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1.
The local structures of ‘host’ and ‘guest’ layers of MoS2 intercalated with M(OH)2 (M=Mn, Co and Ni) prepared via interaction of single-layer MoS2 dispersions and solutions of M2+ salts were studied by X-ray absorption spectroscopy. According to M K-edge extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) results, the electronic structure and atomic environment of the M atoms in the intercalates are similar to that of the crystalline hydroxides M(OH)2. In the Ni intercalate, Mo K-edge EXAFS revealed a structural change of the ‘host’ MoS2 layers similar to that reported for water dispersions of MoS2 single layers. S K-edge XANES data indicate that the change is associated with increased electron density on the S atoms in the matrix. SO42− and Mo″ (4 < n < 6) were detected in the intercalated materials exposed to air, suggesting that transition metal intercalation may increase the susceptibility of the MoS2 layers to oxidation.  相似文献   

2.
BackgroundA growing number of researches indicated the association between plasma trace elements and blood lipids. However, the potential interaction and dose-response relationship were less frequently reported.MethodsIn this study, a total of 3548 participants were recruited from four counties in Hunan Province, South China. Demographic characteristics were collected by face-to-face interviews and inductively coupled plasma mass spectrometry (ICPMS) was used to determine the levels of 23 trace elements in plasma. We applied a fully adjusted generalized linear regression model (GLM) and a multivariate restricted cubic spline (RCS) to estimate the correlation, dose-response relationship and possible interaction between 23 trace elements and four blood lipid markers.ResultsThe results indicated positive dose-response relationships of plasma 66zinc with triglycerides (TG) and low density lipoprotein cholesterol (LDL-C), plasma 78selenium with LDL-C and total cholesterol (TCH), and plasma 59cobalt with high-density lipoprotein cholesterol (HDL-C). There was a negative dose-response relationship between 59cobalt and LDL-C. Further analysis found that 66zinc and 59cobalt had an antagonistic effect on the risk of increased LDL-C level.ConclusionsThis study added new evidence for the potential adverse effects of 66Zn and 78Se on blood lipids, and provided new insight into the threshold value setting for metals as well as the intervention strategy for dyslipidemia.  相似文献   

3.
A combined computational chemistry/crystallographic database analysis of the bonding in late transition metal N-heterocyclic carbene complexes (NHCs) is reported. The metal-carbon bond in these complexes is approximately 4% shorter than a prototypical M-C single bond, e.g., as in a metal-alkyl complex. Two hypotheses are investigated for this bond shortening - multiple-bond character in the metal-carbon linkage of the NHC complex, and a change in the hybridization of the carbenoid carbon to incorporate more p character. The results of this research support the latter hypothesis. The natural bond order analysis also suggests a substantial trans influence for NHC ligands.  相似文献   

4.
冷蒿(Artemisia frigida)挥发性有机化合物(volatile organic compounds, VOCs)具有特殊气味, 在植物受损伤时, 此气味会更加浓烈。该文通过对未损伤与损伤冷蒿VOCs成分分析、地上部分结构观察, 初步揭示了冷蒿VOCs释放与结构之间的关系。结果表明, 未损伤冷蒿VOCs主要含有22种化合物, 其主要成分是莰烯(14.27%)、(E)-乙酸-3-己烯酯(10.85%)、对-伞花烃(9.05%)、桉树脑(39.80%)、α-萜品醇(10.04%)、β-萜品醇(2.48%)、樟脑(5.66%)和(R)-(-)-对薄荷-1-烯-4-醇(3.84%)。损伤较未损伤冷蒿VOCs增加了12种物质, 其中相对含量大于1%的化合物分别为顺-3-己烯醛(1.15%)、2-己烯醛(1.34%)、顺-牻牛儿醇(2.66%)、冰片(4.47%)、(1R,4R)(+)-对-薄荷-2,8-二烯(9.15%)、乙酸冰片酯(1.37%)和4(14), 11-桉叶双烯(1.30%)。冷蒿叶片中栅栏组织发达, 叶柄内具有2-3处栅栏组织, 并且栅栏组织中都具有发达的气室, 同时气室与气孔相连。因此, 损伤较未损伤冷蒿VOCs种类和浓度增多的原因可能为: 冷蒿VOCs合成后大量储存于气室中, 当叶片损伤时, VOCs大量释放出来, 同时合成释放一些新的VOCs, 致使损伤冷蒿VOCs种类和浓度增加。  相似文献   

