Determinants of macaques' space use: A test for the ecological constraints model using GPS collars.

As a central topic in Behavioral Ecology, animal space use involves dynamic responses to social and ecological factors. We collared 22 rhesus macaques (Macaca mulatta) from six groups on Neilingding Island, China, and collected 80,625 hourly fixes over a year. Using this high-resolution location data set, we quantified the macaques' space use at the individual level and tested the ecological constraints model while considering various environmental and human interfering factors. As predicted by the ecological constraints model, macaques in larger groups had longer daily path lengths (DPLs) and larger home ranges. We found an inverted U-shape relationship between mean daily temperatures and DPLs, indicating that macaques traveled farther on mild temperature days, while they decreased DPLs when temperatures were too high or too low. Anthropogenic food subsidies were positively correlated to DPLs, while the effect of rainfall was negative. Macaques decreased their DPLs and core areas when more flowers and less leaves were available, suggesting that macaques shifted their space use patterns to adapt to the seasonal differences in food resources. By applying GPS collars on a large number of individuals living on a small island, we gained valuable insights into within-group exploitation competition in wild rhesus macaques.

Current status and continuing medical education need for general practitioners in Tibet, China: a cross-sectional study.

BACKGROUND: The Tibetan area is one of China's minority regions with a shortage of general practice personnel, which requires further training and staffing. This research helps to understand the current condition and demand for general practitioner (GP) training in Tibetan areas and to provide a reference for promoting GP education and training. METHODS: We conducted a cross-sectional survey using stratified sampling targeting 854 GPs in seven cities within the Tibetan Autonomous Region, utilizing an online questionnaire. Achieving a high response rate of 95.1%, 812 GPs provided invaluable insights. Our meticulously developed self-designed questionnaire, available in both Chinese and Tibetan versions, aimed to capture a wide array of data encompassing basic demographics, clinical skills, and specific training needs of GPs in the Tibetan areas. Prior to deployment, the questionnaire underwent rigorous development and refinement processes, including expert consultation and pilot testing, to ensure its content validity and reliability. In our analysis, we employed descriptive statistics to present the characteristics and current training needs of GPs in the Tibetan areas. Additionally, chi-square tests were utilized to examine discrepancies in training needs across various demographic groups, such as age, job positions, and educational backgrounds of the participating GPs. RESULTS: The study was completed by 812 (812/854, 95.1%) GPs, of whom 62.4% (507/812) were female. The top three training needs were hypertension (81.4%, 661/812), pregnancy management (80.7%, 655/812), and treatment of related patient conditions and events (80.5%, 654/812). Further research shows that the training required by GPs of different ages in "puncturing, catheterization, and indwelling gastric tube use" (64.6% vs. 54.8%, p = 9.5 × 10- 6) varies statistically. GPs in various positions have different training needs in "community-based chronic disease prevention and management" (76.6% vs. 63.9%, p = 0.009). The training needs of GPs with different educational backgrounds in "debridement, suturing, and fracture fixation" (65.6% vs. 73.2%, p = 0.027) were also statistically significant. CONCLUSIONS: This study suggests the need for targeted continuing medical education activities and for updating training topics and content. Course developers must consider the needs of GPs, as well as the age, job positions, and educational backgrounds of GPs practicing in the Tibetan Plateau region. TRIAL REGISTRATION: Not applicable.

C-O Bond Activation in Mononuclear Lanthanide Oxocarbonyl Complexes OLn(η2-CO) (Ln = La, Ce, Pr, and Nd).

