High prevalence and genomic characteristics of carbapenem-resistant Enterobacteriaceae and colistin-resistant Enterobacteriaceae from large-scale rivers in China.

The widespread presence of carbapenem-resistant Enterobacteriaceae (CRE) and mcr-positive Escherichia coli (MCREC) poses a huge threat to both animal and human health. River water environments are vital reservoirs of antibiotic resistance genes, however, the prevalence and characteristics of CRE and MCREC from large-scale rivers in China have not been reported. In the current study, we sampled 86 rivers from four cities in Shandong Province, China in 2021 and analyzed the prevalence of CRE and MCREC. The blaNDM/blaKPC-2/mcr-positive isolates were characterized with methods including PCR, antimicrobial susceptibility testing, conjugation, replicon typing, whole-genome sequencing and phylogenetic analysis. We found that the prevalence of CRE and MCREC in 86 rivers was 16.3% (14/86) and 27.9% (24/86), respectively and eight rivers carried both mcr-1 and blaNDM/blaKPC-2. A total of 48 Enterobacteriaceae isolates (10 ST11 Klebsiella pneumoniae with blaKPC-2, 12 blaNDM-positive E. coli and 26 MCREC carrying only mcr-1) were obtained in this study and 47 displayed multidrug resistance (MDR). Notably, 10 of the 12 blaNDM-positive E. coli isolates also harbored the mcr-1 gene. The blaKPC-2 gene was located within mobile element ISKpn27-blaKPC-2-ISKpn6 on novel F33:A-:B- non-conjugative MDR plasmids in ST11 K. pneumoniae. The dissemination of blaNDM was mediated by transferable MDR IncB/O plasmids or IncX3 plasmids while mcr-1 was primarily disseminated by highly similar IncI2 plasmids. Notably, these waterborne IncB/O, IncX3 and IncI2 plasmids were all highly similar to previously identified plasmids from animal and human isolates. A phylogenomic analysis revealed that the CRE and MCREC isolates from water environments might be derived from animals and trigger infections in humans. The high prevalence of CRE and MCREC in large-scale environmental rivers is alarming and needs sustained surveillance due to the potential risk for transmission to humans via the food chain (irrigation) or direct contact.

Whole-Genome Analysis of blaNDM-Bearing Proteus mirabilis Isolates and mcr-1-Positive Escherichia coli Isolates Carrying blaNDM from the Same Fresh Vegetables in China.

The global spread of colistin or carbapenem-resistant Enterobacteriaceae (CRE) has been a pressing threat to public health. Members of Enterobacteriaceae, especially Proteus mirabilis and Escherichia coli, have been prevalent foodborne pathogens and such pathogens from fresh vegetables have triggered foodborne illness in China. However, reports about CRE, especially P. mirabilis from fresh vegetables, are still lacking. In this study, we identified five blaNDM-positive P. mirabilis and five blaNDM-positive generic E. coli concurrently from five fresh vegetables in two markets from China, and four of the five E. coli also carried mcr-1. The 10 isolates were characterized with methods including antimicrobial susceptibility testing, conjugation, whole-genome sequencing and phylogenetic analysis. All 10 isolates were multidrug-resistant (MDR). blaNDM-5 in five E. coli isolates and one P. mirabilis carrying blaNDM-5 was located on similarly transferable IncX3 plasmids, while transferably untypable plasmids were the carriers of blaNDM-1 in four P. mirabilis isolates from different types of vegetables/markets. mcr-1 in the four blaNDM-5-positive E. coli was located on similarly non-conjugative IncHI2 MDR plasmids lacking transfer region. Notably, ISCR1 complex class 1 integron capable of capturing blaNDM-1 was found on all untypable plasmids from P. mirabilis, and five copies of ISCR1 complex class 1 integron containing blaNDM-1 even occurred in one P. mirabilis, which showed high-level carbapenem resistance. Plasmid and phylogenetic analysis revealed that the blaNDM-positive P. mirabilis and E. coli from fresh vegetables might be derived from animals and transmitted to humans via the food chain. The concurrence of blaNDM-positive P. mirabilis and E. coli carrying both mcr-1 and blaNDM in different types of fresh vegetables eaten raw is alarming and threatens food safety. Sustained surveillance of these foodborne pathogens among fresh vegetables is urgent to ensure the health of food consumers. We report for the first time the concurrence of blaNDM-positive P. mirabilis and mcr-1-bearing E. coli carrying blaNDM from the same fresh vegetables.