5.
Four flavonoids quercetin (QU), luteolin (LU), taxifolin (TA) and (+)-catechin (CA) with the same A- and B-rings but different C-ring substituents have been investigated for their binding to bovine serum albumin (BSA) in the absence and presence of Cu2+ by means of various spectroscopic methods such as fluorescence, UV-visible and circular dichroism (CD). The results indicated that hydroxyl group at 3-position increased the binding affinities between flavonoids and BSA. The values of the binding affinities were in the order: QU > CA > TA > LU. The presence of Cu2+ affected the interactions of flavonoids with BSA significantly. The binding affinities of QU and TA for BSA were decreased about 6.7% and 13.2%. However, the binding affinities of LU and CA for BSA were increased about 43.0% and 20.7%. The formation of Cu2+-flavonoid complex and steric hindrance together influenced the binding affinities of QU, LU and TA for BSA, while the conformational change of BSA may be the main reason for the increased binding affinity of CA for BSA. However, the quenching mechanism for QU, LU, TA and CA to BSA was based on static quenching combined with non-radiative energy transfer irrespective of the absence or presence of Cu2+. The UV-visible results showed the change in BSA conformation and the formation of flavonoid-Cu2+ complex. The CD results also explained the conformational changes of BSA on binding with flavonoids.  相似文献   

6.
Fungal biofilters have been recently studied as an alternative to the bacterial systems for the elimination of hydrophobic volatile organic compounds (VOC). Fungi foster reduced transport limitation of hydrophobic VOCs due to their hydrophobic surface and extended gas exchange area associated to the hyphal growth. Nevertheless, one of their principal drawbacks is their slow growth, which is critical in the start‐up of fungal biofilters. This work compares the use of different carbon sources (glycerol, 1‐hexanol, wheat bran, and n‐hexane) to reduce the start‐up period and sustain high n‐hexane elimination capacities (EC) in biofilters inoculated with Fusarium solani. Four parallel experiments were performed with the different media and the EC, the n‐hexane partition coefficient, the biomass production and the specific consumption rate were evaluated. Biofilters were operated with a residence time of 1.3 min and an inlet n‐hexane load of 325 g m−3reactor h−1. The time to attain maximum EC once gaseous n‐hexane was fed was reduced in the three experiments with alternate substrates, as compared to the 36 days needed with the control where only n‐hexane was added. The shortest adaptation period was 7 days when wheat bran was initially used obtaining a maximum EC of 160 g m−3reactor h−1 and a critical load of 55 g m−3reactor h−1. The results were also consistent with the pressure drop, the amount of biomass produced and its affinity for the gaseous n‐hexane, as represented by its partition coefficient. Biotechnol. Bioeng. 2011; 108:758–765. © 2010 Wiley Periodicals, Inc.  相似文献   

7.

Background

Non-invasive diagnostic strategies aimed at identifying biomarkers of lung cancer are of great interest for early cancer detection. The aim of this study was to set up a new method for identifying and quantifying volatile organic compounds (VOCs) in exhaled air of patients with non-small cells lung cancer (NSCLC), by comparing the levels with those obtained from healthy smokers and non-smokers, and patients with chronic obstructive pulmonary disease. The VOC collection and analyses were repeated three weeks after the NSCLC patients underwent lung surgery.

Methods

The subjects'' breath was collected in a Teflon® bulb that traps the last portion of single slow vital capacity. The 13 VOCs selected for this study were concentrated using a solid phase microextraction technique and subsequently analysed by means of gas cromatography/mass spectrometry.