Fundamental investigation of metal-CO interactions is of great importance for the development of high-performance catalysts to CO activation. Herein, a series of side-on bonded mononuclear lanthanide (Ln) oxocarbonyl complexes OLn(η2-CO) (Ln = La, Ce, Pr, and Nd) have been prepared and identified in solid argon matrices. The complexes exhibit uncommonly low C-O stretching bands near 1630 cm-1, indicating remarkable C-O bond activation in these Ln analogues. The η2-CO ligand in OLn(η2-CO) can be claimed as an anion on the basis of the experimental observations and quantum chemistry investigations, although the CO anion is commonly considered to be unstable with electron auto-detachment. The CO activation in OLn(η2-CO) is attributed to the photoinduced intramolecular charge transfer from LnO to CO rather than the generally accepted metal → CO π back-donation, which conforms to the traditional Dewar-Chatt-Duncanson motif. Energy decomposition analysis combined with natural orbitals for chemical valence calculations demonstrates that the bonding between LnO and η2-CO arises from the combination of dominant ionic forces (>76%) and normal Lewis "acid-base" interactions. The fundamental findings provide guidelines for the catalyst design of CO activation.

CO Oxidation to CO2 on Uranium Dioxide Molecules through Intermediate O2U(η1-CO).

Investigations on the reactions of uranium oxide molecules with CO offer new inspiration for the design of promising high-efficiency catalysts for CO activation using actinide materials. Herein, we contribute a combined matrix-isolation infrared spectroscopic and theoretical study of CO oxidation to CO2 on uranium dioxide (UO2) molecules in solid argon. The reaction intermediate O2U(η1-CO) is generated spontaneously at the bands of 1893.0, 870.6, and 801.3 cm-1 during codeposition and annealing. Upon the following irradiation, CO2 is substantially produced by the consumption of O2U(η1-CO), indicating the catalytic conversion of CO to CO2 through the intermediate O2U(η1-CO). In C18O isotopic substitution experiments, the yields of 16OC18O convincingly confirm that one of the oxygen atoms in CO2 derives from UO2. The reaction pathways are discussed based on the theoretical and experimental results.

F2BMF (M = B and Al) Molecules: A Matrix Infrared Spectra and Theoretical Calculations Investigation.

Reactions of laser-ablated B and Al atoms with BF3 have been explored in the 4 K excess neon through the matrix isolation infrared spectrum, isotopic substitutions and quantum chemical calculations. The inserted complexes F2BMF (M = B, Al) were identified by anti-symmetric and symmetric stretching modes of F-B-F, and the F-11B-F stretch modes are at 1336.9 and 1202.4 cm-1 for F211B11BF and at 1281.5 and 1180.8 cm-1 for F211BAlF. The CASSCF analysis, EDA-NOCV calculation and the theory of atoms-in-molecules (AIM) are applied to investigate the bonding characters of F2BBF and F2BAlF molecules. The bonding difference between boron and aluminum complexes reveals interesting chemistries, and the FB species stabilization by a main group atom was first observed in this article.

Beryllium Dimer Reactions with Acetonitrile: Formation of Strong Be-Be Bonds.

Laser ablated Be atoms have been reacted with acetonitrile molecules in 4 K solid neon matrix. The diberyllium products BeBeNCCH3 and CNBeBeCH3 have been identified by D and 13C isotopic substitutions and quantum chemical calculations. The stabilization of the diberyllium species is rationalized from the formation of the real Be-Be single bonds with bond distances as 2.077 and 2.058 Å and binding energies as -27.1 and -77.2 kcal/mol calculated at CCSD (T)/aug-cc-pVTZ level of theory for BeBeNCCH3 and CNBeBeCH3, respectively. EDA-NOCV analysis described the interaction between Be2 and NC···CH3 fragments as Lewis "acid-base" interactions. In the complexes, the Be2 moiety carries positive charges which transfer from antibonding orbital of Be2 to the bonding fragments significantly strengthen the Be-Be bonds that are corroborated by AIM, LOL and NBO analyses. In addition, mono beryllium products BeNCCH3, CNBeCH3, HBeCH2CN and HBeNCCH2 have also been observed in our experiments.

Antibacterial activity and underlying mechanism of Meconopsis quintuplinervia Regel extract against the acne-causing bacteria Propionibacterium acnes and Staphylococcus aureus.