[Effects of soil fauna on microbial community during litter decomposition of Populus simonii and Fargesia spathacea in the subalpine forest of western Sichuan, China.] / å·è¥¿äºšé«˜å±±æ£®æž—åœŸå£¤åŠ¨ç‰©å¯¹æ¨æ ‘å’Œç®­ç«¹å‡‹è½ç‰©åˆ†è§£è¿‡ç¨‹ä¸­å¾®ç”Ÿç‰©ç¾¤è½çš„å½±å“.

To understand the relationship between soil fauna and microorganism in the detrital food chain during litter decomposition, leaf litters of poplar (Populus simonii) and fargesia (Fargesia spathacea) in a subalpine forest of western Sichuan were taken as study objects. Phospholipid fatty acid (PLFAs) biomarker method was used to determine the effects of soil fauna on the abundance, structure and diversity of microbial community during the decomposition of leaf litter of two species from April 2016 to April 2018 with in situ control experiment. The results showed that the presence of soil fauna significantly affected the microbial PLFAs content during the decomposition of both species, reducing the PLFAs content in the first 240 days and increasing the PLFAs content in the 360 to 480 days. Soil fauna participation reduced the ratio of fungi to bacteria in the decomposition of poplar litter, and increased the ratio of gram-positive bacteria (G+) to gram-negative bacteria (G-), which had the opposite effect on the ratio of fungi/bacteria and G+/G- in the decomposition of fargesia litter. Microbial diversity and evenness maintained a high level in 120th and 480th days of the decomposition, and decreased sharply in 360th and 720th days of decomposition. Soil fauna participation significantly affected microbial diversity and evenness of poplar litter, but it had no signifi-cant effect on fargesia litter. The effects of soil fauna on the changes of litter PLFAs content were different with the decomposition days and tree species. The interaction between soil fauna and microbial community during litter decomposition in subalpine forest varied with seasons and tree species.

Exploring the mechanism of alkene hydrogenation catalyzed by defined iron complex from DFT computation.

UB3LYP computation including dispersion and toluene solvation has been carried to elucidate the mechanisms of alkene hydrogenation catalyzed by bis(imino)pyridine iron dinitrogen complex (iPrPDI)Fe(N2)2, which has low stability towards N2 dissociation. The coordinatively unsaturated complexes, (iPrPDI)Fe(N2) and (iPrPDI)Fe(1-C4H8), favor open-shell singlet ground states. On the basis of our computations, we propose a new mechanism of 1-butene coordination and hydrogenation after N2 dissociation. The hydrogenation of 1-butene undergoes a concerted open-shell singlet transition state involving H2 dissociation, C-H bond formation and C=C bond elongation, as well as the subsequent C-H reductive elimination. In the whole alkene hydrogenation, the H-H bond cleavage is the rate-determining step. Graphical abstract The alkene hydrogenation catalyzed by redox-active pyridine(diimine)-chelate iron complex follows the open-shell singlet state path.

[Effects of naphthalene on soil respiration, dissolved organic matter and microbial biomass in the subalpine forest of western Sichuan, China]. / 萘对川西亚高山森林土壤呼吸、可溶性有机质和微生物生物量的影响.