Results

The levels of the selected VOCs ranged from 10-12 M for styrene to 10-9 M for isoprene. None of VOCs alone discriminated the study groups, and so it was not possible to identify one single chemical compound as a specific lung cancer biomarker. However, multinomial logistic regression analysis showed that VOC profile can correctly classify about 80 % of cases. Only isoprene and decane levels significantly decreased after surgery.

Conclusion

As the combination of the 13 VOCs allowed the correct classification of the cases into groups, together with conventional diagnostic approaches, VOC analysis could be used as a complementary test for the early diagnosis of lung cancer. Its possible use in the follow-up of operated patients cannot be recommended on the basis of the results of our short-term nested study.  相似文献   

8.
Kinetics and equilibria of cyanine dyes thiazole orange (TO) and benzothiazole orange (BO) self-aggregation and binding to CT-DNA are investigated in aqueous solution at 25 degrees C and pH 7. Absorbance spectra and T-jump experiments reveal that BO forms J-aggregates while TO forms more stable H-aggregates. Fluorescence and absorbance titrations show that TO binds to DNA more tightly than BO. TO stacks externally to DNA for low polymer-to-dye concentration ratios (C(P)/C(D)) while dye intercalation occurs for high values of C(P)/C(D). T-jump and stopped-flow experiments performed at high C(P)/C(D) agree with reaction scheme D+S <=> D,S <=> DS(I) <=> DS(II) where the precursor complex D,S evolves to a partially intercalated complex DS(I) which converts to the more stable intercalate DS(II). Non-electrostatic forces play a major role in D,S stabilization. Last step is similar for both dyes suggesting accommodation of the common benzothiazole residue between base pairs. Experiments using poly(dA-dT).poly(dA-dT) and poly(dG-dC).poly(dG-dC) confirm base pair preference for TO.  相似文献   

9.
赵路佳  李春林  胡远满  熊在平 《生态学报》2023,43(24):10023-10031
在外界环境的刺激下,植物会通过释放挥发性有机化合物来维护自身生长。城市是人类活动的主要集聚地,剧烈的人为干扰导致城市环境特征呈现出复杂的变化趋势,从而使城市植物排放挥发性有机化合物的过程与自然界出现较大差异。城市中的植物源挥发性有机化合物(Biogenic Volatile Organic Compounds, BVOCs)会直接与城市中的氧化物质接触,生成二次污染物,并在高温、强光照的条件下发生光化学反应,严重破坏城市大气环境,危害居民健康。总结了城市BVOCs的常见类型、作用机制及现有研究方法,分析了不同时间、空间和人类活动背景下的城市BVOCs排放特征,并进一步梳理了当前研究的不足,提出未来重点研究方向,旨在为大气环境治理、环境空间规划、居民健康保障等方面的城市管理工作提供指导。  相似文献   

10.
Three new cobalt(III) polypyridyl complexes, [Co(L - L)2IIP]3+ where IIP = 2-(2H-isoindol-1-yl)-2H-imidazo[4,5-f][1, 10]phenanthroline, L?=?1) phen (1,10-phenanthroline), 2) bpy (2,2’bipyridyl), 3) dmb (4, 4-dimethyl 2, 2’-bipyridine) have been synthesized, characterized (UV –VIS, IR, 1HNMR and 13C NMR spectroscopy) and screened for their in vitro antibacterial activity against E.coli, Staphylococcus aureus and Bacillus subtilis. The binding of these complexes with calf-thymus DNA (CT-DNA) has been investigated by absorption and fluorescence spectroscopy, viscosity measurements. The experimental studies indicate that complexes bind to CT-DNA by means of intercalation, but with different binding affinities due to differences in the planarity of the ancillary ligand. The complexes promote photocleavage of plasmid DNA from super coiled form I to the open circular form II. The antibacterial activities suggest that the metal complexes are more active as compared to the prepared un-complexed IIP ligand.

