lateral interaction between adjacent nanofibers is adjusted, leading to simultaneous improvement of the phosphorescence and chirality which finally enhances CPP. Importantly, changing the time at which CC is introduced altered the kinetic pathway of the CISA, which enables to effectively manipulate both the final structures of the self-assembled Ag9 -NCs and the output of the optical signals.

Guest-Induced Reversible Single-Crystal-to-Single-Crystal Transformation Involving Displacement of 2D Layers and Spin Crossover Behavior Change in a Hofmann-Type Coordination Polymer.

A novel two-dimensional (2D) Hofmann-type coordination polymer, {FeII(PyHbim)2[Pd(CN)4]}·2CH3OH [1·2CH3OH, PyHbim = 2-(4-pyridyl)benzimidazole], has been synthesized, which can undergo a spontaneous guest exchange, transforming to 1·2H2O in a single-crystal-to-single-crystal (SCSC) manner, shifting from orthorhombic Cmmm to monoclinic C2/m involving the displacement of 2D layers. The solvent-induced SCSC transformation process was reversible and verified through powder X-ray diffraction (PXRD) and single-crystal X-ray crystallography analyses. Both 1·2CH3OH and 1·2H2O exhibit complete and abrupt spin crossover (SCO) behaviors in two steps, while their SCO temperature ranges drastically shift by ca.100 K, spanning room temperature, owing to different intermolecular interactions resulting from diverse interlayer packing manners and host-guest interactions. Besides, a structural phase transition is observed in 1·2CH3OH, contributing to the two-step spin transition.

Vanadium-Silsesquioxane Nanocages as Heterogeneous Catalysts for Synthesis of Quinazolinones.

The functionalization of polyoxovanadate clusters is promising but of great challenge due to the versatile coordination geometry and oxidation state of vanadium. Here, two unprecedented silsesquioxane ligand-protected "fully reduced" polyoxovanadate clusters were fabricated via a facial solvothermal methodology. The initial mixture of the two polyoxovanadate clusters with different colors and morphologies (green plate V14 and blue block V6) was successfully separated as pure phases by meticulously controlling the assembly conditions. Therein, the V14 cluster is the highest-nuclearity V-silsesquioxane cluster to date. Moreover, the transformation from a dimeric silsesquioxane ligand-protected V14 cluster to a cyclic hexameric silsesquioxane ligand-protected V6 cluster was also achieved, and the possible mechanism termed "ligand-condensation-involved dissociation reassembly" was proposed to explain this intricate conversion process. In addition, the robust V6 cluster was served as a heterogeneous catalyst for the synthesis of important heterocyclic compounds, quinazolinones, starting from 2-aminobenzamide and aldehydes. The V6 cluster exhibits high activity and selectivity to access pure quinazolinones under mild conditions, where the high selectivity was attributed to the confinement effect of the macrocyclic silsesquioxane ligand constraining the molecular freedom of the reaction species. The stability and recyclability as well as the tolerance of a wide scope of aldehyde substrates endow the V6 cluster with a superior performance and appreciable potential in catalytic applications.

Silver(I) Complexes with Mefenamic Acid and Nitrogen Heterocyclic Ligands: Synthesis, Characterization, and Biological Evaluation.

Four Ag(I) complexes with mefenamato and nitrogen heterocyclic ligands, [Ag(2-apy)(mef)]2 (1), [Ag(3-apy)(mef)] (2), [Ag2(tmpyz)(mef)2] (3), and {[Ag(4,4'-bipy)(mef)]2(CH3CN)1.5(H2O)2}n (4), (mef = mefenamato, 2-apy = 2-aminopyridine, 3-apy = 3-aminopyridine, tmpyz = 2,3,5,6-tetramethylpyrazine, 4,4'-bipy = 4,4'-bipyridine), were synthesized and characterized. The interactions of these complexes with BSA were investigated by fluorescence spectroscopy, which indicated that these complexes quench the fluorescence of BSA by a static mechanism. The fluorescence data also indicated that the complexes showed good affinity for BSA, and one binding site on BSA was suitable for the complexes. The in vitro cytotoxicity of the four complexes against human cancer cell lines (MCF-7, HepG-2, A549, and MDA-MB-468) and one normal cell line (HTR-8) was evaluated by the MTT assay. Complex 1 displayed high cytotoxic activity against A549 cells. Further studies revealed that complex 1 could enhance the intracellular levels of ROS (reactive oxygen species) in A549 cells, cause cell cycle arrest in the G0/G1 phase, and induce apoptosis in A549 cells in a dose-dependent manner.