The aim of this study was to evaluate the antibacterial activity and underlying mechanism of ethanol extracts of Meconopsis quintuplinervia Regel (EMQ) against the acne-causing bacteria Propionibacterium acnes and Staphylococcus aureus. The study results indicated that EMQ was an effective antibacterial agent against P. acnes and S. aureus, with a DIZ of 14.5 and 13.2mm, MIC of 12.5 and 12.5mg/mL and MBC of 100 and 50mg/mL, respectively. EMQ induced morphological changes to bacterial cells, as determined by electron microscopy. Leakage of alkaline phosphatase and nucleic acids confirmed that EMQ compromised the membrane integrity of bacterial cells. Furthermore, protein analysis revealed that EMQ hindered total protein expression and lowered adenosine triphosphatase activity, while crystal violet staining revealed suppressed biofilm production. Bacterial adhesion analysis demonstrated that EMQ lowered the adhesive capacity of bacterial cells. The main chemical components of EMQ, identified by LC-MS, seem to have important roles in the antimicrobial effects against P. acnes and S. aureus, suggesting EMQ is a promising therapeutic for acne treatment.

Small Intestine Bacterial Overgrowth in Bangladeshi Infants Is Associated With Growth Stunting in a Longitudinal Cohort.

INTRODUCTION: Small intestine bacterial overgrowth (SIBO) is common in children from low-income countries and has been cross-sectionally associated with growth stunting. We sought to determine whether SIBO was associated with poor growth and neurodevelopmental in a longitudinal analysis. METHODS: We measured SIBO by glucose hydrogen breath test (GHBT) at 18, 52, 78, and 104 weeks of life in a prospective longitudinal birth cohort of Bangladeshi children. Sociodemographic information and measures of enteric inflammation were analyzed as covariates. Diarrheal samples were tested for enteropathogens using polymerase chain reaction. Regression models were created using standardized mean GHBT area under the H2 curve (AUC) to determine associations with linear growth and cognitive, language, and motor scores on the Bayley-III Scales of Infant and Toddler Development at 2 years. We also investigated associations between GHBT AUC and enteropathogen exposure. RESULTS: A 1-ppm increase in standardized mean GHBT AUC was associated with a 0.01-SD decrease in length-for-age Z score (P = 0.03) and a 0.11-point decrease in Bayley language score (P = 0.05) at 2 years of age in adjusted analysis. Enteroaggregative Escherichia coli, Enteropathogenic Escherichia coli, Giardia, and Enterocytozoon bieneusi were associated with increased GHBT AUC, whereas Clostridium difficile, norovirus GI, sapovirus, rotavirus, and Cryptosporidium were associated with decreased GHBT AUC. None were consistent across all 4 time points. DISCUSSION: SIBO in the first 2 years of life is associated with growth stunting and decreased language ability in Bangladeshi infants and may represent a modifiable risk factor in poor growth and neurodevelopment in low-income countries.

Matrix-Isolation Infrared Spectra and Electronic Structure Calculations for Dinitrogen Complexes with Uranium Trioxide Molecules UO3(η1-NN)1-4.

Investigations of the interactions of uranium trioxide (UO3) with other species are expected to provide a new perspective on its reaction and bonding behaviors. Herein, we present a combined matrix-isolation infrared spectroscopy and theoretical study of the geometries, vibrational frequencies, electronic structures, and bonding patterns for a series of dinitrogen (N2) complexes with UO3 moieties UO3(η1-NN)1-4. The complexes are prepared by reactions of laser-ablated uranium atoms with O2/N2 mixtures or laser-ablated UO3 molecules with N2 in solid argon. UO3(η1-NN)1-4 are classified as "nonclassical" metal-N2 complexes with increased Δν(N2) values according to the experimental observations and the computed blue-shifts of N-N stretching frequencies and N-N bond length contractions. Electronic structure analysis suggests that UO3(η1-NN)1-4 are σ-only complexes with a total lack of π-back-donation. The energy decomposition analysis combined with natural orbitals for chemical valence calculations reveal that the bonding between the UO3 moiety and N2 ligands in UO3(η1-NN)1-4 arises from the roughly equal electrostatic attractions and orbital mixings. The inspection of orbital interactions from pairwise contributions indicates that the strongest orbital stabilization comes from the σ-donations of the 4σ*- and 5σ-based ligand molecular orbitals (MOs) into the hybrid 7s/6dx2-y2 MO of the U center. The electron polarization induced by electrostatic effects in the Ninner ← Nouter direction provides complementary contributions to the orbital stabilization in UO3(η1-NN)1-4. In addition, the reactions of UO3 with N2 ligands and the origination of the nonclassical behavior in UO3(η1-NN)1-4 are discussed.

