Background: Tuberculosis is a chronic infectious disease and an important public health problem. Despite progress in controlling tuberculosis, the incidence of tuberculosis in China is still very high, with 895000 new cases annually. This case report describes the investigation of a case of severe disseminated tuberculosis in a young adult with normal immune function, conducted to ascertain why a () strain caused such severe disease.
View Article and Find Full Text PDFA pair of cyclophane-encapsulated [Cu(μ-E)] complexes (E = S and Se) were characterized by resonant X-ray diffraction anomalous fine structure (DAFS), revealing unexpected polarization among the three Cu sites attributed to long-range effects of π-stacking interactions with cocrystallized benzene molecules. The resonant K-edge energies of individual Cu sites within the cluster molecules were found to vary as a function of distance from the cocrystallized benzene. This pattern was interpreted in the context of T-shaped, edge-to-face π-stacking with the assistance of theoretical charge density difference calculations.
View Article and Find Full Text PDFBackground: Stroke is a critical complication of cardiac surgery that results in increased mortality and morbidity. Limited treatment options are available for patients with severe neurological deficits, such as impaired consciousness. Acupuncture is a well-known integrative management method for stroke patients.
View Article and Find Full Text PDFIn the study of mononuclear transition metal single molecule magnets (SMMs), extensive research has concentrated on identifying optimal coordination geometries around the central metal ion to enhance SMM properties. However, the role of non-covalent interactions in the second coordination sphere has been relatively underexplored. Here, we study the impact of non-covalent Cl⋯H interactions on the magnetic anisotropy of the central Co(II) ion in the distorted axially compressed octahedral complex CoCl(tu) (1) (tu = SC(NH)).
View Article and Find Full Text PDFAnomalous X-ray diffraction (AXD) and neutron diffraction can be used to crystallographically distinguish between metals of similar electron density. Despite the use of AXD for structural characterization in mixed metal clusters, there are no benchmark studies evaluating the accuracy of AXD toward assessing elemental occupancy in molecules with comparisons with what is determined via neutron diffraction. We collected resonant diffraction data on several homo and heterometallic clusters and refined their anomalous scattering components to determine metal site occupancies.
View Article and Find Full Text PDFNumerous descriptions of structural isomerism in metal complexes do not list any molecular vs ionic isomers. At the same time, one of the most striking examples of structural isomerism in organic chemistry is molecular urea, which has the same atomic composition as the chemically distinct ionic ammonium cyanate. This iconic organic couple now meets its inorganic heterometallic counterpart.
View Article and Find Full Text PDFTwo POM@MOF hybrid materials composed of a copper-based metal-organic framework (MOF) [Cu(CHO)(HO)] (HKUST-1) encapsulating vanadium-substituted Keggin polyoxometalates (POM), [α-PVWO] () and [α-PVWO] (), were prepared and characterized. PVW@HKUST-1 and PVW@HKUST-1 were synthesized hydrothermally by self-assembly of HKUST-1 in the presence of the preformed POMs, [α-PVWO] and [α-PVWO], respectively. The two POM@MOF composites were characterized by X-ray diffraction, TGA, BET surface area analysis and FT-IR and Raman spectroscopy.
View Article and Find Full Text PDFCopper clusters feature prominently in both metalloenzymes and synthetic nanoclusters that mediate catalytic redox transformations of gaseous small molecules. Such reactions are critical to biological energy conversion and are expected to be crucial parts of renewable energy economies. However, the precise roles of individual metal atoms within clusters are difficult to elucidate, particularly for cluster systems that are dynamic under operating conditions.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
November 2024
The vertical flow (VF) method improves generation and collection efficiency in Raman spectroscopy. It enhances all Raman signals, including undesired signals of organic solvents having a considerably large Raman cross section. We constructed a Raman spectrometer using the VF method to overcome this drawback and introduced a spatial line rejection mask to eliminate unnecessary bands.
View Article and Find Full Text PDFStepwise metalation of the hexadentate ligand LH (LH = 1,3,5-CH(NHCH--NHSiMeBu)) affords bimetallic trinuclear clusters (L)FeZn(thf) and (L)FeZn(py). Reactivity studies were pursued to understand metal atom lability as the clusters undergo ligand substitution, redox chemistry, and group transfer processes. Chloride addition to (L)FeZn(thf) resulted in a mixture of species including both all-zinc and all-iron products.
View Article and Find Full Text PDFSince the onset of the COVID-19 pandemic in 2019, the role of weather conditions in influencing transmission has been unclear, with results varying across different studies. Given the changes in border policies and the higher vaccination rates compared to earlier conditions, this study aimed to reassess the impact of weather on COVID-19, focusing on local climate effects. We analyzed daily COVID-19 case data and weather factors such as temperature, humidity, wind speed, and a diurnal temperature range from 1 March to 15 August 2022 across six regions in Taiwan.
View Article and Find Full Text PDFA new perovskite KOsO_{3} has been stabilized under high-pressure and high-temperature conditions. It is cubic at 500 K (Pm-3m) and undergoes subsequent phase transitions to tetragonal at 320 K (P4/mmm) and rhombohedral (R-3m) at 230 K as shown from refining synchrotron x-ray powder diffraction (SXRD) data. The larger orbital overlap integral and the extended wave function of 5d electrons in the perovskite KOsO_{3} allow to explore physics from the regime where Mott and Hund's rule couplings dominate to the state where the multiple interactions are on equal footing.