In addition, a conformational search was carried out by Molecular Dynamics Simulations, and docking revealed that complexes intercalate between base pairs of DNA. The experimental and computational approaches reveal that the length of the intercalator and the nature of ancillary ligand are highly important factors for DNA binding.  相似文献   

11.
AAO (aryl-alcohol oxidase) provides H?O? in fungal degradation of lignin, a process of high biotechnological interest. The crystal structure of AAO does not show open access to the active site, where different aromatic alcohols are oxidized. In the present study we investigated substrate diffusion and oxidation in AAO compared with the structurally related CHO (choline oxidase). Cavity finder and ligand diffusion simulations indicate the substrate-entrance channel, requiring side-chain displacements and involving a stacking interaction with Tyr?2. Mixed QM (quantum mechanics)/MM (molecular mechanics) studies combined with site-directed mutagenesis showed two active-site catalytic histidine residues, whose substitution strongly decreased both catalytic and transient-state reduction constants for p-anisyl alcohol in the H502A (over 1800-fold) and H546A (over 35-fold) variants. Combination of QM/MM energy profiles, protonation predictors, molecular dynamics, mutagenesis and pH profiles provide a robust answer regarding the nature of the catalytic base. The histidine residue in front of the FAD ring, AAO His??2 (and CHO His???), acts as a base. For the two substrates assayed, it was shown that proton transfer preceded hydride transfer, although both processes are highly coupled. No stable intermediate was observed in the energy profiles, in contrast with that observed for CHO. QM/MM, together with solvent KIE (kinetic isotope effect) results, suggest a non-synchronous concerted mechanism for alcohol oxidation by AAO.  相似文献   

12.
Molecular dynamics (MD) simulations and circular dichroism (CD) experiments were carried out on aqueous temporin A and L, two short peptides belonging to an interesting class of natural substances known to be active mainly against Gram-positive/negative bacteria and fungi. Experimental results indicate the higher propensity of temporin L, with respect to temporin A, in forming alpha-helical structures. These results were revisited by long-timescale MD simulations, in which their alpha-helical propensity was investigated in the absence of trifluoroethanol. Results clearly show the higher stability of alpha-helix conformations in temporin L; moreover, an interestingly strong mechanical analogy emerges since both temporins show the same residue interval (from 7 to 10) as the most energetically accessible for alpha-helix formation. Such studies provide some intriguing structural and mechanical evidence that may help in better understanding and rationalizing the conformational behaviour of temporins in water solution and, ultimately, the inner principles of their microbial targets selectivity and mechanism of action at the level of cell membranes.  相似文献   

13.
Odours (OUE) and volatile organic compounds (VOC) emission during biological process used to treat MSW were studied under standardized conditions in order to detect potential risk for workers and population. Results obtained indicated that odours and VOCs emitted depend on the biological stability of waste measured by the dynamic respiration index (DRI) and a very good correlation were found between these parameters (OUE vs. DRI, r = 0.96, p < 0.001, = 6; VOC vs. DRI, r = 0.97, p < 0.001, = 6).GC-MS study of the VOCs indicated the presence of a group of molecules that were degraded during the process. On the other hand, a second group of molecules, i.e. aromatic and halogenated compounds, and furan persisted in the waste sample, although molecule concentrations were always lower than Threshold Limit Value-Time Weighted Average (TLV-TWA).  相似文献   

14.
1. The decomposition of biological material produces a plethora of volatile organic compounds (VOCs), which are implicated in the foraging behaviour of coprophagous and necrophagous insects. Dung beetles (Coleoptera: Scarabaeidae: Scarabaeinae) have an acute olfactory system used to locate food resources. Accordingly, identification of food resource VOCs potentially used in food location is integral to understanding dung beetle foraging ecology. 2. In this study, volatile emissions from dung and carrion of native and introduced animals in New Zealand were analysed using solid‐phase microextraction (SPME) and gas chromatography‐mass spectrometry (GC‐MS). Volatile profiles were compared via principal component analyses (PCAs) and cluster solutions based on attractiveness using canonical discriminant analysis (CDA). 3. A total of 115 compounds were detected from 21 food types. Statistical analyses showed that dung and carrion volatile profiles clustered according to attractiveness to the dung beetle Saphobius edwardsi, and that different dung types formed distinct clusters and grouped separately from carrion. 4. This study suggests that volatile profiles emitted by food resources used by dung beetles are complex, producing distinct odours, which potentially mediate foraging decisions.  相似文献   