Adaptive responses to mTOR gene targeting in hematopoietic stem cells reveal a proliferative mechanism evasive to mTOR inhibition.

The mechanistic target of rapamycin (mTOR) is a central regulator of cell growth and an attractive anticancer target that integrates diverse signals to control cell proliferation. Previous studies using mTOR inhibitors have shown that mTOR targeting suppresses gene expression and cell proliferation. To date, however, mTOR-targeted therapies in cancer have seen limited efficacy, and one key issue is related to the development of evasive resistance. In this manuscript, through the use of a gene targeting mouse model, we have found that inducible deletion of mTOR in hematopoietic stem cells (HSCs) results in a loss of quiescence and increased proliferation. Adaptive to the mTOR loss, mTOR-/- HSCs increase chromatin accessibility and activate global gene expression, contrary to the effects of short-term inhibition by mTOR inhibitors. Mechanistically, such genomic changes are due to a rewiring and adaptive activation of the ERK/MNK/eIF4E signaling pathway that enhances the protein translation of RNA polymerase II, which in turn leads to increased c-Myc gene expression, allowing the HSCs to thrive despite the loss of a functional mTOR pathway. This adaptive mechanism can also be utilized by leukemia cells undergoing long-term mTOR inhibitor treatment to confer resistance to mTOR drug targeting. The resistance can be counteracted by MNK, CDK9, or c-Myc inhibition. These results provide insights into the physiological role of mTOR in mammalian stem cell regulation and implicate a mechanism of evasive resistance in the context of mTOR targeting.

Particulated juvenile cartilage allograft for the treatment of osteochondral lesions of the talus is associated with a high complication rate and a high failure rate at short-term follow-up: A systematic review.

PURPOSE: The purpose of this systematic review was to evaluate the clinical and radiological outcomes together with the complication rates and failure rates at short-term follow-up following particulated juvenile cartilage allograft (PJCA) for the management of osteochondral lesions of the talus (OLT). METHODS: During October 2023, the PubMed, Embase and Cochrane library databases were systematically reviewed to identify clinical studies examining outcomes following PJCA for the management of OLTs. Data regarding study characteristics, patient demographics, lesion characteristics, subjective clinical outcomes, radiological outcomes, complications and failures were extracted and analysed. RESULTS: Twelve studies were included. In total, 241 patients underwent PJCA for the treatment of OLT at a weighted mean follow-up of 29.0 ± 24.9 months. The weighted mean lesion size was 138.3 ± 59.6 mm2 . Prior surgical intervention was recorded in seven studies, the most common of which was microfracture (65.9%). The weighted mean American Orthopaedic Foot and Ankle Society score improved from a preoperative score of 58.5 ± 3.2 to a postoperative score of 83.9 ± 5.3. The weighted mean postoperative magnetic resonance observation of cartilage repair tissue (MOCART) score was 48.2 ± 3.3. The complication rate was 25.2%, the most common of which was allograft hypertrophy (13.2%). Thirty failures (12.4%) were observed at a weighted mean time of 9.8 ± 9.6 months following the index procedure. CONCLUSION: This systematic review demonstrated a moderate improvement in subjective clinical outcomes following PJCA for the treatment of OLT at short term follow-up. However, postoperative MOCART scores were reported as poor. In addition, a high complication rate (25.2%) and a high failure rate (12.4%) at short-term follow-up was observed, calling into question the efficacy of PJCA for the treatment of large OLTs. In light of the available evidence, PJCA for the treatment of large OLTs cannot be currently recommended. LEVEL OF EVIDENCE: Level IV.

Synthesis, Structural Characterization, and Hirschfeld Surface Analysis of a New Cu(II) Complex and Its Role in Photocatalytic CO2 Reduction.

