Synthesis and Mosquito Repellent Properties of 2,2-Dialkyl- and 2-Alkyl-4,4-dimethyl-N-acetyloxazolidines

Nineteen novel N-acetyl-2,2-dialkyloxazolidines ( 2 ) and N-acetyl-2-alkyl-4,4-dimethyloxazolidines ( 3 ) were synthesized from commercially available carbonyl compounds and ethanolamine or 2-amino-2-methyl-1-propanol. Their bioactivity against laboratory-reared mosquitoes was compared in patch tests to known N-acetyl-2-alkyloxazolidines ( 1 ) and N,N-diethyl-m-toluamide (deet insect repellent). Isomeric composition measurements by [¹³C]NMR spectroscopy favoured the Z rotational isomer for samples of 2 (91–96% Z) and the E rotational isomer for samples of 3 (66–71% E), in agreement with molecular mechanics calculations on rotational isomers of model oxazolidines. Samples of 1 were previously shown to exist in solution mostly as the Z isomer (60–70% Z). Within the optimal molecular weight range for these experimental chemicals, the duration of repellency against Aedes aegypti (L.), Anopheles quadrimaculatus Say and Anopheles albimanus Wiedemann generally followed the order: 1 > 2 >deet> 3 . Bioassay data are discussed in relation to the equilibrium populations of rotational isomers for substituted N-acetyloxazolidines.     

Phosphorus forms as affected by abandoned anthills (Formica polyctena Förster) in forest soils: sequential extraction and liquid-state 31P-NMR spectroscopy

Ants are known to concentrate phosphorus (P) inside their nests via collection of food and litter. To elucidate the possible effects on long-term availability of soil P, five anthills abandoned by Red wood ant (Formica polyctena Förster) > 5—20 years ago were characterized for soil P forms in a temperate Danish deciduous forest. Sequentially extracted P fractions and liquid-state ³¹P nuclear magnetic resonance (NMR) spectra were obtained on surface samples (0—10 cm) from abandoned anthills and adjacent topsoil; in addition one representative soil profile in an abandoned anthill was investigated. The results show that different inorganic and all organic P fractions were enriched by a factor of 2.0—3.3 inside anthills relative to the surrounding soil. The soil underneath the abandoned anthill had higher P contents until 50-cm depth. Phosphorus composition was less affected by former anthill construction. Only the younger anthills revealed a preferential accumulation of labile organic P forms such as Na-HCO₃ extractable P or diester P. The accumulation of the stable and moderate labile P forms, however, persisted for ≥ 20 years after abandonment. We concluded that former ant activity enhanced long-term P availability of soil due to high local P inputs, whereas changes of the P form distribution lasted 5—10 years after nest abandonment.     

Complete Lipooligosaccharide Structure from Pseudoalteromonas nigrifaciens Sq02-Rifr and Study of Its Immunomodulatory Activity

Lipopolysaccharides (LPS) are surface glycoconjugates embedded in the external leaflet of the outer membrane (OM) of the Gram-negative bacteria. They consist of three regions: lipid A, core oligosaccharide (OS), and O-specific polysaccharide or O-antigen. Lipid A is the glycolipid endotoxin domain that anchors the LPS molecule to the OM, and therefore, its chemical structure is crucial in the maintenance of membrane integrity in the Gram-negative bacteria. In this paper, we reported the characterization of the lipid A and OS structures from Pseudoalteromonas nigrifaciens Sq02-Rif^r, which is a psychrotrophic Gram-negative bacterium isolated from the intestine of Seriola quinqueradiata. The immunomodulatory activity of both LPS and lipid A was also examined.     