The effects of naphthalene on soil respiration, dissolved organic matter and microbial biomass, and its inhibition efficiency for soil fauna of subalpine forest in western Sichuan were studied by in situ control experiment. The results showed that naphthalene application significantly inhibited the individual density and group number of soil macro- and meso-/micro- arthropods, with the individual density being decreased by 76.3%-78.5% and 83.3%-84.8% respectively, and the number of groups being decreased by 48.3%-56.1% and 45.8%-58.3%, respectively. The seasonal dynamics of soil respiration rate showed single peak curves in both naphthalene treatment and control. The lowest and the highest soil respiration rates were observed in February and August, respectively. The naphthalene treatment had little effect on soil respiration. Compared with the control, naphthalene treatment significantly reduced the contents of soil dissolved carbon and dissolved nitrogen in August and October as well as microbial biomass carbon (MBC) in April and August, but increased MBC/MBN in April. The naphthalene treatment and sampling time significantly interacted to affect the MBC and MBN, but had no significant effect on individual density, the number of groups of soil fauna and DC content. In all, naphthalene as biocide could effectively inhibit the soil arthropods and had no significant effect on soil respiration, but it had varying degrees of effects on soil carbon and nitrogen components in subalpine forest of western Sichuan.

[Diversity of soil nematode communities in the subalpine and alpine forests of western Sichuan, China.] / 川西亚高山/é«˜å±±æ£®æž—åœŸå£¤çº¿è™«å¤šæ ·æ€§.

In order to understand the diversity of soil nematodes in the subalpine/alpine forests of the eastern Qinghai-Tibet Plateau, soil nematodes in the primary forest, mixed forest and secondary forest of Abies faxoniana were extracted by elutriation and sugar-centrifugation method in July 2015, and the composition and structure characteristics of soil nematode communities were studied in the three forests at different altitudes. A total of 37950 soil nematodes were collected, which belonged to 20 families and 27 genera, and the mean density was 4217 ind·100 g-1 dry soil. Filenchus was the dominant genus in the primary forest, and Filenchus and Pararotylenchus in the mixed forest and secondary forest, respectively. The individual number of each dominant genus was significantly affected by forest type. All nematode individuals were classified into the four trophic groups of bacterivores, fungivores, plant-parasites and omnivore-predators. The fungivores were dominant in the primary and secondary forest and the bacterivores in the mixed forest. The number of soil nematode c-p (colonizer-persister) groups of c-p 1, c-p 2, c-p 3 and c-p 4 accounted for 6.1%, 51.1%, 30.0% and 12.7% of the total nematode abundance, respectively. The maturity index (MI), the total maturity index (∑MI) and the plant parasitic index (PPI) of soil nematodes decreased gradually with the increase of altitude. The nematode channel ratio in the mixed forest was higher than 0.5, but that in the primary forest and secondary forest was below 0.5. The forest type significantly affected the soil nematode maturity index and channel ratio, but the forest type, soil layer and their interaction had no significant effect on the diversity index. There were obvious diffe-rences in the composition, nutrient structure and energy flow channel of soil nematodes in the subalpine/alpine forests of western Sichuan, providing an important reference for understanding the function of soil nematodes in soil processes of this region.

[Effects of naphthalene on soil respiration, nutrients and enzyme activities in the subalpine forest of western Sichuan, China]. / è˜å¯¹å·è¥¿äºšé«˜å±±æ£®æž—åœŸå£¤å‘¼å¸ã€å »åˆ†å’Œé ¶æ´»æ€§çš„å½±å“.

As a biocide to reduce soil and litter faunal populations in field experiments, naphthalene has been widely used in the study of ecological functions of soil fauna, but the non-target effects of naphthalene bring about enormous uncertainty to its application. In order to understand whether there were non-target effects of naphthalene in subalpine forest soil, soil in the subalpine forests of west Qinghai-Tibet Plateau was taken as study object. The short-term responses of soil respiration rate, nutrient content and enzyme activity to naphthalene were studied in microcosms. The results showed that soil respiration rate was significantly suppressed by application of naphthalene within 0-10 days, and then showed a significant promotion effect. Naphthalene significantly affected the dynamics of soil NH4+-N and NO3--N contents. With application of naphthalene, the highest contents of NH4+-N and NO3--N occurred at the 3rd and 7th day, respectively. But they were observed at the 45th and 52nd day with no-naphthalene, respectively. Moreover, soil dissolved carbon content in the naphthalene microcosms showed a sharp increase and then decrease dynamic at the 3rd day, while small change was detected in the no-naphthalene microcosms. Dissolved nitrogen content in both the naphthalene and no-naphthalene microcosms showed an increase at first and then decreased subsequently during the study period. Similar dynamics were found for the soil enzyme activities in both the naphthalene and no-naphthalene microcosms. The highest activities of urease, nitrate reductase and nitrite reductase in both the naphthalene and no-naphthalene microcosms were at the 45th, 38th and 10th day, respectively. In addition, the interaction of naphthalene treatment and sampling time had significant effects on soil respiration rate, the contents of NH4+-N, NO3--N and dissolved nitrogen, but had no significant effects on soil dissolved carbon content, and the activities of invertase, nitrate reductase and nitrite reductase. In a short time, the non-target effect of naphthalene as a biocide to reduce soil fauna abundance might have an important influence on the soil nitrogen cycling in subalpine forest of western Sichuan.