View Article and Find Full Text PDFThe design and synthesis of polyhedra using coordination-driven self-assembly has been an intriguing research area for synthetic chemists. Metal-organic polyhedra are a class of intricate molecular architectures that have garnered significant attention in the literature due to their diverse structures and potential applications. Hereby, we report Cu-MOP, a bifunctional metal-organic cuboctahedra built using 2,6-dimethylpyridine-3,5-dicarboxylic acid and copper acetate at room temperature.
View Article and Find Full Text PDFN6-methyladenosine (mA) is a crucial RNA modification that regulates diverse biological processes in human cells, but its co-transcriptional deposition and functions remain poorly understood. Here, we identified the RNA helicase DDX21 with a previously unrecognized role in directing mA modification on nascent RNA for co-transcriptional regulation. DDX21 interacts with METTL3 for co-recruitment to chromatin through its recognition of R-loops, which can be formed co-transcriptionally as nascent transcripts hybridize onto the template DNA strand.
View Article and Find Full Text PDFWe propose a methodology to mitigate angular color variation in full-color micron-scale LED arrays. By simulating light field distribution for red (AlGaAs) and green/blue (GaN) light across various RGB micro-LED sizes, we can select matching light field patterns for RGB chips, reducing angular color variation from 0.0201 to 0.
View Article and Find Full Text PDFEnterovirus infection and enterovirus infection with severe complications (EVSC) are critical issues in several aspects. However, there is no suitable predictive tool for these infections. A climate factor complex (CFC) containing several climate factors could provide more effective predictions.
View Article and Find Full Text PDFCharge density waves (CDWs) involved with electronic and phononic subsystems simultaneously are a common quantum state in solid-state physics, especially in low-dimensional materials. However, CDW phase dynamics in various dimensions are yet to be studied, and their phase transition mechanism is currently moot. Here we show that using the distinct temperature evolution of orientation-dependent ultrafast electron and phonon dynamics, different dimensional CDW phases are verified in CuTe.
View Article and Find Full Text PDFBackground: Subarachnoid hemorrhage (SAH) is a life-threatening neurological disease that usually has a poor prognosis. Neurogenesis is a potential therapeutic target for brain injury. Ketone metabolism also plays neuroprotective roles in many neurological disorders.
View Article and Find Full Text PDFUnderstanding the electronic structures of high-valent metal complexes aids the advancement of metal-catalyzed cross coupling methodologies. A prototypical complex with formally high valency is [Cu(CF ) ] (1), which has a formal Cu(III) oxidation state but whose physical analysis has led some to a Cu(I) assignment in an inverted ligand field model. Recent examinations of 1 by X-ray spectroscopies have led previous authors to contradictory conclusions, motivating the re-examination of its X-ray absorption profile here by a complementary method, resonant diffraction anomalous fine structure (DAFS).
View Article and Find Full Text PDFMetalation of the polynucleating ligand LH (1,3,5-C H (NC H -4-F-2-NSiMe Bu) ) with two equivalents of Zn(N(SiMe ) ) affords the dinuclear product ( LH )Zn (1), which can be further deprotonated to yield ( L)Zn Li (OEt ) (2). Transmetalation of 2 with NiCl (py) yields the heterometallic, trinuclear cluster ( L)Zn Ni(py) (3). Reduction of 3 with KC affords [KC ][( L)Zn Ni] (4) which features a monovalent Ni centre.
View Article and Find Full Text PDFDithienylethenes (DTEs) are a promising class of organic photoswitches that can be used to create crystalline solids with properties controlled by light. However, the ability of DTEs to adopt multiple conformations, only one of which is photoactive, complicates the rational design of these materials. Herein, the synthesis and structural characterization of 19 crystalline solids containing a single DTE molecule are described.
View Article and Find Full Text PDFStudies of multinuclear metal complexes are greatly enhanced by resonant diffraction measurements, which probe X-ray absorption profiles of crystallographically independent metal sites within a cluster. In particular, X-ray diffraction anomalous fine structure (DAFS) analysis provides data that can be interpreted akin to site-specific XANES, allowing for differences in metal K-edge resonances to be deconvoluted even for different metal sites within a homometallic system. Despite the prevalence of Cu-containing clusters in biology and energy science, DAFS has yet to be used to analyze multicopper complexes of any type until now.
View Article and Find Full Text PDFOrganofunctionalized tetranuclear clusters [(M Cl) (V O) {((HOCH CH )(H)N(CH CH O))(HN(CH CH O) )} ] (1, M=Co, 2: M=Zn) containing an unprecedented oxometallacyclic {M V Cl N O } (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo-alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single-crystal X-ray diffraction structure analysis. The isostructural clusters are formed of edge-sharing octahedral {VO N} and trigonal bipyramidal {MO NCl} units.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
December 2023
Because of sulfite's potential toxicity, there is a growing concern about detecting and controlling its concentration in foods, alcoholic beverages, pharmaceuticals, and environmental samples to ensure public health. A branched polyethyleneimine-coated silver nano-star (AgNS@PEI) surface-enhanced Raman scattering (SERS) substrate was synthesized in this study for use as a sensitive, simple, rapid, stable, and reproducible non-destructible sulfite detection analytical technique. The seed morphology of the nano-star was created by using hydroxylamine (NHOH) solution as a primary reducing agent, followed by a slow secondary reduction by trisodium citrate dihydrate (HOC(COONa)(CHCOONa) 2HO), resulting in the complete growth of the silver nano-star.
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