光降解在凋落物分解中的作用

近年来,越来越多的研究者认识到光降解可能在凋落物分解中发挥着重要作用.本文对光降解的作用机制,光降解在碳循环、养分循环中的作用,光降解与微生物分解的关系,以及影响光降解的因素进行了综述.光降解对凋落物分解过程同时具有正效应和负效应,正效应指光降解通过氧化有机质,或是改变凋落物自身理化性质使其更易淋溶和分解,负效应指高光辐射对分解者产生不利影响从而押制微生物分解.在光降解过程中光化学矿化产生CO2是生态系统碳流失的主要机制.除紫外光外,可见光中的蓝、绿光波段也对凋落物的降解产生影响.光降解作用的大小受到水分状况、凋落物化学性质和凋落物的暴露面积的影响.最后,讨论了该领域有待深入研究的方向,指出今后应当重点对光降解研究方法,光降解与环境因子的交互作用,光降解作用的空间差异,光降解与微生物分解的相互关系及其作用强度进行研究.     

Toxicity of Binary Mixtures of Enantiomers in Chiral Organophosphorus Insecticides: The Significance of Joint Effects Between Enantiomers

The existence of enantiomer‐enriched mixtures of chiral pesticides in the environment is overwhelmingly positive. However, interactions between enantiomers have not been considered so far in risk assessments. Here, we chose three organophosphorus pesticides as representative chiral pesticides to investigate the possible interaction mode between each pair of enantiomers both in in vivo and in vitro. Data show that the enantiomers of methamidophos and profenofos have a simple additive effect, <zaq;1> whereas fensulfothion acts as an antagonist in AChE‐inhibition model. In contrast, enantiomers of methamidophos and fensulfothion had an additive effect in an acute toxicity test against Daphnia magna. A synergistic effect was observed in the joint toxicity of the profenofos enantiomers. The ability for enantiospecific biodegradation in the in vivo model contributed to the different interaction observed between the in vitro and in vivo models. Moreover, binding affinities were suspected as another reason for the different mode of action of mixture enantiomers. Our study recommends using a joint research model to treat chiral compounds in the real environment. Chirality 25:787–792, 2013. © 2013 Wiley Periodicals, Inc.     

Binding and photochemistry of enantiomeric 2-(3-benzoylphenyl)propionic acid (ketoprofen) in the human serum albumin environment.

Global analysis of circular dichroism multiwavelength data and time resolved fluorescence was applied to investigate the interaction of R(-)- and S(+)-ketoprofen (KP) with human serum albumin (HSA) in buffer solution at neutral pH. The most stable drug:protein adducts of 1 : 1 and 2 : 1 stoichiometry were characterized as regards the stability constants and the absolute circular dichroism spectra. The spectra of the diastereomeric 1 : 1 conjugates are negative with minima at ca. 350 nm for R(-)-KP and 330 nm for S(+)-KP, those of the 2 : 1 complexes are both negative with minimum at 340 nm and quite similar in shape to each other, thereby showing that the protein loses chiral recognition capability upon multiple binding. HSA intrinsic time resolved fluorescence data obtained exciting at 295 nm point to Trp 214 being located in the secondary binding site for both KP enantiomers. The photodegradation of the S(+)- and R(-)-KP:HSA complexes was studied by steady state photolysis using lambda(irr) > 320 nm. No decrease of the photodegradation quantum yields was observed in 1 : 1 complexes. An induction time for the photodegradation course in 2 : 1 complexes was observed. Transient absorption spectroscopy at lambda(exc) = 355 nm showed that triplet KP species were formed with stereo-differentiated lifetimes and high quantum yields (0.7-0.9). Secondary transients were consistent with the occurrence of photodecarboxylation and/or photoreduction within the protein matrix.     

Nefopam enantiomers: preclinical pharmacology/toxicology and pharmacokinetic characteristics in healthy subjects after intravenous administration