Theoretical investigation of the mechanism for the cycloaddition of CO2 to epoxides catalyzed by a magnesium(II) porphyrin complex.

The cycloaddition of CO2 to epoxides, catalyzed by Mg(TPP)/TBAI (TPP = tetraphenylporphyrin; TBAI = tetrabutylammonium iodide), was investigated using DFT methods. Epoxides with various substituents were studied to explore steric and electronic effects on the reaction mechanism. Computational results show that the cycloaddition proceeds according to a much easier mechanism in the presence of Mg(TPP) and TBAI than the mechanism that takes place when Mg(TPP) is used as the catalyst. A preference for the epoxide ring-opening to occur at the methine (Cα) or methylene (Cß) carbon was noted. The ring-closing step leading to the formation of a five-membered carbonate is predicted to determine the reaction rate. For alkyl-substituted epoxides, the ß pathway is favorable since steric factors are dominant; for epoxides with a strongly electron-donating group and styrene oxide, the reaction is mainly controlled by electronic factors and proceeds along the α pathway. When the epoxide has a strongly electron-withdrawing group (CF3), both steric and electronic effects play important roles. The calculated reactivity of epoxides with CO2 catalyzed by Mg(TPP)/TBAI is in good agreement with that observed experimentally.

A computational study on the insertion of CO2 into (PSiP)palladium allyl σ-bond.

The insertion of CO2 into the (PSiP)palladium-allyl bond has been investigated using DFT. Three possible modes of CO2 insertion into (PSiP)Pd-allyl bond have been calculated, that is, direct 1.2-insertion mode, metallo-ene mode, and SE2 mode. The metallo-ene mode is the most favorable via the six-membered ring transition state. The results of calculations are consistent with the regioselectivity observed experimentally. The steric and electronic effects of different phosphine substituents have been evaluated by ONIOM and energy decomposition analysis (EDA) methods. For the phosphine substituents P(i-Pr)2 and PPh2, the contribution of electronic effect is greater than that of steric effect for the CO2 insertion into (PSiP)Pd-allyl bond; while for the phosphine substituent PMe2, the contribution of steric effect is slightly greater than that of electronic effect.

A new class of cuprous bromide cluster-based hybrid materials: direct observation of the stepwise replacement of hydrogen bonds by coordination bonds.