Insights into the Metal-CO Bond in O2M(η1-CO) (M = Cr, Mo, W, Nd, and U) Complexes.

Investigations on the structures and bonding properties of metal carbonyl compounds provide fundamental understandings on the origin of small-molecule activations. Herein, the geometry and bonding trends of a series of isovalent metal oxocarbonyl complexes O2M(η1-CO) (M = Cr, Mo, W, Nd, and U) were studied by combined matrix-isolation infrared spectroscopy and advanced quantum chemical calculations. The title complexes present red shift of C-O stretching bands in the range from 122 to 244 cm-1, indicating the difference of CO activation ability for the series of isovalent metal dioxides. Density functional theory calculations predict T-shaped structures with a C2v symmetry for all the title molecules. O2Nd(η1-CO) bears little resemblance to the other complexes in bonding characters because of the weak interactions between the NdO2 and CO moiety. For the other complexes, natural localized molecular orbital analysis reveals a gradual increase of covalent character in M-CO bonds along the metal series Cr → Mo → W→ U. Energy decomposition analysis with natural orbitals for chemical valence calculations demonstrates that the M-CO bonding patterns conform to the conventional Dewar-Chatt-Duncanson motif. The contributions from orbital interactions in total attractions increase from Cr (41.7%) to U (52.7%). The breakdown of the orbital term into pairwise interactions shows that contributions of the M ← CO σ donation decrease from Cr (59.2%) to U (28.4%), while the M → CO π* backdonation increases significantly from Cr (23.8%) to U (67.3%). The more effective overlap and the better energy matching of U 5f and U 6d valence orbitals with CO π* orbitals result in much stronger U → CO π backdonation than the other metal elements.

Ethanol extract of Nepeta angustifoia C. Y. Wu ameliorates hyperuricemia in fructose-induced mice.

As a popular medicinal plant traditionally used in Tibet of China, Nepeta angustifolia C. Y. Wu is mainly administered to treat apoplexia, cerebral haemorrhage, fainting and epilepsy and other symptoms, while its effect on hyperuricemia is still unclear. In the present study, we evaluated the improvement of the 70% ethanol extract of Nepeta angustifolia C. Y. Wu in fructose-induced hyperuricemic mice. The results revealed that Nepeta angustifolia C. Y. Wu significantly decreased blood glucose and blood lipid levels, as well as lowering the urinary levels of uric acid, creatinine and urea nitrogen. Meanwhile, it effectively restored the serum levels of uric acid, creatinine and urea nitrogen and inhibited serum and hepatic XOD activities and renal oxidative stress, while suppressing the secretions of TNF-α, IL-1ß and IL-6 in kidney. Nepeta angustifolia C. Y. Wu also attenuated the infiltration of inflammatory cells and reduced the production and accumulation of glycogen and collagen, while restoring the dysregulated protein expressions of renal URAT1, GLUT9, OAT1 and OAT3. In summary, our results support the idea that Nepeta angustifolia C. Y. Wu is a promising agent for treating hyperuricemia.

Intermediates of Carbon Monoxide Oxidation on Praseodymium Monoxide Molecules: Insights from Matrix-Isolation IR Spectroscopy and Quantum-Chemical Calculations.

