1H-, 13C-, 19F-, 31P-NMR-Charakterisierung der Produkte der Alkoholyse von Trichlorophosphazen-N-Phosphoryldichlorid durch Trifluoroethanol

¹H, ¹³C, ¹⁹F, ³¹P N.M.R. Characterization of the Alcoholysis Products of Trichlorophosphazene-N-phosphoryldichloride by Trifluoroethanol Since polychlorophosphazenes can be obtained by polycondensation of P₂NOCl₅ the classical substitution of Cl by CF₃CH₂O in these polymers was transposed to P₂NOCl₅. The formation of mono, di, or pentaester depends on the molar ratio of the reactants. By reaction of CF₃CH₂OH on the pentaester a tetrasubstituted derivative of tetrachlorodiphosphorylimid is obtained. All products are characterized by mass spectroscopy and ¹H, ¹³C, ¹⁹F, and ³¹P n.m.r.     

Influence of the 4,6-O-benzylidene, 4,6-O-phenylboronate, and 4,6-O-polystyrylboronate protecting groups on the stereochemical outcome of thioglycoside-based glycosylations mediated by 1-benzenesulfinyl piperidine/triflic anhydride and N-iodosuccinimide/trimethylsilyl triflate

The effect of 4,6-O-benzylidene acetals, 4,6-O-phenylboronate esters, and 4,6-O-polystyrylboronate esters on the stereoselectivity of couplings to galacto-, gluco-, and mannopyranosyl thioglycosides, otherwise protected with benzyl ethers, has been investigated by the benzenesulfinyl piperidine/trifluoromethanesulfonic anhydride (BSP), diphenyl sulfoxide/trifluoromethanesulfonic anhydride (Ph(2)SO), and N-iodosuccinimide/trimethylsilyl trifluoromethanesulfonate (NIS/TMSOTf) methods. The BSP and Ph(2)SO methods give comparable results in all three systems whereas the NIS method affords significantly different stereoselectivities in both the gluco and manno, but not the galacto series. The benzylidene acetal and boronate esters influence the stereochemistry in a similar manner in the beta-selective manno series and the alpha-selective galacto series but show significant differences with the glucose donors. The differences between the glucose, galactose, and mannose series reflect the established differences in reactivity and, especially for mannose, those in the anomeric effect and are best interpreted in terms of changes in the relative energetics between the alpha- and beta-covalent triflate intermediates and the various contact ion pairs with which they are necessarily in equilibrium.     

X射线荧光光谱(XRF)法测定绿泥石中镁、铝、硅、磷、钾、钙、钛、铁元素含量

建立了X射线荧光光谱法测定绿泥石中镁、铝、硅、磷、钾、钙、钛、铁元素含量的快速分析方法。以标准物质及标准物质与基准试剂氧化镁、氧化钙人工混合配制标样的方法建立标准工作曲线,重点讨论了熔剂和脱模剂的选取。最佳熔样条件：采用8.0g四硼酸锂和偏硼酸锂混合熔剂(质量比67: 33)+0.8g样品并添加溴化锂作为脱模剂,熔样温度1100℃,熔样时间10min。该方法相对标准偏差(n=12)均小于5.57%,绿泥石样品测定结果与化学法一致,硅酸盐标准物质测定结果均满足不确定度要求。     

大钟拍声的调整实验

阐明大钟拍声的发生原理,并用大钟振动拍的理论模型说明拍的特性,从而控制清晰度。在实验钟上附着质量,根据附着质量位置的不同,能够改变其非对称程度,进一步调整拍频,同时用有限元分析的结果和等效圆环理论计算的结果对比。引入等效圆环理论,通过建立一个理论上带有附加质量的轴对称圆环模型,达到具有和大钟相同的振动特性。根据模型,得到在大钟特定位置附加的质量,以同时调整所需拍的清晰度和周期。在大钟多个位置进行实验,并进行有限元分析,验证了该理论的有效性。     

Inclusion Complex between Local Anesthetic/2-hydroxypropyl-β-cyclodextrin in Stealth Liposome

The drugs delivery system in the treatment of diseases has advantages such as reduced toxicity, increased availability of the drug, etc. Therefore, studies of the supramolecular interactions between local anesthetics (LAs) butamben (BTB) or ropivacaine (RVC) complexed with 2-hydroxypropyl-β-cyclodextrin (HP-βCD) and carried in Stealth liposomal (SL) are performed. ¹H-NMR nuclear magnetic resonance (DOSY and STD) were used as the main tools. The displacements observed in the ¹H-NMR presented the complexion between LAs and HP-βCD. The diffusion coefficients of free BTB and RVC were 7.70 × 10⁻¹⁰ m² s⁻¹ and 4.07 × 10⁻¹⁰ m² s⁻¹, and in the complex with HP-βCD were 1.90 × 10⁻¹⁰ m² s⁻¹ and 3.64 × 10⁻¹⁰ m² s⁻¹, respectively, which indicate a strong interaction between the BTB molecule and HP-βCD (98.3% molar fraction and Ka = 72.279 L/mol). With STD-NMR, the encapsulation of the BTB/HP-βCD and RVC/HP-βCD in SL vesicles was proven. Beyond the saturation transfer to the LAs, there is the magnetization transfer to the hydrogens of HP-βCD. BTB and RVC have already been studied in normal liposome systems; however, little is known of their behavior in SL.     