Although a variety of functional metal-organic frameworks (MOFs) have been synthesized, post-modified, and applied in various areas, there is little knowledge about how molecular cluster building units are stepwise evolved into MOFs via intermediates. Coordination bonds are generally stronger than hydrogen bonds, and thus equivalent replacement of X-H···Y hydrogen bonds by X-M-Y coordination bonds can transform hydrogen bond networks into MOFs. In this work, solvothermal in situ reduction reactions of CuBr2 and 1,4-diazoniabicyclo[2,2,2]octane (DABCO) generated a myriad of tunable photoluminescent cuprous body-centered cubic bromide cluster-based networks with the general formula [Cu4+xH4-xBr6(DABCO)4](HCO2)2·S (x = 0, 0.56, 0.81, 1.27, 1.39, 2.56, 2.78, and 4 for compounds 1-8, respectively). All of these compounds crystallize in the cubic space group with the largest volume difference being only 5.2%, but they belong to three remarkably different kinds of crystals. Complex 1 is a molecular crystal and consists of tetrahedral [Cu4Br6(HDABCO)4](2+) clusters with monodentate HDABCO groups that are supported via N-H···Br synthons in the hydrogen bond network. Compound 8 is a [Cu8Br6](2+) cube cluster-based MOF with bridged DABCO ligands. Complexes 2-7 are seemingly impossible Cu/H-substituted solid solutions of 1 and 8. The CuBr framework components in 1-8 are Cu4Br6, Cu4.56Br6, Cu4.81Br6, Cu5.27Br6, Cu5.39Br6, Cu6.56Br6, Cu6.78Br6, and Cu8Br6, respectively. Crystallization kinetics studies revealed that the [Cu4Br6(HDABCO)4](2+) cluster-based hydrogen bond network (1) was initially formed such that N-H···Br hydrogen bonds could be stepwise replaced by N-Cu-Br coordination bonds to form the [Cu8Br6](2+) cube cluster-based MOF (8) via solid solutions. These observations directly reveal the equivalence and transformation between the N-H···Br hydrogen bond and the N-Cu-Br coordination bond and the evolutionary mechanism of a molecular crystal to a MOF via solid solutions, which is of fundamental importance in materials but has never before been revealed. DFT calculations suggest that equivalent replacement of a N-H···Br hydrogen bond by a N-Cu-Br coordination bond is exothermic and exergonic, which also supports the transformation from molecule 1 to MOF 8.

Interaction between water-soluble rhodium complex RhCl(CO)(TPPTS)2 and surfactants probed by spectroscopic methods.

The interactions of rhodium complex RhCl(CO)(TPPTS)(2) [TPPTS=P(m-C(6)H(4)SO(3)Na)(3)] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and (1)H NMR measurements. The presence of four different species of RhCl(CO)(TPPTS)(2) in cationic cetyltrimethylammonium (CTAB) solution has been demonstrated: free rhodium complex, rhodium complex bound to CTAB monomer, rhodium complex bound to CTAB premicelles, rhodium complex bound to CTAB micelles. The spectroscopy data show that RhCl(CO)(TPPTS)(2) can adsorb on the interface of cationic CTAB micelles by strong electrostatic attraction, weakly bind to the nonionic polyoxyethylene (20) sorbitan monolaurate (Tween 20) micelles by hydrophobic interaction, and does not interact with anion sodium dodecyl sulfate (SDS) micelles due to the strong electrostatic repulsion.

A computational study on the chemical fixation of carbon dioxide with epoxide catalyzed by LiBr salt.

The chemical fixation of carbon dioxide with 2,3-epoxypropyl phenyl ether catalyzed by LiBr salt to produce a five-membered cyclic carbonate, 4-(phenoxymethyl)-1,3-dioxolan-2-one, has been extensively investigated at the B3LYP density functional level of theory. The solvent effects have been studied by means of a PCM model. All possible pathways are examined, and their corresponding energetics are demonstrated. Our results reveal that the overall reaction comprises three main steps: epoxide ring-opening, carbon dioxide insertion, and ring-closure of cyclic carbonate, none of which contains significantly large barriers. On the basis of the computed free energies of activation, the rate-determining step can be the ring-opening of epoxide or the ring-closure of cyclic carbonate with variation in the reaction conditions in N-methylpyrrolidinone (NMP) solvent. Our calculations indicate that path 2 is more favorable than path 1 in the gas phase, while both of them exist possibly in NMP solvent. The overall reaction is exothermic. Furthermore, the free energy profiles of all reaction pathways along the minima energy path in the gas phase and in NMP solvent were obtained and compared. It is shown that NMP solvent does not change the general trends for the reaction potential energy surfaces.

A comprehensive theoretical study on the coupling reaction mechanism of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl.