Nefopam (NEF) is a potent analgesic compound administered as a racemic mixture. Previous in vitro and in vivo studies with nefopam enantiomers have shown that (+)nefopam [(+)NEF] is substantially more potent than (-)nefopam [(-)NEF]. Differences between enantiomers have also been suggested in metabolic studies in vitro. The impact of these differences in vivo is not known because there is little or no information on the relative plasma concentrations of the enantiomers or on their kinetics. In this study, individual enantiomers of nefopam were synthesized and examined for acute toxicity in male and female rats and mice. Pharmacologic properties of enantiomers were examined using in vitro binding assays and antinociceptive tests in rats and mice. Additionally, a pharmacokinetic study was conducted in human volunteers. Subjects were administered 20 mg nefopam as Acupan(R) either as a 5- or 20-min intravenous infusion. In a control phase, subjects were administered only vehicle. Blood samples were collected through the following 24 h. Plasma samples were analyzed for individual enantiomers using a chiral assay developed for this purpose. The pharmacologic differences of previous studies were confirmed in receptor binding assays and in the hot plate and the formalin tests in mice. Neither enantiomer demonstrated substantial activity in the tail flick test in rats. No significant differences were revealed between LD(50) values of nefopam enantiomers after oral or intravenous administration in male and female rats or mice. There were no significant differences in AUC(0-infinity), C(max), or half-life between enantiomers following intravenous administration. Based on these findings, there is currently no compelling rationale to justify administering or monitoring individual enantiomers.     

Evaluation of chiral discrimination of highly negatively charged enantiomers by quaternary ammonium beta-cyclodextrin using 1H NMR

The positively charged quaternary ammonium cyclodextrin, QA-beta-CD, was previously used as a chiral selector to achieve baseline resolution of two of the dianionic enantiomers of disodium 3-(p-isothiocyanatophenoxy)-3-(p-isothiocyanatophenyl)propane-1,2-disulfate by capillary electrophoresis. The basis of the chiral discrimination between QA-beta-CD and the enantiomers was investigated by (1)H NMR spectroscopy. COSY and NOESY spectra were used to infer the role that molecular interactions and the stereocenters have upon association of QA-beta-CD with the enantiomers. A parallel two-step complexation model is used to rationalize the NMR and the chiral discrimination observed during separation of the enantiomers.     

Enantioselective chromatography of alkyl derivatives of 5-ethyl-5-phenyl-2-thiobarbituric acid studied by semiempirical AM1 method

Complexation of alkyl derivatives of 5-ethyl-5-phenyl-2-thiobarbituric acid (2-thiophenobarbital) enantiomers by beta-cyclodextrin was investigated by the AM1 method. The inclusion complexes of beta-cyclodextrin with neutral and anionic forms of these enantiomers have been modeled and energetically optimized. The chiral discrimination of enantiomers was analyzed in terms of differences in the interaction energies. The calculated interaction energies between each enantiomer of the investigated 2-thiobarbiturates and beta-cyclodextrin confirm the ability of beta-cyclodextrin to act as a mobile phase additive in reversed-phase HPLC to separate enantiomers by liquid chromatography and rationalize their order of elution.     

有机污染物在表层土壤中光降解的研究进展

土壤是承载有机污染物的重要介质,而光降解是降解土壤表层有机污染物的一种非常重要的非生物转化途径。研究土壤表层有机物的光降解对认识污染物土壤环境行为有非常重要的意义。20世纪90年代以来对土壤中有机污染物的光降解研究有了大量报道。本文阐述了土壤组成和质地、土壤湿度、土壤pH值和土壤厚度等因素对光解影响的研究现状;介绍了目前研究土壤光降解所采用的研究方法：土壤表层直接光解、土壤悬浮液光解、溶剂萃取与光降解联合处理,及其研究土壤光降解应用的动力模型;对不同农药和其它有机污染物在土壤中的光降解研究进行了综述,并对今后的研究作了展望。     

Stereoselective pharmacokinetics of ibuprofen in rats: effect of enantiomer-enantiomer interaction in plasma protein binding

Stereoselective pharmacokinetics of ibuprofen (IB) enantiomers were studied in rats. Unidirectional conversion from R-ibuprofen (R-IB) to S-ibuprofen (S-IB) was observed following intravenous administration. S-IB concentrations in plasma following racemate administration were simulated according to a conventional compartmental model using the parameters obtained after the administration of individual enantiomers, and resulted in overestimation of S-IB concentrations. Binding of IB enantiomers measured in rat plasma was stereoselective, the binding of R-IB being more favorable than that of S-IB. Moreover, there are interactions between IB enantiomers in binding, which may cause the increase of distribution volumes of IB enantiomers in the presence of their antipodes. Hence simulated S-IB concentrations according to a conventional compartment model were significantly greater than those observed. Indeed, when the enantiomer-enantiomer interactions were taken into account, simulation of S-IB concentrations in plasma following racemate administration was in good agreement with observed values. Therefore, interactions between stereoisomers as well as dispositional stereoselectivity have to be considered when pharmacokinetics of stereoisomers after administration of the racemate are compared to those after administration of individual isomers. Chirality 9:354-361, 1997. © 1997 Wiley-Liss, Inc.     