Enantioselective 1,3-Dipolar Cycloaddition Using (Z)-α-Amidonitroalkenes as a Key Step to the Access to Chiral cis-3,4-Diaminopyrrolidines

The enantioselective 1,3-dipolar cycloaddition between imino esters and (Z)-nitroalkenes bearing a masked amino group in the β-position was studied using several chiral ligands and silver salts. The optimized reaction conditions were directly applied to the study of the scope of the reaction. The determination of the absolute configuration was evaluated using NMR experiments and electronic circular dichroism (ECD). The reduction and hydrolysis of both groups was performed to generate in an excellent enantiomeric ratio the corresponding cis-2,3-diaminoprolinate.     

Effect of Bauhinia monandra Kurz Leaf Preparations on Embryonic Stages and Adult Snails of Biomphalaria glabrata (Say, 1818), Schistosoma mansoni Cercariae and Toxicity in Artemia salina

Biomphalaria glabrata snails constitute the main vector of schistosomiasis in Brazil, and Bauhinia monandra Kurz, the leaves of which contain BmoLL lectin with biocidal action, is a plant widely found on continents in which the disease is endemic. This work describes the composition of B. monandra preparations and the effect on embryos and adult snails, their reproduction parameters and hemocytes. We also describe the results of a comet assay after B. glabrata exposure to sublethal concentrations of the preparations. Additionally, the effects of the preparations on S. mansoni cercariae and environmental monitoring with Artemia salina are described. In the chemical evaluation, cinnamic, flavonoid and saponin derivatives were detected in the two preparations assessed, namely the saline extract and the fraction. Both preparations were toxic to embryos in the blastula, gastrula, trochophore, veliger and hippo stages (LC₅₀ of 0.042 and 0.0478; 0.0417 and 0.0419; 0.0897 and 0.1582; 0.3734 and 0.0974; 0.397 and 0.0970 mg/mL, respectively) and to adult snails (LC₅₀ of 6.6 and 0.87 mg/mL, respectively), which were reproductively affected with decreased egg deposition. In blood cell analysis, characteristic cells for apoptosis, micronucleus and binucleation were detected, while for comet analysis, different degrees of nuclear damage were detected. The fraction was able to cause total mortality of the cercariae and did not present environmental toxicity. Therefore, B. monandra preparations are promising in combating schistosomiasis since they can control both the intermediate host and eliminate the infectious agent, besides being safe to the environment.     

Effect of Ylang-Ylang (Cananga odorata Hook. F. & Thomson) Essential Oil on Acute Inflammatory Response In Vitro and In Vivo

The aim of this study is to evaluate the phytochemical profile, oral acute toxicity, and the effect of ylang-ylang (Cananga odorata Hook. F. & Thomson) essential oil (YEO) on acute inflammation. YEO was analyzed by gas chromatography/mass spectrometry. For in vitro tests, YEO was assessed using cytotoxicity, neutrophil chemotaxis induced by N-formyl methionyl leucyl phenylalanine (fMLP), and phagocytic activity tests. YEO was orally administered in zymosan-induced peritonitis, carrageenan-induced leukocyte rolling, and adhesion events in the in situ microcirculation model and in carrageenan-induced paw edema models. YEO (2000 mg/kg) was also tested using an acute toxicity test in Swiss mice. YEO showed a predominance of benzyl acetate, linalool, benzyl benzoate, and methyl benzoate. YEO did not present in vitro cytotoxicity. YEO reduced the in vitro neutrophil chemotaxis induced by fMLP and reduced the phagocytic activity. The oral treatment with YEO reduced the leukocyte recruitment and nitric oxide production in the zymosan-induced peritonitis model, reduced rolling and adherent leukocyte number induced by carrageenan in the in situ microcirculation model, and reduced carrageenan-induced edema and mechanical hyperalgesia. YEO did not present signs of toxicity in the acute toxicity test. In conclusion, YEO affected the leukocyte activation, and presented antiedematogenic, anti-hyperalgesic, and anti-inflammatory properties.     

Effect of Biodegradable Coatings on the Growth of Aspergillus flavus In Vitro,on Maize Grains,and on the Quality of Tortillas during Storage

The fungus Aspergillus flavus causes serious damage to maize grains and its by-products, such as tortilla. Currently, animal and plant derivatives, such as chitosan and propolis, and plant extract residues, respectively, are employed as alternatives of synthetic fungicides. The objective of this research was to evaluate the efficacy of several formulations based on propolis-chitosan-pine resin extract on the in vitro growth of A. flavus, the growth of maize grain plantlets and the quality of stored tortillas at 4 and 28 °C. The most outstanding formulation was that based on 59.7% chitosan + 20% propolis nanoparticles + 20% pine resin extract nanoparticles; since the in vitro conidia germination of A. flavus did not occur, disease incidence on grains was 25–30% and in tortillas, 0% infection was recorded, along with low aflatoxin production (1.0 ppb). The grain germination and seedling growth were markedly reduced by the nanocoating application. The percentage weight loss and color of tortillas were more affected by this coating compared to the control, and the rollability fell within the scale of non-ruptured at 4 °C and partially ruptured at 28 °C. The next step is to evaluate the toxicity of this formulation.     

Essential Conditions for the Full Synergy of Probability of Occurrence Distributions

In this contribution, we specify the conditions for assuring the validity of the synergy of the distribution of probabilities of occurrence. We also study the subsequent restriction on the maximal extension of the strict concavity region on the parameter space of Sharma–Mittal entropy measures, which has been derived in a previous paper in this journal. The present paper is then a necessary complement to that publication. Some applications of the techniques introduced here are applied to protein domain families (Pfam databases, versions 27.0 and 35.0). The results will show evidence of their usefulness for testing the classification work performed with methods of alignment that are used by expert biologists.