A new Cu(II) complex, [CuL1L2(CH3COO)2(H2O)]·H2O, was synthesized by the reaction of Cu(CH3COO)2·H2O, 6-phenylpyridine-2-carboxylic acid (HL1), and 4-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]pyridine (L2) in ethanol-water (v:v = 1:1) solution. The Cu(II) complex was characterized using elemental analysis, IR, UV-vis, TG-DTA, and single-crystal X-ray analysis. The fluorescence properties of the copper complex were also evaluated. The structural analysis results show that the Cu(II) complex crystallizes in the triclinic system with space group P-1. The Cu(II) ion in the complex is five-coordinated with one O atom (O2) and one N atom (N1) from one 6-phenylpyridine-2-carboxylate ligand (L1), one N atom (N2) from 4-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]pyridine ligand (L2), one O atom (O4) from acetate, and one O atom (O5) from a coordinated water molecule, and it adopts a distorted trigonal bipyramidal geometry. Cu(II) complex molecules form a two-dimensional layer structure through intramolecular and intermolecular O-H…O hydrogen bonding. The two-dimensional layer structures further form a three-dimensional network structure by π-π stacking interactions of aromatic rings. The analysis of the Hirschfeld surface of the Cu(II) complex shows that the H…H contacts made the most significant contribution (46.6%) to the Hirschfeld surface, followed by O…H/H…O, N…H/H…N and C…H/H…C contacts with contributions of 14.2%, 13.8%, and 10.2%, respectively. In addition, the photocatalytic CO2 reduction using Cu(II) complex as a catalyst is investigated under UV-vis light irradiation. The findings reveal that the main product is CO, with a yield of 10.34 µmol/g and a selectivity of 89.4% after three hours.

The comparison of postoperative outcomes in Morton's neuroma excision between plantar versus dorsal approach: A systematic review and meta-analysis.

BACKGROUND: Current literature lacks comprehensive information comparing the clinical outcomes of plantar and dorsal approaches for Civinini-Morton syndrome, also known as Morton's neuroma. This systematic review and meta-analysis was conducted to evaluate and compare the clinical outcomes of neurectomy for Morton's neuroma, focusing on the differences between the plantar and dorsal approach. METHODS: Our comprehensive literature review adhered to the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines and utilized databases including PubMed, Embase, Web of Science, and the Cochrane Library. Data investigated in this study included postoperative sensory loss, scar tenderness, reoperation, histopathology, complications, pain score, patient satisfaction, functional scores, and time to weight bearing. RESULTS: Total eight studies were included in this study. In aggregate, 237 neuromas underwent excision using the plantar approach, while 312 neuromas were treated via the dorsal approach. A significantly higher rate of postoperative reduced sensory was found in the dorsal group: 48.5 % (64/132) Vs. 62.0 % (80/129) with the relative ratio (RR) of 0.79 (95 % CI, 0.64-0.97). A significantly higher rate of postoperative scar tenderness was noted in the plantar group: 16.7 % (32/192) Vs. 6.2 % (14/225) with the RR of 2.27 (95 % CI, 1.28-4.04). Regarding the histopathology, 99.3 % (143/144) and 97.1 % (134/138) accuracy rate was confirmed in the plantar approach and dorsal approach, respectively, with the RR of 1.02 (95 % CI, 0.98-1.07). Overall reoperations and complications were not different between groups at 5.3 % (10/189) and 8.8 % (19/216) in the plantar group versus 6.1 % and 12.0 % (35/291) in dorsal group. CONCLUSIONS: We recommend detailed discussions with patients prior to surgery to weigh the advantages and disadvantages of each approach.

Temperature-Controlled Selective Formation of Silver Nanoclusters and Their Transformation to the Same Product.

Herein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO4 2- and/or Cl-), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20-80 °C). Interestingly, fine-tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4-bis(pyrid-4-yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage-reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability.

The significance of heterotopic ossification following total ankle arthroplasty: a systematic review and meta-analysis.