Broken symmetry between RNA enantiomers in a crystal lattice

Explaining the origin of the homochirality of biological molecules requires a mechanism of disrupting the natural equilibrium between enantiomers and amplifying the initial imbalance to significant levels. Authors of existing models have sought an explanation in the parity-breaking weak nuclear force, in some selectively acting external factor, or in random fluctuations that subsequently became amplified by an autocatalytic process. We have obtained crystals in which l- and d-enantiomers of short RNA duplexes assemble in an asymmetric manner. These enantiomers make different lattice contacts and have different exposures to water and metal ions present in the crystal. Apparently, asymmetry between enantiomers can arise upon their mutual interactions and then propagate via crystallization. Asymmetric racemic compounds are worth considering as possible factors in symmetry breaking and enantioenrichment that took place in the early biosphere.     

Electroencephalographic effects of thiopentone and its enantiomers in the rat

Electrophysiological studies with some chiral barbiturates have shown that one enantiomer can be excitant while the other is depressant. Thiopentone, a chiral barbiturate, has both differences in potency between enantiomers and biphasic effects on the electroencephalogram (EEG). This study investigated whether a differential EEG activity between the enantiomers of thiopentone could account for the biphasic effects. Rats were administered rac-, R- or S-thiopentone to determine the nature and time course of quantitative EEG effects. Two studies using computer-controlled i.v. infusions of the three drugs were performed in groups of animals previously prepared with EEG electrodes and/or arterial blood sampling cannulae. Study 1 used several stepwise increments in plasma drug concentration over 35 min, followed by washout. Study 2 used a 4 min period of constant plasma drug concentration, followed by washout. In both studies, both enantiomers and racemate caused an initial EEG activation followed by deactivation. Quantitative enantioselectivity was found for depression. The extent of depression was significantly less for R-thiopentone (P=0.008) and racthiopentone (P=0.038) than for S-thiopentone; recovery from depression appeared to be faster for R-thiopentone than either rac- or S-thiopentone. Fatality was only found with S-thiopentone (3/7 animals in Study 2). R-thiopentone plasma concentrations were approximately 8% less than those of S-thiopentone in rats treated with racthiopentone. Although small differences in clearance between enantiomers were found that may influence recovery, they were not large enough to account for the reported differences in potency between the two enantiomers.     

Parity nonconservation and the origin of biological chirality: Theoretical calculations

Recent theoretical calculations concerning the hypothesized connection between the parity violating weak interactions and the origin of biological chirality are extended in order to assess the relative importance of differential beta radiolysis of enantiomers and the energy difference between enantiomers. It is found that the largest chiral, polarizations are produced at lower temperatures where beta radiolysis dominates. At higher temperatures the energy difference between enantiomers dominates but the chiral polarization is appreciably smaller.     

Stereoselective plasma protein binding and target tissue distribution of clausenamide enantiomers in rats

Stereoselective differences in pharmacokinetics between clausenamide (CLA) enantiomers have been found after intravenous and oral administration of each enantiomer to rats. The differences could be associated with protein binding of CLA enantiomers. By equilibrium dialysis methods, the binding of CLA enantiomers to rat plasma protein was investigated. The results showed that mean percentages of (-) and (+)CLA in the bound form were 28.5% and 38.0%, respectively, indicating that the unbound fraction of (-)CLA was higher than that of (+)CLA, which provided an explanation for stereoselective pharmacokinetics of CLA enantiomers in rats. The results also showed that there were species differences in plasma protein binding of (-)-isomer between rats (28.5%) and rabbits (47.2%). Furthermore, effects of plasma protein binding on the distribution of CLA enantiomers to their possible target tissues were observed. The amount of (-)CLA in brain was greater than that of (+)CLA 15 min after administration of each enantiomer to rats. But the results were reverse at 4 h postdose. Further studies in distributional kinetics showed that (-)CLA had a more rapid absorption and distribution to hippocampus, cortex, and cerebellum than (+) CLA. (+)CLA had greater values for T(max), t(1/2) (beta), and AUC(0) (-->infinity), and smaller ones for CL/F and V(d)/F than its antipode. The data indicated that the distribution of (-) and (+)CLA in their target tissues was stereoselective. The stereoselective distribution might be involved in the metabolism and transport of two enantiomers in the central nerve system.     