Identifying reaction intermediates in gas-phase investigations will provide understanding for the related catalysts in fundamental aspects including bonding interactions of the reaction species, oxidation states (OSs) of the anchored atoms, and reaction mechanisms. Herein, carbon monoxide (CO) oxidation by praseodymium monoxide (PrO) molecules has been investigated as a model reaction in solid argon using matrix-isolation IR spectroscopy and quantum-chemical calculations. Two reaction intermediates, OPr(η1-CO) and OPr(η2-CO), have been trapped and characterized in argon matrixes. The intermediate OPr(η2-CO) shows an extremely low C-O stretching band at 1624.5 cm-1. Quantum-chemistry studies indicate that the bonding in OPr(η1-CO) is described as "donor-acceptor" interactions conforming to the Dewar-Chatt-Duncanson motif. However, the bonding in OPr(η2-CO) results evidently from a combination of dominant ionic forces and normal Lewis "acid-base" interactions. The electron density of the singly occupied bonding orbital is strongly polarized to the CO fragment in OPr(η2-CO). Electronic structure analysis suggests that the two captured species exhibit Pr(III) OSs. Besides, the pathways of CO oxidation have been discussed.

F2BMF (M = V, Nb, and Ta) and FBMF2 (M = Nb and Ta): A Combined Matrix Isolation Infrared Spectroscopic and Quantum Chemical Investigation.

Through matrix isolation infrared spectrometry and quantum chemical calculations, the reactions of laser ablated V, Nb, and Ta with boron trifluoride were investigated in excess solid neon at 4 K. The possible reaction products FBMF2, F2BMF, and BMF3 (M = V, Nb, and Ta) were calculated at the B3LYP, BPW91, and CCSD(T) levels of theory. The B-M bond strength in FBMF2 molecules is confirmed by energy decomposition analysis-natural orbitals for chemical valence calculations, CASSCF calculation, and natural bond orbital analysis, which favors one σ bond and two half π bonds.

Fluoroborylene Complexes FBMF2 (M = Sc, Y, La, Ce): Matrix Infrared Spectra and Quantum Chemical Calculations.

Laser-ablated group 3 transition metal and cerium atom reactions with boron trifluoride were explored in excess solid neon at 4 K through matrix isolation infrared spectroscopy and quantum chemical calculations. The fluoroborylene complexes FBMF2 (M = Sc, Y, La, Ce) were trapped in inert gas and identified by the isotopic substitutions. The observed frequencies of FBMF2 were reproduced by DFT, NEVPT2, and CASSCF calculations. From Sc to La, the observed F-11B stretching mode has been observed at 1391.9 cm-1 (Sc), 1370.8 cm-1 (Y), and 1337.1 cm-1(La); however, for Ce this mode shifts up to 1340.8 cm-1, which is due to relativistic effects. The electron localization function (ELF) analysis and the theory of atoms in molecules (AIM) were applied to investigate the character of the B-M bond in FBMF2 molecules, which favors bond order 1.5.

Boron-Transition-Metal Triple-Bond FB≡MF2 Complexes.

The boron-transition-metal triple-bond complexes FB≡MF2 (M= Ir, Os, Re, W, Ta) were trapped in excess solid neon and argon through metal atom reactions with boron trifluoride and identified by matrix isolation infrared spectroscopy and quantum chemical calculations. The FB≡MF2 molecule features very high 11B-F stretching frequencies at 1586.6 cm-1 (Ir), 1526.6 cm-1 (Os), 1505.5 cm-1 (Re), and 1453.2 cm-1 (W), respectively. The very high strength of B≡M bonds with triple-bonding character is confirmed by EDA-NOCV calculations and the active molecular orbital and NBO analysis. The experimental observation of FB stabilization by heavy transition-metal atoms with triple bonds opens the door to design new boron-transition-metal complexes.

Matrix infrared spectroscopy of F2BMF and FB[triple bond, length as m-dash]WF2 (M = Cr, Mo and W) complexes and quantum chemistry calculations.