PURPOSE: The purpose of this systematic review and meta-analysis was to evaluate the prevalence and clinical significance of heterotopic ossification (HO) following total ankle replacement (TAR). METHODS: During August 2023, the PubMed, Embase and Cochrane library databases were systematically reviewed to identify clinical studies reporting HO following TAR. Data regarding surgical characteristics, pathological characteristics, subjective clinical outcomes, ankle range of motion, radiographic outcomes, reoperation rates were extracted and analysed. RESULTS: Twenty-seven studies with 2639 patients (2695 ankles) at a weighed mean follow-up time of 52.8 ± 26.9 months were included. The pooled prevalence rate was 44.6% (0.25; 0.66). The implant with the highest rate of HO was the INBONE I (100%) and BOX (100%) implants. The most common modified Brooker staging was grade 1 (132 patients, 27.0%). Random effects models of standardized mean differences found no difference in American orthopedic foot and ankle society (AOFAS) scores, visual analog scale scores (VAS) and ankle range of motion (ROM) between patients with HO and patients without HO. Random effects models of correlation coefficients found no correlation between AOFAS, VAS and ROM and the presence of HO. The surgical intervention rate for symptomatic HO was 4.2%. CONCLUSION: This systematic review and meta-analysis found that HO is a common finding following TAR that is not associated with inferior clinical outcomes. Surgical intervention was required only for moderate-to-severe, symptomatic HO following TAR. This study is limited by the marked heterogeneity and low level and quality of evidence of the included studies. Further higher quality studies are warranted to determine the precise prevalence and impact of HO on outcomes following TAR.

Polyvinyl alcohol hydrogel implant for the treatment of hallux rigidus is associated with a high complication rate and moderate failure rate at short-term follow-up: a systematic review.

PURPOSE: Moderate-to-severe hallux rigidus is a debilitating pathology that is optimally treated with surgical intervention. Arthrodesis produces reliable clinical outcomes but is limited by restriction in 1st metatarsophalangeal joint range of motion. The advent of polyvinyl alcohol hydrogel (PVA) implants have produced early promise based on initial trials, but more recent studies have called into question the efficacy of this procedure. The purpose of this systematic review was to evaluate the clinical and radiological outcomes following the use of PVA for hallux rigidus. METHODS: The MEDLINE, EMBASE and Cochrane library databases were systematically reviewed using the preferred reporting items for systematic reviews and meta-analyses guidelines. 18 studies were included. RESULTS: In total, 1349 patients (1367 feet) underwent PVA at a weighted mean follow-up of 24.1 ± 11.1 months. There were 168 patients (169 feet) included in the cheilectomy cohort and 322 patients (322 feet) included in the arthrodesis cohort. All 3 cohorts produced comparable improvements in subjective clinical outcomes. Postoperative imaging findings in the PVA cohort included joint space narrowing, peri-implant fluid, peri-implant edema and erosion of the proximal phalanx. The complication rate in the PVA cohort, cheilectomy cohort and arthrodesis cohort was 27.9%, 11.8% and 24.1%, respectively. The failure rates in the PVA cohort, cheilectomy cohort and arthrodesis cohort was 14.8%, 0.3% and 9.0%, respectively. CONCLUSION: This systematic review demonstrated that PVA produced a high complication rate (27.9%) together with concerning postoperative imaging findings at short-term follow-up. In addition, a moderate failure rate (14.8%) and secondary surgical procedure rate (9.5%) was noted for the PVA cohort. The findings of this review calls into question the efficacy and safety of PVA for the treatment of hallux rigidus. LEVEL OF EVIDENCE: IV.

In-Office Needle Arthroscopy for the Foot and Ankle.

In-office needle arthroscopy (IONA) has been a readily available tool dating back to the 1990s, primarily for diagnostic purposes. This technique was not fully accepted and implemented because of significant limitations with the image quality and lack of instrumentation available to simultaneously treat the identified pathologies. However, recent advancements in IONA technology have made it possible to perform arthroscopic procedures under local anesthesia in the office setting, which once required a full operating suite. IONA has revolutionized how we treat foot and ankle pathologies in our practice. IONA allows the patient to be an active participant in the procedure and provides an interactive experience. IONA can be used to treat a range of foot and ankle pathologies, including anterior ankle impingement, posterior ankle impingement, osteochondral lesions of the ankle joint, hallux rigidus, lateral ankle ligament repair, and tendoscopic treatment of Achilles, peroneal, and posterior tibial tendon disorders. Excellent outcomes with regard to subjective clinical outcomes, return to play times, and complications have been reported following IONA for these pathologies.

Supramalleolar osteotomy for the treatment of ankle osteoarthritis leads to favourable outcomes and low complication rates at mid-term follow-up: a systematic review.