15.
Probabilistic risk assessment was conducted to evaluate health risks caused by eight volatile organic compounds (VOCs) (benzene, toluene, xylene, ethylbenzene, styrene, formaldehyde, acetaldehyde, and acrolein) in five commuting modes (car, air-conditioned bus, non-air-conditioned bus, subway, and bicycle) in Guangzhou. Monte Carlo method and the contribution to variance method were applied to obtain the more scientific evaluation results and the more influential variables. The results revealed that the carcinogenic risk of air-conditioned bus and car were the highest, followed by bicycle, non-air-conditioned bus, and subway. The probability of the risk exceeding 10?6 was approximately 90%, 62%, 62%, 91%, and 92%, respectively. Moreover, the noncarcinogenic risk of air-conditioned bus and car were the highest, followed by non-air-conditioned bus, bicycle, and subway. It indicated that subway, non-air-conditioned bus, and bicycle are better commuting choices for city dwellers to reduce health risks and alleviate traffic pressure. Formaldehyde, benzene, and acrolein contribute to a significant proportion in health risk and should be the prior controlled organic pollutants. Sensitivity analysis suggests that exposure time is the most influential parameter for carcinogenic and noncarcinogenic risk, followed by concentrations of VOCs in air and exposure duration.  相似文献   

16.
The P2 protein is a small, extrinsic protein of the myelin membrane in the peripheral nervous system that structurally belongs to the fatty acid binding proteins (FABPs) family, sharing with them a 10 strands beta-barrel structure. FABPs appear to be involved in cellular fatty acid transport, but very little is known about the role of P2 in the metabolism of peripheral myelin lipids. Study of protein conformation at different pHs is a useful tool for the characterization of the unfolding mechanisms and the intrinsic conformational properties of the protein, and may give insight into factors that guide protein folding pathways. In particular, low pH conditions have been shown to induce partially folded states in several proteins. In this paper, the acidic unfolding of purified P2 protein was studied with both spectroscopic techniques and molecular dynamics simulation. Both experimental and computational results indicate the presence of a partly folded state at low pH, which shows structural changes mainly involving the lid that is formed by the helix-turn-helix domain. The opening of the lid, together with a barrel relaxation, could regulate the ligand exchanges near the cell membrane, supporting the hypothesis that the P2 protein may transport fatty acids between Schwann cells and peripheral myelin.  相似文献   

17.
Allelopathy has been suggested as a mechanism promoting the monoculture formation of some invasive exotic plants. Previous studies have shown that hydrophobic extracts of the roots and soil of exotic bitou bush (Chrysanthemoides monilifera spp. rotundata (DC.) T. Norl.) inhibited the seedling growth of five Australian native plants, including the dominant acacia (Acacia longifolia var. sophorae (Labill.) F. Muell.). Based on this finding, we compared the hydrophobic root and soil chemical profiles of bitou bush and acacia to determine whether bitou bush roots release allelopathic compounds that are novel to the invaded system. We detected three compounds that were exclusive to the bitou bush root and soil, and seven compounds that were common to the bitou bush and acacia roots but only present in the bitou bush soil. The compounds unique to the bitou bush invaded soil were all sesqui- and diterpenes. Several of these compounds were found to inhibit the seedling growth of a native sedge, Isolepis nodosa (Rott.) R. Br. Of particular interest are the sesquiterpenes: β-maaliene, α-isocomene, β-isocomene, δ-cadinene, 5-hydroxycalamenene and 5-methoxycalamenene which were found in high concentrations in the bitou bush root and soil extracts and exhibited phytotoxic activity. Therefore, we present evidence to suggest that bitou bush exudes low molecular weight volatile compounds into the soil which inhibit native plant seedling growth. The reduced establishment of native plants via allelopathy is likely to create space and contribute to the invasion of bitou bush on the eastern Australian coast.  相似文献   