Determination of absolute configuration of ketamine enantiomers by HPLC-CD-UV technique

Recognizing that the stereochemical structure of NMDA receptor antagonist ketamine provides valuable data about the relationship between its conformation and absolute configuration by CD-UV analysis, a method for the identification of ketamine enantiomers is proposed which avoids the need for authentic samples of the enantiomers. The ketamine enantiomers were separated by HPLC using Chiralcel OJ stationary phase. The in situ registration of CD and UV spectra, together with the application of the octant rule for cyclohexanone derivatives, makes possible the direct assignment of the eluted ketamine enantiomers.     

Effect of temperature on the reversal in the retention order of the enantiomers of mosapride on Chiral-AGP

The retention order of the enantiomers of mosapride could be controlled by column temperature and mobile phase pH. In the presented paper, temperature studies have been used to study the thermodynamics of the reversal in retention order. A linear relationship was obtained plotting the logarithm of the capacity factor versus the inverted column temperature. However, at higher mobile phase pHs, the logarithm of the separation factor versus the inverted column temperature showed a non-linear behaviour and at the highest mobile phase pH used (pH=7.4), an optimum in the separation factor was observed. The plots showed that the thermodynamics for the two enantiomers of mosapride differ in the studied mobile phase pH interval. Thermodynamic values, enthalpy and entropy were calculated and showed that at a low mobile phase pH, the enantiomeric resolution was caused by differences in enthalpy between the two enantiomers. However, at a higher mobile phase pH, the chiral discrimination was a result of entropy effects. High correlation was obtained between experimental and predicted separation factors at different mobile phase pHs.     

An accounting of C‐based trace gas release during abiotic plant litter degradation

Recent studies showed that photochemical breakdown (photodegradation) of plant material accounts for a substantial portion of litter decomposition and subsequent trace gas release in ecosystems under high radiative load and low precipitation. In the absence of solar radiation, thermal degradation may also cause trace gas release at temperatures below the ignition point. These observations suggest that the abiotic processes of photodegradation and thermal degradation of plant litter may be important in understanding global trace gas budgets. In a laboratory incubation study, we performed a simultaneous carbon (C) accounting of CO₂, CO, and CH₄ produced as a byproduct of photodegradation and thermal degradation of six different plant litter types that varied in chemical composition. The patterns of trace gas release during photodegradation and thermal degradation differed considerably across the six plant materials, suggesting that chemical composition of litter may influence the rates of abiotic degradation. There was a strong positive correlation between the rates of trace gas release during photodegradation and temperature. A significant portion of trace gases were produced during low temperature (< 100 °C) thermal degradation of litter in the absence of solar radiation, which was also positively correlated to temperature. In addition, both thermal degradation and photodegradation occurred in the absence of O₂. This indicates that the mechanism formerly accepted as photo‐oxidation may only be one of several photodegradation processes. We speculate that the direct breakdown of chemical groups such as carboxyl, carbonyl, and methoxyl groups may result in CO₂, CO, and CH₄ release. We suggest that the combined processes of thermal and photodegradation of litter may be a previously under accounted source of C‐based trace gases from terrestrial systems.     

Enantioselective assay of β-receptor antagonists present in microdialysis and plasma samples of rats

The enantiomers of alprenolol, metoprolol, and propranolol have been separated on an enantioselective cellulase column and analysed using a fully automated HPLC system involving coupled column chromatography and fluorescence detection. The assays had sufficient selectivity and sensitivity to investigate the disposition of these β₂-receptor antagonists in blood and brain extracellular fluid of rats. A cellulase column was used as the first column to separate the enantiomers giving separation factors between 2.9 and 4.3. After the separation, the enantiomers were trapped on two small precolumns by the use of a switching valve and were then introduced on an achiral C₁₈ analytical column by eluting the small columns backward. The enantiomers in blood and brain tissue dialysates were analysed by direct injection of 8 μl samples. The limit of quantitation was 0.025–0.4 μg/ml of the different enantiomers. Plasma samples were analysed after a simple extraction procedure. The intraassay precision of the lowest quality control plasma samples (0.2–0.8 μg rac drug/ml) was 4–8% for the different enantiomers. © 1995 Wiley-Liss, Inc.     

The influence of aging on the stereoselective pharmacokinetics of propranolol in the rat.

The influence of aging on the pharmacokinetics and the tissue distribution of (R)- and of (S)-propranolol was studied in 3-, 12-, and 24-month-old rats. After both iv and oral administration of rac-propranolol, the plasma concentrations were higher for the (R)- than for the (S)-enantiomer. For the tissue concentrations, the reverse was true. The free fraction of (S)-propranolol in plasma was about 4 times larger than that of (R)-propranolol, and this is the main factor responsible for the differences in kinetics between the two enantiomers. There was a suggestion for a difference in tissue binding between the two enantiomers. With aging, the plasma and tissue concentrations of both enantiomers increase, probably due to a decrease in blood clearance. Tissue binding did not change much with aging. Notwithstanding the marked differences between the kinetics of the propranolol enantiomers, the changes which occur with aging affect both enantiomers to the same degree.     