PURPOSE: The purpose of this systematic review was to evaluate both the clinical and radiographic outcomes following supramalleolar osteotomy (SMO) in patients with ankle osteoarthritis, and to analyse the level of evidence (LOE) and quality of evidence (QOE) of the included studies. METHODS: A systematic review of the MEDLINE, EMBASE, and Cochrane Library databases was performed in accordance with the Preferred Reporting Items for Systematic Reviews and Meta-Analyses guidelines. Studies reporting clinical data following SMO for the treatment of ankle osteoarthritis were included and assessed. The level and quality of evidence of the included studies were also evaluated. RESULTS: Twenty-four studies with 1160 patients (1182 ankles) were included. Overall, 78.8% patients presented with post-traumatic ankle osteoarthritis. The weighted mean AOFAS score improved from 52.6 ± 9.7 (range 33.8-78.4) preoperatively to 78.1 ± 5.7 postoperatively at weighted mean follow-up of 50.4 ± 18.6 months (range 24.5-99.0). The most frequently utilised radiographic parameter was the tibial anterior surface angle, which improved from a preoperative weighted mean of 86.3° ± 5.6° (range 76.0°-102.0°) to a postoperative weighted mean of 89.9° ± 3.7° (range 84.9°-99.6°). The complication rate was 5.1% with non-union as the most commonly reported complication (1.6%). Secondary procedures were carried out in 28.2% of patients, the most common of which was implant and hardware removal (17.6%). The failure rate was 6.8%. Two studies were LOE II, 3 studies were LOE III, and 19 studies were LOE IV. The mean Modified Coleman Methodology Score was 59.3 ± 6.6 and the mean MINORS criteria score of all the included studies was 9.5 ± 3.7. CONCLUSION: This systematic review demonstrates good clinical and radiological outcomes, together with a low failure rate at mid-term follow-up following supramalleolar osteotomy in patients with ankle osteoarthritis. However, a moderate reoperation rate (28.2%) was reported. A low failure rate (6.8%) was reported, which must be interpreted in light of the shortcomings of the design of the included studies and a relatively short follow-up period. In addition, there is a low level and quality of evidence in the current literature with inconsistent reporting of data which underscores the need for further higher quality research to be conducted. Our review highlights that SMO may be an effective and safe procedure in the setting of early-to-intermediate-stage ankle osteoarthritis. LEVEL OF EVIDENCE: IV.

Increased incidence of acute achilles tendon ruptures in the peri-pandemic COVID era with parallels to the 2021-22 NFL season.

PURPOSE: Acute Achilles tendon ruptures (AATRs) are a common sporting injury, whether for recreational athletes or elite athletes. Prior research has shown returning to physical activity after extended periods of inactivity leads to increased rates of musculoskeletal injuries. The purpose of this study was to investigate rates of acute Achilles' tendon ruptures at a single academic institute in the peri-COVID era, with corollary to the recent NFL season. METHODS: A retrospective search was conducted using current procedural terminology to identify the total number of Achilles acute primary repair surgeries performed from years 2017 to 2021. Non-operatively managed AATRs were identified from the same electronic medical record using ICD-10 codes. NFL data were obtained from publicly available sites according to previously validated studies. RESULTS: A total of 588 patients who sustained AATRs and underwent primary surgical repair were identified, primarily men (75.7%, n = 445), with an average age of 43.22 ± 14.4 years. The number and corresponding incidence of AATR repairs per year was: 2017: n = 124 (21.1%), 2018: n = 110 (18.7%), 2019: n = 130 (22.1%), 2020: n = 86 (14.6%), 2021: n = 138 (23.5%), indicating a 7.5% decrease in rate of AATRs from 2019 to 2020, followed by an 8.9% increase in incidence from 2020 to 2021. Within the NFL, the number of AATRs resulting in an injured reserve stint increased every regular season from 2019 to 2020: n = 11 (21.2%), to 2020-2021: n = 17 (32.7%), to this past 2021-2022 season: n = 24 (46.2%). CONCLUSION: AATR surgeries seem to have increased in 2021 following a 2020 COVID pandemic-induced quarantine for recreational athletes at a single academic institution and for professional athletes in the NFL, although these results are of questionable clinical significance. This provides prognostic information when counseling patients and athletes on return to activity or sport. LEVEL OF EVIDENCE: Level IV.

Lower re-rupture rates but higher complication rates following surgical versus conservative treatment of acute achilles tendon ruptures: a systematic review of overlapping meta-analyses.