氢氟酸对发酵前后玉米秸秆有机质结构的影响

为了验证氢氟酸(HF)处理是否可改变不同降解程度有机质的性质和结构,本研究配制不同浓度(0、2%、10%)HF对发酵前后的玉米秸秆进行酸洗处理,结合常用化学表征手段、分子生物标志物技术和稳定碳同位素比值,探究酸洗液和固体样品中有机质性质的变化。结果表明：发酵后玉米秸秆有机氮含量增加1.15～1.51倍,有机碳含量变化不明显,导致C/N显著降低,但是不同浓度HF处理后,有机碳和有机氮含量并没有明显改变;发酵前、后玉米秸秆中有机质的δ¹³C值分别是-12.83‰±0.25‰、-13.63‰±0.09‰,不同浓度HF处理发酵前和发酵后的玉米秸秆的δ¹³C基本不变;发酵前、后玉米秸秆固体中木质素总量分别为(18.81±7.44)、(12.01±1.75)mg·g^-1,HF处理发酵后玉米秸秆中木质素的降解参数和来源参数不变。HF处理会导致部分溶解性有机质的流失,发酵后玉米秸秆中含氧官能团优先降解,部分溶出性木质素流失,但木质素的结构不会改变。     

Improved Isolation Procedures for Okadaic Acid Group Toxins from Shellfish (Mytilus edulis) and Microalgae (Prorocentrum lima)

Okadaic acid (OA) group toxins may accumulate in shellfish and can result in diarrhetic shellfish poisoning when consumed by humans, and are therefore regulated. Purified toxins are required for the production of certified reference materials used to accurately quantitate toxin levels in shellfish and water samples, and for other research purposes. An improved procedure was developed for the isolation of dinophysistoxin 2 (DTX2) from shellfish (M. edulis), reducing the number of purification steps from eight to five, thereby increasing recoveries to ~68%, compared to ~40% in a previously reported method, and a purity of >95%. Cell densities and toxin production were monitored in cultures of Prorocentrum lima, that produced OA, DTX1, and their esters, over ~1.5 years with maximum cell densities of ~70,000 cells mL⁻¹ observed. Toxin accumulation progressively increased over the study period, to ~0.7 and 2.1 mg L⁻¹ of OA and DTX1 (including their esters), respectively, providing information on appropriate harvesting times. A procedure for the purification of OA and DTX1 from the harvested biomass was developed employing four purification steps, with recoveries of ~76% and purities of >95% being achieved. Purities were confirmed by LC-HRMS, LC-UV, and NMR spectroscopy. Additional stability observations led to a better understanding of the chemistry of these toxins.     

IWSF-FA模袋混凝土抗压强度、孔隙结构和物质组成

为优化模袋混凝土衬砌性能,合理利用当地粉煤灰和废弃硅粉代替部分水泥制备模袋混凝土衬砌.通过抗压强度试验、固体紫外试验、核磁共振和热重试验研究双掺粉煤灰-工业废弃硅粉替代适量水泥后对模袋混凝土抗压特性、内部孔隙结构和水化物质组成的影响.结果表明:合理双掺工业废弃硅粉和粉煤灰(如FA15S4)可以提高模袋混凝土的抗压强度;紫外吸收光谱表明其水化产物C-S-H和CH组成优于其他组别;核磁共振T₂谱分布呈现“三峰结构”,左峰信号幅度最高,双掺工业废弃硅粉-粉煤灰有利于改善其内部孔隙结构.并且双掺工业废弃硅粉和粉煤灰后,热学性质良好.建立了基于BP神经网络理论的模袋混凝土早期抗压强度预测模型,预测结果与试验测试值的最大相对误差为2.7%.研究结果可为工业废弃硅粉和粉煤灰混凝土在水工衬砌工程中的应用提供参考依据.     

龙竹半纤维素的提取分离及结构表征

龙竹竹粉经脱蜡及脱淀粉后,再经亚氯酸钠脱木素制得综纤维素,进一步用二甲亚砜(DMSO)以及KOH溶液提取,经乙醇沉淀后制得半纤维素H1和H2,得率分别为18.7%和39.8%。对半纤维素组分H1和H2进行糖分析、红外光谱以及核磁共振分析。结果表明,龙竹半纤维素为乙酰化的L-阿拉伯糖基-4-O-甲基葡萄糖醛酸木聚糖,其中阿拉伯糖连接在木聚糖主链的C-3位,4-O-甲基葡萄糖醛酸连接在木聚糖主链的C-2位,而乙酰基连接在木聚糖主链的C-2位或C-3位。