Experimental studies of competition between enantiomers in chiral liquid chromatography through their system peaks

Competition between the (+)- and (?) enantiomers of 2,2,2-trifluoro-1-(9-anthryl) ethanol as mobile phase additives was indicated by the chromatographic behavior of their system peaks. Two types of chiral stationary phases were used, one based on dinitrobenzoylphenylglycine and the other on dinitrobenzylphenylethylamine plus tartaric acid. The racemic mixture was used as the mobile phase additive and k′ of their system peaks was studied as a function of the mixture concentration in the mobile phase in both cases. A shift in k′ of the two system peaks was observed and considered as an indication that competition occurred. The areas of the two system peaks were also studied as a function of the concentration of the enantiomers in the samples, using two different compositions of the mobile phase. The dependency of system peaks' area on the sample composition indicated whether competition between the enantiomers occurred. One mobile phase contained 0.1 mM of the racemic mixture, where the area of the two retained system peaks behaved independently, i.e., only the peak corresponding to the enantiomer was affected by its presence in the sample. The other mobile phase contained 0.75 mM of the racemic mixture, and both peaks were affected by the injection of any one of the enantiomers. The interdependency of the system peaks' area on both the enantiomers indicated that their distribution in the chiral system was interrelated due to mutual interactions. A quantitative treatment of the interdependency and competition was excluded, due to the irreversible adsorption of the two enantiomers on the chiral stationary phase after using overloading concentrations. This irreversible adsorption was visualized by the appearance of two retained system peaks of the two residual enantiomers. These system peaks were detected only when the sample contained pure enantiomers due to competition between the enantiomer in the sample with the residual enantiomers in the stationary phase. © 1994 Wiley-Liss, Inc.     

A conformational alpha-helix to beta-sheet transition accompanies racemic self-assembly of polylysine: an FT-IR spectroscopic study

The self-assembly of polylysine chains with opposite chiral senses is an intriguing phenomenon, suggesting that subtle hydrational effects may be a driving force of protein aggregation. We have used FT-IR spectroscopy to characterize the alpha-helix-to-beta-sheet conformational transition that accompanies the aggregation of single and mixed enantiomers of polylysine. The preferential racemic self-assembly not only takes place at a lower temperature, but is also less prone to repulsive electrostatic interactions between lysine charged side chains, caused by decreasing pH (pD). While the process is generally irreversible, it yet appears to proceed in a stepwise manner through a sequence of thermodynamically, rather than kinetically controlled events involving gradual destabilization of alpha-helices. Interestingly, although the alpha/beta-transition is in either case (single or mixed enantiomers) an endothermic process, it may also be induced by freezing of water, which leads to markedly more complete (and irreversible) aggregation of the mixed enantiomers. Relevance of these findings has been discussed in the context of protein aggregation studies.     

Shedding light on plant litter decomposition: advances, implications and new directions in understanding the role of photodegradation

Litter decomposition contributes to one of the largest fluxes of carbon (C) in the terrestrial biosphere and is a primary control on nutrient cycling. The inability of models using climate and litter chemistry to predict decomposition in dry environments has stimulated investigation of non-traditional drivers of decomposition, including photodegradation, the abiotic decomposition of organic matter via exposure to solar radiation. Recent work in this developing field shows that photodegradation may substantially influence terrestrial C fluxes, including abiotic production of carbon dioxide, carbon monoxide and methane, especially in arid and semi-arid regions. Research has also produced contradictory results regarding controls on photodegradation. Here we summarize the state of knowledge about the role of photodegradation in litter decomposition and C cycling and investigate drivers of photodegradation across experiments using a meta-analysis. Overall, increasing litter exposure to solar radiation increased mass loss by 23% with large variation in photodegradation rates among and within ecosystems. This variation was tied to both litter and environmental characteristics. Photodegradation increased with litter C to nitrogen (N) ratio, but not with lignin content, suggesting that we do not yet fully understand the underlying mechanisms. Photodegradation also increased with factors that increased solar radiation exposure (latitude and litter area to mass ratio) and decreased with mean annual precipitation. The impact of photodegradation on C (and potentially N) cycling fundamentally reshapes our thinking of decomposition as a solely biological process and requires that we define the mechanisms driving photodegradation before we can accurately represent photodegradation in global C and N models.