PURPOSE: To systematically review and evaluate the current meta-analyses for the treatment of acute Achilles tendon rupture (AATR). This study can provide clinicians with a clear overview of the current literature to aid clinical decision-making and the optimal formulation of treatment plans for AATR. METHODS: Two independent reviewers searched PubMed and Embase on June 2, 2022 based on the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. Assessment of evidence was twofold: level of evidence (LoE) and quality of evidence (QoE). LoE was evaluated using published criteria by The Journal of Bone and Joint Surgery and the QoE by the Assessing the Methodological Quality of Systematic Reviews (AMSTAR) scale. Pooled complication rates were highlighted for significance in favour of one treatment arm or no significance. RESULTS: There were 34 meta-analyses that met the eligibility criteria, with 28 studies of LoE 1, and the mean QoE was 9.8 ± 1.2. Significantly lower re-rupture rates were reported with surgical (2.3-5%) versus conservative treatment (3.9-13%), but conservative treatment was favoured in terms of lower complication rates. The re-rupture rates were not significantly different between percutaneous repair or minimally invasive surgery (MIS) compared to open repair, but MIS was favoured in terms of lower complication rates (7.5-10.4%). When comparing rehabilitation protocols following open repair (four studies), conservative treatment (nine studies), or combined (three studies), there was no significant difference in terms of re-rupture or obvious advantage in terms of lower complication rates between early versus later rehabilitation. CONCLUSION: This systematic review found that surgical treatment was significantly favoured over conservative treatment for re-rupture, but conservative treatment had lower complication rates other than re-rupture, notably for infections and sural nerve injury. Open repair had similar re-rupture rates to MIS, but lower complication rates; however, the rate of sural nerve injuries was lower in open repair. When comparing earlier versus later rehabilitation, there was no difference in re-rupture rates or obvious advantage in complications between open repair, conservative treatment, or when combined. The findings of this study will allow clinicians to effectively counsel their patients on the postoperative outcomes and complications associated with different treatment approaches for AATR. LEVEL OF EVIDENCE: IV.

Arsenic release dynamics of paddy field soil during groundwater irrigation and natural flooding.

Irrigation water in rice cultivation significantly affects the arsenic (As) mobilization in the paddy field soil. This research assessed the effect of rainwater (RW) and groundwater (GW) on the dissolution dynamics of arsenic (As) in paddy field soil. Up-flow column flooding experiments were conducted continuously for 80 d with simulated RW and GW to evaluate As dissolution phenomena in actual field conditions. Arsenic dissolution from the soil was lower in GW (309 µg/kg) irrigation than in RW flooding conditions (1086 µg/kg). The redox potential (Eh) of the soil pore water decreased, and pH increased over-irrigation time in both flooding conditions. The dissolution of arsenic (As) and iron (Fe) in the soil pore increased, while the dissolution of manganese (Mn) decreased over flooding time. The release of As in the soil pore water was attributed to the dissolution of Fe-As and Mn-As minerals and microbial reduction of As. Fe-As dissolution ratios in the soil pore water were relatively low and estimated as 0.68 mol/mol and 4.9 mol/mol for RW and GW, respectively. The dissolution of As and Mn dominated in the initial phase (0-40 d) of flooding, while the dissolution of As and Fe dominated in the second phase (40-80 d). The release of As was much lower in GW flooding than in RW flooding conditions. The Presence of Ca, Mg, and Mn in the GW facilitated the reduction of As dissolution by precipitating Ca-As and Mg-As and the oxidizing dissolved Mn in the soil pore water. The findings of this study provide valuable insights into the mechanisms of As release during monsoon flooding and groundwater flooding to assess the potential risks of As contamination in rice grown in paddy field soils.

Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters.

Accurate identifying and in-depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect-activity relationships. Yet, atomically precise coinage-metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed-ligand strategy to synthesizing an intrinsically chiral and metal-deficient copper hydride-rich NC [Cu57 H20 (PET)36 (TPP)4 ]+ (Cu57 H20 ). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu57 H20 features a cube-like Cu8 kernel embedded in a corner-missing metal-ligand shell of Cu49 (PET)36 (TPP)4 . Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono-lacunary polyoxometalates. Theoretical calculations demonstrate that the above-mentioned point vacancy causes one surface hydride exposed as an interfacial capping µ3 -H- , which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu57 H20 shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well-defined chiral metal-deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis.