Laser-ablated group 6 transition metal atoms react with BF3 to yield typical transition metal inserted complexes F2B-MF (M = Cr, Mo, and W) and terminal borylene complex FB[triple bond, length as m-dash]WF2. These products are investigated by using infrared spectroscopy, isotopic substitution and theoretical frequency calculations. The inserted complexes F2B-MF (M = Cr, Mo, and W) were identified by antisymmetric and symmetric stretching modes of F-B-F. The FB[triple bond, length as m-dash]WF2 molecule has a 11B-F (10B-F) stretching frequency at 1453.2 (1505.0) cm-1 and the triple bond between boron and tungsten is confirmed by EDA-NOCV calculations, CASSCF calculation and NBO analysis. Furthermore, the bonding for tungsten complexes is compared with that of molybdenum and chromium complexes, which reveals interesting differences in their chemistries.

Probing the Electronic Structure and Chemical Bonding of Uranium Nitride Complexes of NU-XO (X = C, N, O).

Uranium(III) compounds are very reactive and exhibit a broad range of chemical-bonding tendencies owing to the spatially diffused valence orbitals of uranium. A systematic study on the geometries, electronic structures, and chemical bonding of NU-XO (X = C, N, O) is performed using relativistic quantum chemistry approaches. The NU-CO and NU-NO complexes have an end-on structure, that is, (NU) (η1-CO) and (NU) (η1-NO), whereas NU-OO adopts a side-on ((NU) (η2-O2)) structure. The electronic structure analysis shows that UN exhibits efficient activation reactivity to molecules, especially to NO and O2, because of the significant U 7s/5f → XO 2π* electron transfer. Thus, the oxidation state of U is +V with the dianion ligand NO2- and O22- in NU-NO and NU-OO, respectively. Instead, U retains its usual +III oxidation state in NU-CO with a neutral CO ligand. The significant stability of NU-XO (X = C, N, O) is determined by the covalent U-X bonding which contains both X → U σ-, π-donation from the X lone pair and U 5f → XO 2π* back-donation contributions. The significant back-donation to the antibonding X-O 2π* orbital results in the obvious weakening of the X-O bonding.

Correction: Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule.

Correction for 'Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule' by Zhen Pu et al., Phys. Chem. Chem. Phys., 2017, 19, 8216-8222.

Ammonia Activation by Ce Atom: Matrix-Isolation FTIR and Theoretical Studies.

The activation of ammonia by cerium atom has been investigated in solid argon using infrared spectroscopy and density functional theoretical calculations. The results reveal that the spontaneous formation of CeNH3 complex on annealing is the initial step in the reactions of cerium atoms with ammonia. The CeNH3 complexes rearrange to generate the inserted HCeNH2 molecules on irradiation. A "triplet-singlet" spin conversion occurs along the reaction path in which HCeNH2 (3A″) isomerizes into H2CeNH (1A'). The H2CeNH molecules finally decompose to yield HCeN + H2 upon photolysis. The periodic trend and differences for the M + NH3 (M = Ti, Zr, Hf, Ce, Th) systems are discussed on the basis of the present and previous works. DFT calculations predict that the most stable ground state for HHfNH2 and HThNH2 is singlet due to the stronger relativistic effects in Hf and Th atoms, while that for HTiNH2, HZrNH2, and HCeNH2 is triplet. Besides, the H2-elimination process is different for Ce and M (Ti, Zr, Hf, Th) cases.

Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule.

Herein, an experimental study of the vibrational spectra of HCeN was carried out in solid argon, followed by theoretical investigations of molecular structures and the nature of Ce[triple bond, length as m-dash]N bond. The absorption band at 937.7 cm-1 with the 1.0311 14N/15N isotopic shift ratio is characteristic of Ce[triple bond, length as m-dash]N stretching band for HCeN, showing a 94 cm-1 higher shift relative to that of the diatomic CeN molecule. This large frequency shift indicates a much stronger Ce[triple bond, length as m-dash]N bond in HCeN, which is confirmed by DFT calculations. Qualitative orbital interaction and orbital composition analyses suggest that the addition of the H ligand to the Ce center will activate the 4f valence shell and strengthen the covalent bond between Ce and N, which may contribute to enhance the Ce[triple bond, length as m-dash]N triple bond in the HCeN molecule.