天目湖水环境与渔业生产及旅游发展的关系

根据2001年6月-2002年5月在天目湖进行的每月一次的全湖周年观测以及相关的历史资料,全面分析了天目湖水环境的演变趋势,发现天目湖水质下降极为明显,并且随着渔业生产和游客的逐年增加,呈现出加速恶化的趋势,水质恶化主要表现为蓝藻、绿藻迅速繁殖,感官质量下降.分析原因,主要是由于上游围湖养鱼、湖内放养及附近宾馆饭店排放出大量氮磷营养盐所致.针对当前天目湖水环境现状,提出了保护水源、改善水质的对策措施:(1)严格控制污染源;(2)退渔还湖,恢复水生植被;(3)调整养殖结构;(4)恢复植被,控制面源氮磷入湖量;(5)加强流域管理,确定水源保护地;(6)实施生态旅游.     

A metal-mediated hydride shift mechanism for xylose isomerase based on the 1.6 A Streptomyces rubiginosus structures with xylitol and D-xylose

The crystal structure of recombinant Streptomyces rubiginosus D-xylose isomerase (D-xylose keto-isomerase, EC 5.3.1.5) solved by the multiple isomorphous replacement technique has been refined to R = 0.16 at 1.64 A resolution. As observed in an earlier study at 4.0 A (Carrell et al., J. Biol. Chem. 259: 3230-3236, 1984), xylose isomerase is a tetramer composed of four identical subunits. The monomer consists of an eight-stranded parallel beta-barrel surrounded by eight helices with an extended C-terminal tail that provides extensive contacts with a neighboring monomer. The active site pocket is defined by an opening in the barrel whose entrance is lined with hydrophobic residues while the bottom of the pocket consists mainly of glutamate, aspartate, and histidine residues coordinated to two manganese ions. The structures of the enzyme in the presence of MnCl2, the inhibitor xylitol, and the substrate D-xylose in the presence and absence of MnCl2 have also been refined to R = 0.14 at 1.60 A, R = 0.15 at 1.71 A, R = 0.15 at 1.60 A, and R = 0.14 at 1.60 A, respectively. Both the ring oxygen of the cyclic alpha-D-xylose and its C1 hydroxyl are within hydrogen bonding distance of NE2 of His-54 in the structure crystallized in the presence of D-xylose. Both the inhibitor, xylitol, and the extended form of the substrate, D-xylose, bind such that the C2 and C4 OH groups interact with one of the two divalent cations found in the active site and the C1 OH with the other cation. The remainder of the OH groups hydrogen bond with neighboring amino acid side chains. A detailed mechanism for D-xylose isomerase is proposed. Upon binding of cyclic alpha-D-xylose to xylose isomerase, His-54 acts as the catalytic base in a ring opening reaction. The ring opening step is followed by binding of D-xylose, involving two divalent cations, in an extended conformation. The isomerization of D-xylose to D-xylulose involves a metal-mediated 1,2-hydride shift. The final step in the mechanism is a ring closure to produce alpha-D-xylulose. The ring closing is the reverse of the ring opening step. This mechanism accounts for the majority of xylose isomerase's biochemical properties, including (1) the lack of solvent exchange between the 2-position of D-xylose and the 1-pro-R position of D-xylulose, (2) the chemical modification of histidine and lysine, (3) the pH vs. activity profile, and (4) the requirement for two divalent cations in the mechanism.     

Stereoselective synthesis of a C-glycosylic compound (a "methyl C-glycoside") through a regioselective free-radical ring-opening reaction. A single-crystal X-ray structure determination

Readily available 3,4,6-tri-O-acetyl-D-glucal was converted to 2,6-anhydro-5,7-O-benzylidene-1,3,4-trideoxy-D-arabino-hept-3-enitol, a methyl C-glycosylic compound. Cyclopropanation of 4,6-O-benzylidene-D-glucal, followed by tributylstannyl radical-mediated regioselective ring opening of the 1,2-cyclopropano sugar led to a 2,6-anhydro-1-deoxyheptose, (a "methyl C-beta-D-glycoside"). The stereochemistry of the 1,2-cyclopropano sugar and the "methyl C-glycoside" were confirmed by single-crystal X-ray diffraction studies.     

口腔锥形束CT联合微创拔牙技术对埋伏阻生牙患者牙槽完整度及张口受限度的影响

摘要 目的：探讨口腔锥形束CT联合微创拔牙技术对埋伏阻生牙患者牙槽完整度及张口受限度的影响。方法：选取我院2017年1月到2023年2月收治的50例埋伏阻生牙患者作为研究对象,应用随机数字表法将其分为观察组与对照组,每组25例。对照组应用传统拔牙技术进行治疗,观察组采取口腔锥形束CT联合微创拔牙技术治疗,对比两组患者术后疼痛、面部肿胀、牙槽完整度,术后即刻和术后3 d的炎症因子水平,术后张口受限程度以及菌斑指数（PLI）,龈沟出血指数（SBI）、龈沟探诊深度（SPD）、牙龈指数（GI）等牙周健康指标水平。结果：观察组患者视觉模拟量表（VAS）评分、面部肿胀程度以及牙槽完整度评分明显低于对照组（P＜0.05）;术后即刻两组患者白细胞介素-6（IL-6）、白细胞介素-1（IL-1）、肿瘤坏死因子-α（TNF-α）相关炎症因子水平对比无明显差异（P＞0.05）,术后3 d两组患者IL-6、IL-1、TNF-α相关炎症因子水平均降低,且观察组低于对照组（P＜0.05）;观察组患者开口度正常的比例明显高于对照组,中度、重度张口受限度比例明显低于对照组（P＜0.05）;治疗前两组患者GI、SPD、SBI、PLI水平对无明显差异（P＞0.05）,治疗后两组患者GI、SPD、SBI、PLI水平均降低,观察组低于对照组（P＜0.05）。结论：口腔锥形束CT联合微创拔牙技术针对埋伏阻生牙进行治疗与传统拔牙相比能够改善患者术后疼痛、面部肿胀程度,减轻术后张口受限程度,减轻炎症反应水平,提升牙周健康程度,值得临床应用推广。     