Limited evidence of adjuvant biologics with bone marrow stimulation for the treatment of osteochondral lesion of the talus: a systematic review.

PURPOSE: To evaluate the complication rates, continuous functional outcome scores, and return to play data following bone marrow stimulation (BMS) versus biologics ± BMS for the treatment of osteochondral lesion of the talus (OLT). METHODS: A systematic review was performed. The PubMed and Embase databases were searched using specific search terms and eligibility criteria according to the PRISMA guidelines. The level of evidence was assessed using published criteria by The Journal of Bone & Joint Surgery, and the quality of evidence using the Modified Coleman Methodology Score. Continuous variables were presented as mean ± standard deviation and categorical variables as frequencies (percentages). RESULTS: BMS versus BMS + hyaluronic acid (HA): no complications in either treatment arm were reported. The mean American Orthopaedic Foot and Ankle Society score was 43.5 to 67.3 points and 44.0 to 72.4 points, respectively. The mean 10 mm Visual Analogue Scale pain score was 7.7 to 3.8 points and 7.5 to 2.5 points, respectively. BMS versus BMS + concentrated bone marrow aspirate (CBMA): the pooled overall complication rate was 17/64 (26.6%) versus 11/71 (15.5%), respectively (non-significant). The pool revision rate was 15/64 (23.4%) versus 6/71 (8.5%), respectively (p = 0.016). There has been a notable poor reporting of complication rates for the use of ADSC and PRP as adjuvant biological therapies to BMS for the treatment of OLT. CONCLUSION: There was an overall limited comparative clinical evidence of adjuvant biologics with BMS versus BMS alone for the treatment of OLT. BMS + HA and BMS + CBMA can provide superior outcomes, albeit the currently limited evidence. Further studies are warranted to establish the true clinical superiority of the various biologics ± BMS versus BMS alone. These studies must also compare the various biologics against one another to determine, if any, the optimal biologic for OLT. Clinicians should counsel patients accordingly on these findings as required. LEVEL OF EVIDENCE: Level III.

Anatomy of the tibial nerve in relation to the tarsal tunnel: A cadaveric study.

BACKGROUND: Tarsal tunnel syndrome (TTS) is typically caused by an anatomical variant or mechanical compression of the tibial nerve (TN) with variable success after surgical treatment. METHOD: 40 lower-leg specimens were obtained. Dissections were appropriately conducted. Extremities were prepared under formaldehyde solution. The tibial nerve and branches were dissected for measurements and various characteristics. RESULTS: The flexor retinaculum had a denser consistency in 22.5% of the cases and the average length was 51.9 mm. The flexor retinaculum as an independent structure was absent and 77.2% of cases as an undistinguished extension of the crural fascia. The lateral plantar nerve (LPN) and abductor digiti minimi (ADM) nerve shared same origin in 80% of cases, 34.5% bifurcated proximal to the DM (Dellon-McKinnon malleolar-calcaneal line) line 31.2% distally and 34.3% at the same level. CONCLUSION: Understanding the tibial nerve anatomy will allow us to adapt our surgical technique to improve the treatment of this recurrent pathology.

Synthesis, Molecular Docking and Biological Evaluation of 2-Aryloxy-N-Phenylacetamide and N'-(2-Aryloxyoxyacetyl) Benzohydrazide Derivatives as Potential Antibacterial Agents.

A new class of 2-aryloxy-N-phenylacetamide and N'-(2-aryloxyoxyacetyl) benzohydrazide derivatives with different active moieties were synthesized and screened for their antibacterial activity. Structural characterization of synthesized compounds was performed using HR-MS, 1 H-NMR, and 13 C-NMR spectral data. Amongst the synthesized compounds, 4-{2-[2-(2-chloroacetamido)phenoxy]acetamido}-3-nitrobenzoic acid (3h) and 2-chloro-N-(2-{2-[2-(2-chlorobenzoyl)hydrazinyl]-2-oxoethoxy}phenyl)acetamide (3o) have shown good antibacterial activity against a selected panel of bacteria. Besides, compounds also exhibited bactericidal activity against P. aeruginosa (3h, 0.69 µg/mL) and S. aureus (3o, 0.62 µg/mL) as evident by MBC and time-kill kinetics studies. In silico molecular docking and ADMET properties of newly synthesized compounds revealed that compounds could be considered as promising antibacterial agents.