Solution structure of molybdic acid from Raman spectroscopy and DFT analysis

Protonation of produces the well-characterized polymolybdates, but at concentrations below 10⁻³ M the dominant species is monomeric molybdic acid, H₂MoO₄. It is likely to be the species adsorbed on manganese oxide, a process thought to control levels in the ocean, because of the strong proton dependence of adsorption. The molecular structure of H₂MoO₄ is elusive, since it occurs only in dilute solutions. Using 244 nm laser excitation, near resonance with O → Mo charge-transfer electronic transitions of H₂MoO₄, we have detected a 919 cm⁻¹ Raman band assignable to ν_sMoO. Using DFT, we have computed geometries and vibrational modes for the various structures consistent with the H₂MoO₄ formula. We tested the computations on a series of Mo(VI) oxo complexes with known vibrational frequencies, at several levels of theory. Best agreement with experimental values, at reasonable computational cost, was obtained with the B3LYP functional, employing a LANL2DZ ECP basis set for Mo and the 6-311+G(2df,p) basis set for O and H. Among the possible H₂MoO₄ structures only those based on the MoO₃ unit, with one, two or three coordinated water molecules, gave a scaled frequency for ν_sMoO that was within two standard deviations of 919 cm⁻¹. Best agreement was obtained for MoO₃(H₂O)₃. The MoO₂ and MoO structures gave frequencies that were too high. The Mo(OH)₆ structure could be excluded, because its vibrational frequencies shift down strongly upon H/D exchange, whereas the 919 cm⁻¹H₂MoO₄ band shifts up 1 cm⁻¹ in D₂O.     

Natural niche for organohalide-respiring Chloroflexi

The phylum Chloroflexi contains several isolated bacteria that have been found to respire a diverse array of halogenated anthropogenic chemicals. The distribution and role of these Chloroflexi in uncontaminated terrestrial environments, where abundant natural organohalogens could function as potential electron acceptors, have not been studied. Soil samples (116 total, including 6 sectioned cores) from a range of uncontaminated sites were analyzed for the number of Dehalococcoides-like Chloroflexi 16S rRNA genes present. Dehalococcoides-like Chloroflexi populations were detected in all but 13 samples. The concentrations of organochlorine ([organochlorine]), inorganic chloride, and total organic carbon (TOC) were obtained for 67 soil core sections. The number of Dehalococcoides-like Chloroflexi 16S rRNA genes positively correlated with [organochlorine]/TOC while the number of Bacteria 16S rRNA genes did not. Dehalococcoides-like Chloroflexi were also observed to increase in number with a concomitant accumulation of chloride when cultured with an enzymatically produced mixture of organochlorines. This research provides evidence that organohalide-respiring Chloroflexi are widely distributed as part of uncontaminated terrestrial ecosystems, they are correlated with the fraction of TOC present as organochlorines, and they increase in abundance while dechlorinating organochlorines. These findings suggest that organohalide-respiring Chloroflexi may play an integral role in the biogeochemical chlorine cycle.     

Synthesis of polyglycerol phosphate by Bacillus stearothermophilus.

A particulate enzyme preparation from Bacillus stearothermophilus synthesized 1,3-poly(glycerol phosphage) from CDPglycerol at an optimum pH of 8.0 and the reaction was stimulated by divalent cations. Km for CDPglycerol was 0.18 mM. The synthesis was inhibited by CMP, CDP, and CTP and by concentrations of CDP-glycerol above 0.49 mM. The reaction was irreversible, The product had an average chain length of 8 glycerol units. About two thirds of the polymers were synthesized in entirety while the ramainder were attached to some acceptor by their phosphate end. The enzome was able to synthesize only a limited amount of polymer.     

Dynamic compression counteracts IL-1β induced inducible nitric oxide synthase and cyclo-oxygenase-2 expression in chondrocyte/agarose constructs

Background  

Nitric oxide and prostaglandin E₂ (PGE₂play pivotal roles in both the pathogenesis of osteoarthritis and catabolic processes in articular cartilage. These mediators are influenced by both IL-1β and mechanical loading, and involve alterations in the inducible nitric oxide synthase (iNOS) and cyclo-oxygenase (COX)-2 enzymes. To identify the specific interactions that are activated by both types of stimuli, we examined the effects of dynamic compression on levels of expression of iNOS and COX-2 and involvement of the p38 mitogen-activated protein kinase (MAPK) pathway.     

Multicopper oxidase involvement in both Mn(II) and Mn(III) oxidation during bacterial formation of MnO2

Global cycling of environmental manganese requires catalysis by bacteria and fungi for MnO₂ formation, since abiotic Mn(II) oxidation is slow under ambient conditions. Genetic evidence from several bacteria indicates that multicopper oxidases (MCOs) are required for MnO₂ formation. However, MCOs catalyze one-electron oxidations, whereas the conversion of Mn(II) to MnO₂ is a two-electron process. Trapping experiments with pyrophosphate (PP), a Mn(III) chelator, have demonstrated that Mn(III) is an intermediate in Mn(II) oxidation when mediated by exosporium from the Mn-oxidizing bacterium Bacillus SG-1. The reaction of Mn(II) depends on O₂ and is inhibited by azide, consistent with MCO catalysis. We show that the subsequent conversion of Mn(III) to MnO₂ also depends on O₂ and is inhibited by azide. Thus, both oxidation steps appear to be MCO-mediated, likely by the same enzyme, which is indicated by genetic evidence to be the MnxG gene product. We propose a model of how the manganese oxidase active site may be organized to couple successive electron transfers to the formation of polynuclear Mn(IV) complexes as precursors to MnO₂ formation.     