The mechanistic details of the coupling reaction of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl to yield cyclic carbonate were elucidated by density functional theory (DFT) calculations at the B3LYP/6-311G** level. Our results reveal that the overall reaction is stepwise and considered to include two processes. In process 1, CO(2) insertion into the Cu(I)-C bond of copper(I) cyanomethyl affords activated carbon dioxide carriers. In process 2, O-coordination of propylene oxide molecule to the electrophilic copper center of carriers occurs. Herein, three possible pathways were investigated, and the calculated reaction free energy profiles were compared. It was found that carrier 8 reacting with propylene oxide is more favored than the other two carriers (6 and 7) both kinetically and thermodynamically. Several factors, such as the composition of catalyst, the coordinate environment of copper, and the symmetry of frontier molecular orbitals, affected the reaction mechanisms, and the outcomes were identified. The overall reaction is exothermic. In addition, natural bond orbital (NBO) analysis has been performed to study the effects of charge transfer and understand the nature of different interactions between atoms and groups. The present theoretical study explains satisfactorily the early reported experimental observations well and provides a clear profile for the cycloaddition of carbon dioxide with propylene oxide promoted by NCCH(2)Cu.

[Apoptosis versus proliferation activities of pulmonary artery smooth muscle cells in pulmonary arterial hypertension associated with chronic obstructive pulmonary disease].

OBJECTIVE: To investigate the apoptosis versus proliferation activities of pulmonary artery smooth muscle cells (PASMC) in pulmonary hypertension (PH) associated with chronic obstructive pulmonary disease (COPD) and pulmonary vascular structural remodeling. METHODS: Forty-five patients were divided into three groups: patients without COPD and PH (non-COPD group, n = 15), COPD patients without PH (COPD with non-PH group, n = 15) and patients with PH associated with COPD (COPD with PH group, n = 15). Lung tissue samples were obtained from surgically resected specimens. The remodeling of pulmonary arteries were observed under microscope, and the changes of morphology-the ratio of the thickness of the wall to the external diameter of the pulmonary arterioles (WT%) and the ratio of the area of the wall to that of the pulmonary arterioles (WA%) were analyzed by computer-based image analysis system. The proliferation of PASMC was detected by proliferating cell nuclear antigen (PCNA) with immunohistochemical technique, and TUNEL (terminal deoxynu-cleotidyl transferase (TdT)-mediated deoxyuridine triphosphate (dUTP)-digoxigenin nick end labeling) was used for the detection of the apoptosis of PASMC. RESULTS: In the COPD with non-PH group, the arterial walls were thicker and the lumens narrower than that of the non-COPD group. In the COPD with PH group, the walls were thicker and the lumens narrower than that of the COPD with non-PH group. In the COPD with non-PH group and the COPD with PH group, the WT% and WA% [(20 +/- 4)% and (35 +/- 5)%; (28 +/- 5)% and (50 +/- 6)%, respectively] were higher than those of the non-COPD group (16 +/- 3)% and (25 +/- 3)% (P < 0.01), and the WT% and WA% of the COPD with PH group were higher than those of the COPD with non-PH group (P < 0.01). Both proliferative and apoptotic PASMC were found in the patients of the three groups. The proliferation indexes (PI) of the COPD with non-PH group and the COPD with PH group [(19 +/- 5)% and (38 +/- 7)%] were significantly higher than that of the non-COPD group [(8 +/- 2)%, P < 0.01], while the apoptosis indexes (AI) [(4.5 +/- 1.3)% and (3.1 +/- 1.3)%] were lower than that of the non-COPD group [(6.9 +/- 1.9)%, P < 0. 01]. The PI of the COPD with non-PH group was lower than that of the COPD with PH group; the AI was higher than that of the COPD with PH group (P < 0.05). The PaO(2) of the COPD with non-PH group and the COPD with PH group was negatively related with the PI (r = -0.519, P = 0.003), but positively related to the AI of the PASMC (r = 0.441, P = 0.015). CONCLUSION: The imbalance of the increased proliferation and decreased apoptosis of PASMC may contribute to the pulmonary vascular structural remodeling and pulmonary arterial hypertension in patients of COPD. Hypoxia is one of the main causes of increased proliferation and decreased apoptosis of the PASMC.