18.
8-Hydroxyquinoline (8HyQ) and its derivatives are the important constituents in a variety of pharmaceutical compounds. The effect of protonation and deprotonation of 8HyQ on its electronic structure and fluorescence was investigated using B3LYP/6-311G** level of theory. We also investigated the interaction of chemosensor, 8HyQ, with different transition metals (Zn2+, Fe2+, Ni2+ and Co2+) at the same level. Our results revealed that 8HyQ displays an unusual fluorescence intensity–proton transfer relationship with diminished emission in a protonated form but enhanced emission in a deprotonated form. The Zn2+, Fe2+, Ni2+ and Co2+ complexes of 8HyQ, which were investigated at the same level of theory, showed that the order of binding energies was 8HyQ-Ni2+>8HyQ-Zn2+>8HyQ-Co2+>8HyQ-Fe2+. Time-dependent density functional theory calculations indicated that Zn ion enhances the fluorescence of 8HyQ as a consequence of the inhibition of the proton transfer. The results are in good agreement between the predicted properties of transition metal complexes of 8HyQ and previously published experimental and theoretical results. A natural bond orbital analysis was performed to understand the nature of hydrogen-bonding interaction in 8HyQ and also to reveal the inter-relations between electronic structure and other properties.  相似文献   

19.
The surface pressure isotherms of chlorophyll a, monogalactosyldiacylglycerol and phytol at the air-water interface were studied on a Langmuir trough at 20.0±0.5°C. The subphase was a phosphate buffer, 10?3 M at pH 8.0. The extrapolated limiting areas per molecule are 115, 82 and 38 Å2/molecule, respectively. The isotherms of eight mixtures of chlorophyll a with monogalactosyldiacylglycerol and eight mixtures of chlorophyll a with phytol, covering in both cases the whole range of molar fractions have also been measured. The results for the mixed monolayers were analysed in terms of the additivity rule. They show that a small negative deviation with respect to ideality is observed upon mixing chlorophyll a with monogalactosyldiacylglycerol. However, chlorophyll a forms an ideal two-dimensional solution when mixed with phytol. The excess free energies of mixing of chlorophyll a with monogalactosyldiacylglycerol as a function of concentration were calculated from the surface pressure isotherms at 10, 15, 20 and 25 mN·m?1. The values are negative, reflecting the interaction prevailing between these components in the monolayers. For the four surface pressures studied, the excess free energies are symmetrical with respect to the mode fraction. The values for an equimolar mixture range from ?300 to ?540 J·mol?1 at 10 and 25 mN·m?1, respectively. A comparison between the thermodynamics of mixing of chlorophyll a with monogalactosyldiacylglycerol and phytol suggests that the polar head of monogalactosyldiacylglycerol together with the polar groups of chlorophyll a are probably involved in the interaction. However, this does not completely rule out the possibility that structural effects due to a different packing of chlorophyll a with monogalactosyldiacylglycerol and phytol may also be involved. Furthermore it is shown that the small interactions between these constituents are not inconsistent with the specific coupling existing between the apoprotein of the chlorophyll a-protein complexes and chlorophyll a.  相似文献   

20.
Parabroteas sarsi is a predaceous calanoid copepod commonly found in South Andes lakes. Feeding experiments were carried out in order to estimate the predation rates and attack patterns on different cladoceran prey. Predation rates were related with prey sizes. The smallest prey, Bosmina longirostris, was ingested up to 5 prey pred–1 h–1 while the largest, Daphnia middendorffiana, only at 0.12 prey pred–1 h–1. The functional response of P. sarsi differed when confronted with different prey although in all cases, the number of kills increased with prey density. A saturation of ingestion rates at high prey densities was only observed for B. longirostris and Ceriodaphnia dubia juveniles. Remains seldom appeared at the end of the experiments, implying that the predator consumed prey totally. Yet, in all experiments carried out with Daphnia ambigua and D. middendorffiana, remains, including soft parts, were found. Direct observations of attack and of number and types of remains showed interference of handling by tail, helmet, and size of the prey.  相似文献   

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