Effect of ultraviolet radiation on survival, infectivity and maturation of Schistosoma mansoni cercariae

S. mansoni cercariae exposed to ultraviolet radiation for 1, 3, 5, 10 and 20 s as well as non-irradiated cercariae remained actively motile 30 min post-irradiation. Thereafter the activity decreased with increasing dose level of radiation and age of cercariae. There was no significant difference between the rates of attachment of the batches of cercariae. The recovery rates (0-49% of cercariae to which mice were exposed) of adult worms were, however, significantly different from the number of cercariae calculated to have attached to the mice (93.5-100% of cercariae to which mice were exposed). Maturation and penetration rates were dependent on radiation exposure levels. Numbers of eggs deposited in the liver of mice as well as hatchability rate of eggs varied significantly with the levels of exposure to radiation.     

文山松毛虫质型多角体病毒形态结构及理化性质的研究

对文山松毛虫质型多角体病毒的形态结构及理化特性进行了研究,多角体大部分为六边形,少数为四边形及近园形,其大小在0.47～2.45μ之间,平均为1.1μ。病毒粒子呈球形,无囊膜,致密的核芯区由一层外壳包裹,直径为60nm。病毒粒子表面有12个刺突,放大图象可见其亚单位排列。多角体蛋白的主要成分为一种,分子量为26200道尔顿,多角体蛋白氨基酸组成中不含半胱氨酸;其碱性氨基酸与酸性氨基酸之比为1:2.16。病毒粒子结构蛋白含五条多肽组分。用SDS-热酚法提取所得核酸,其热变性紫外吸收OD_(260)值增加51.6％。抗核酸酶S_1。Tm值为86℃。在1％琼脂糖凝胶电泳中可分为9个片段,而在5％PAGE中,则可分为10个片段。各片段大小在0.66×10~6～2.85×10~6道尔顿之间,总分子量为15.35×10~6。电镜分析研究显示了CPV RNA在0.4μ、0.8μ和1.2μ处有三个分布峰。     

An Investigation into the Rate and Control of Assimilate Movement from Leaves in Pisum sativum

Export studies were made on leaves of Pisum by monitoring the¹⁴CO₂-treated source leaf at its surface at frequent intervals.Radiocarbon levels of fresh leaf samples showed a good correlationwith results from the more conventional methods of radiocarbonestimation which involve destructive analysis. The rate of export was highest in plants which had been defoliated,except for the source leaf 20 h or more before the start ofthe export study. Removal of the shoot apex reduced export andprogressive reduction in sink capacity was associated with decreasedexport rates, particularly over short time periods. Export rateswere similar in defoliated and non-defoliated plants where theshoot apex and the roots had been excised. This suggested thata decrease in the source resulted in higher export rates fromthe remaining source only when active sinks were present; thisin turn suggests that, at least under these conditions, activeremoval of photosynthate is more important in controlling exportthan the photosynthate build-up in the leaf itself. The non-destructive technique enabled comparisons to be madebetween export curves for individual plants. It was found thatin experiments replicated in time, the same relationship betweentreatments was present on different days and the shape of theexport curves was similar but the absolute values for exportedradiocarbon sometimes varied considerably.     

Schistosoma mansoni: effect of a protein-free host diet on tegument.

The effect of a protein deficiency in the host's diet on the tegument of Schistosoma mansoni is described. Both the infected and the uninfected hamsters, fed on the diet, were stunted in growth; but the effect of the diet was more pronounced on the infected hamsters. The parasites recovered from both the liver and the mesenteric veins of animals fed on the diet from the time of infection were also retarded in growth. The tegument of both groups of parasites were reduced in height as compared with the tegument of control worms. The worms recovered from the liver of the hamsters were less adversely affected than the worms recovered from the mesenteric veins, in the sense that the tegument did not show any sign of degeneration, as was found in the latter group of parasites. In the worms from the mesenteric veins, the external plasma membrane was approximately half the thickness of the external plasma membrane of control worms. The invaginations of the external plasma membrane of experimental worms penetrated deeply into the tegument and in most instances almost reached the basal plasma membrane. Prolonged feeding of the hosts on the experimental diet resulted in the disintegration of the tegument in localised areas of the body. There was no adverse effect on adult worms of an established infection after the hosts were transferred to the protein-free diet for up to 3 wk. The ability of the tegument to regenerate after transferring the hosts from the experimental diet to normal laboratory diet (control diet) was demonstrated.