Crystal structure of phenylacetic acid degradation protein PaaG from Thermus thermophilus HB8

Microbial degradation of phenylacetic acid proceeds via the hybrid pathway that includes formation of a coenzyme A thioester, ring hydroxylation, non‐oxygenolytic ring opening, and β‐oxidation‐like reactions. A phenylacetic acid degradation protein PaaG is a member of the crotonase superfamily, and is a candidate non‐oxygenolytic ring‐opening enzyme. The crystal structure of PaaG from Thermus thermophilus HB8 was determined at a resolution of 1.85 Å. PaaG consists of three identical subunits related by local three‐fold symmetry. The monomer is comprised of a spiral and a helical domain with a fold characteristic of the crotonase superfamily. A putative active site residue, Asp136, is situated in an active site cavity and surrounded by several hydrophobic and hydrophilic residues. The active site cavity is sufficiently large to accommodate a ring substrate. Two conformations are observed for helix H2 located adjacent to the active site. Helix H2 is kinked at Asn81 in two subunits, whereas it is kinked at Leu77 in the other subunit, and the side chain of Tyr80 is closer to Asp136. This indicates that catalytic reaction of PaaG may proceed with large conformational changes at the active site. Asp136 is the only conserved polar residue in the active site. It is located at the same position as those of 4‐chlorobenzoyl‐CoA dehalogenase and peroxisomal Δ³,Δ²‐enoyl‐CoA isomerase, indicating that PaaG may undergo isomerization or a ring‐opening reaction via a Δ³,Δ²‐enoyl‐CoA isomerase‐like mechanism. Proteins 2009. © 2009 Wiley‐Liss, Inc.     

Impact of anthropogenic disturbances on beetle communities of French Mediterranean coastal dunes

In coastal dunes, influenced by anthropogenic activities such as tourism, it is important to determine the relative influence of environmental factors at different spatial scales to evaluate the sensitivity of local communities to disturbances. We analyzed beetle communities of 14 dunes of the French Mediterranean coast: four in the relatively preserved Camargue area, and ten in the Var department, where tourism is intensive. Beetle communities were studied three times in early spring using sand sampling. Species-environment relationships were evaluated at the regional, landscape and local scale using redundancy analysis (RDA) and variability partitioning. About 28 species were identified, of which 15 were sand-specialist species, which accounted for more than 93% of total abundance. The beetle communities of Camargue were significantly different from those of the Var department owing to the pullulation of a Tenebrionid species (Trachyscelis aphodioides Latr.) in the Var, except for one restored dune where the community was very similar to those of Camargue. Our results showed no longitudinal gradient between the two regions. Local factors (dune height, preservation and disturbance index) significantly explained most of the variation in the dominance of T. aphodioides, while some other local factors were important for other psammophilous species. This study also suggests that dune beetle communities are strongly affected on beaches intensively managed for tourism, but beetles are still abundant in much disturbed sites.     

Exploring the activation mechanism of TRPM8 channel by targeted MD simulations

The TRPM8 cation channel belongs to the superfamily of transient receptor potential (TRP) channels. It is involved in non-painful cool sensation and triggered by diverse chemical and physical stimuli whose precise activation mechanism is still unknown. The study presents a set of targeted molecular dynamics (MD) simulations involving selected complexes of the TRPM8 channel whose homology model was recently generated by some of us. More in detail, the MD simulations concerned the TRPM8 alone and in complex with agonists and antagonists. These simulations were focused on voltage sensor module and designed to validate the ligand induced activation mechanism as hypothesized in our previous study. The obtained results are in encouraging agreement with the proposed mechanism and allow a clear discrimination between agonists and antagonists. In addition, the MD runs confirm that the agonist binding triggers a set of concatenate conformational shifts which induce the approaching of the S3 segment toward the S4 segment and culminate in an extension of the latter. By introducing suitable constraints, the reported MD simulations were rendered as fast as possible in order to achieve a truly productive compromise between reliability and computational costs. The obtained results emphasize that suitably targeted MD runs can be fast enough to be systematically applied to predict the bioactivity of large datasets providing it as an useful tool in rational ligand design process.     

Regioselective ring opening of exo- and endo-3,4-benzylidene acetals of arabinopyranoside derivatives with Lewis acids and reducing agents

Dioxolane type 3,4-benzylidene acetals of benzyl β-l-arabinose either as a mixture or pure exo- and endo-isomers cleavaged with BF₃·OEt₂/Et₃SiH in dichloromethane or acetonitrile regioselectively, provided the 4-O-benzyl-3-hydroxy derivative. The reaction with TiCl₄/Et₃SiH or Cu(OTf)₂/Et₃SiH provided a mixture of 3- and 4-O-benzyl derivatives whereas with Cu(OTf)₂/BH₃·THF gave only hydrolyzed product. The regioselectivity of the reaction was proved to be directed by the acetyl substitution at C-2. Benzyl substitution provided a mixture of 3- and 4-O-benzyl derivatives in 1:1 ratio whereas non-substitution yielded the same mixture in 2:1 ratio.