Synthesis of Natural Product Inspired Compound Collections

Mimicking nature synthetically : The successful development of multistep stereoselective syntheses gives access to natural product inspired compound collections having carbo‐, oxa‐,and azacyclic scaffold structures which promise to provide sources for new reagents in medicinal chemistry and chemical biology research.

     

Enhanced skin permeation of salicylate by ion-pair formation in non-aqueous vehicle and further enhancement by ethanol and l-menthol

Enhancement of skin permeability of salicylate from non-aqueous vehicle by ion-pair formation with either alkylamines or benzylamine as model cationic ions was examined in excised guinea pig dorsal skin. Solubility of salicylate in isopropyl myristate (IPM) was increased by the addition of either alkylamines or benzylamine as counter ions. The increase was more significant in the presence of amines with longer alkyl chains. Flux of salicylate increased in the presence of these amines due to the increase in the solubility. Maximum flux was observed in the presence of n-hexylamine, which induced an 11-fold increase due to 137-fold increase in solubility. Flux and permeability coefficients of salicylate in the presence of n-butylamine, n-hexylamine, iso-octylamine and benzylamine as counter ions in IPM were larger than those of the non-ionic form of salicylic acid. Flux of 3-methylsalicylate (3-CH3 substituent) and that of 5-hydroxysalicylate (5-OH substituent) were smaller than that of salicylate in the presence of n-hexylamine. After partition to the skin surface, the ion-pair is suggested to dissociate and permeate separately according to the study using lidocaine as the counter ion. Flux of salicylate increased in the presence of benzylamine as the counter ion by the addition of 15% ethanol and 15% ethanol plus 1% l-menthol due to further improvement in the solubility as well as an increase in the permeability coefficient.     

The synthesis of 3,3‐dimethyl‐2‐(1‐aryl‐1h‐pyrazol‐4‐yl)‐3h‐indoles

2,3,3‐Trimethylindolenine and 5‐chloro‐2,3,3‐trimethylindolenine were converted into β‐diformyl compounds by the action of the Vilsmeier reagent at 50°C. The dialdehydes reacted with various arylhydrazines and 2‐pyridylhydrazine to produce mono‐hydrazones as mixtures of cis and trans isomers. Heating the hydrazones in refluxing ethanol produced 3,3‐dimethyl‐2‐(1‐aryl‐1H‐pyrazol‐4‐yl)‐3H‐indoles in excellent yields. Reaction of the β‐diformyl compounds with hydrazine itself led directly to 3,3‐dimethyl‐2‐(pyrazol‐4‐yl)‐3H‐indoles.     

First order transition to oscillation death through an environment

The emergence of dynamical abrupt transitions for the first time in an ensemble of identical limit-cycle and chaotic oscillators coupled via a common environment is reported. The transition from the oscillatory state to the death state and vice versa, in these networks of oscillators are found not only discontinuous as well as irreversible in the parameter space. This first order phase transition in these systems is termed as Explosive Death. The occurrence of such transition is studied in details by using an appropriate order parameter for both limit-cycle and chaotic oscillators, in particular, Stuart–Landau and Rössler oscillators. The backward transition point for this phenomenon is obtained analytically using linear stability analysis and is found to be consistent with the numerical results.     

Effect of Bi‐content on hardness and micro‐creep behavior of Sn‐3.5Ag rapidly solidified alloy

In the present paper, the influence of 1, 3, 5 and 10 % Bi (weight %) as ternary additions on structure, melting and mechanical properties of rapidly solidified Sn‐3.5Ag alloy has been investigated. The effect of Bi was discussed based on the experimental results. The experimental results showed that the alloys of Sn‐3.5Ag, Sn‐3.5Ag‐1Bi and Sn‐3.5Ag‐3Bi are composed of two phases; Ag₃Sn IMC embedded in Sn matrix phase, which indicated that the solubility of Bi phase in Sn‐matrix was extended to 3 % as a result of rapid solidification. Bi precipitation in Sn matrix was only observed in Sn‐3.5Ag‐5Bi and Sn‐3.5Ag‐10Bi alloys. Also, addition of Bi decreased continuously the melting point of the eutectic Sn‐3.5Ag alloy to 202.6 °C at 10 % Bi. Vickers hardness of Sn‐3.5Ag rapidly solidified alloy increased with increasing Bi content up to 3 % due to supersaturated solid solution strengthening hardening mechanism of Bi phase in Sn matrix, while the alloys contain 5 and 10 % Bi exhibited lower values of Vickers hardness. The lower values can be attributed to the precipitation of Bi as a secondary phase which may form strained regions due to the embrittlement of Bi atom. In addition, the effect of Bi addition on the micro‐creep behavior of Sn‐3.5Ag alloy as well as the creep rate have been described and has been calculated at room temperature. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

以脉冲萃取柱利用三异辛胺从高浓度铀溶液中回收铀

利用三异辛胺(TOA)纯化Gattar小型试验工厂的高浓度铀溶液(洗脱液的铀浓度7 g·L^-1),研究了脉冲萃取柱的性能。利用实验室级脉冲萃取柱进行了实验室规模的溶剂萃取实验和后续实验。结果表明,在室温、pH=1和有机相与水相的比例(V_O/V_A)约为1.8：1时,加入二(2-乙基己基)磷酸(D2EHPA)使其与TOA的比例(V_D2EHPA/V_TOA)为2：3,可使萃取克服Cl-的抑制效应,提高效率。将结论用于考察试验工厂级萃取柱的流体力学和传质性能,结果表明用脉冲萃取柱萃取铀可以达到97%的萃取效率,具有可行性。     

Characterization and Comparison of Commercial Chinese Cereal and European Grape Vinegars Using 1H NMR Spectroscopy Combined with Multivariate Analysis

A holistic and comparative quality assessment of vinegars from different countries is needed with international trade of vinegar become frequent. In this study, compounds characterization and comparison of commercial‐grade Chinese cereal and European grape vinegars were performed using ¹H NMR spectroscopy coupled with principal component analysis (PCA) and orthogonal projection to latent structures discriminate analysis (OPLS‐DA). The results showed that Balsamic vinegars of Modena were clearly discriminated by higher amount of fructose and glucose, while Chinese aromatic vinegar and aged vinegars were characterized by higher amount of amino acids, volatile compounds, succinate and betaine. On the other hand, flavoring compounds in Chinese rice vinegar and European wine vinegars are less than the others. These characteristic components are associated with the special raw materials and producing process of each types of vinegar and endow them special flavor. The results obtained in this study provide a global insight into vinegar through a ¹H NMR based compounds analysis that allows a holistic quality assessment and comparison of vinegars from different manufacture origins.     

Application of the aza-Wittig reaction for efficient synthesis of diversely substituted benzo[f]Chromeno[2,3-d]pyrimidine and benzo[f]chromeno[2,3-d][1,2,4]triazolopyrimidine derivatives

An efficient synthesis of novel benzo[f]Chromeno[2,3-d]pyrimidine and unknown benzo[f]chromeno[2,3-d][1,2,4]triazolopyrimidine derivatives is described utilizing ethyl-2-amino-4-phenyl-4H-benzo[f]chromene-3-carboxylate as precursor via aza-Wittig reaction. The process proved to be simple, high-yielding, and efficient.     

Thermal width of quarkonium from holography

Nuclear effects in deep inelastic scattering at low $x$ are phenomenologically described changing the typical dynamical and/or kinematical scales characterizing the free nucleon case. In a holographic approach, this rescaling is an analytical property of the computed structure function $F_2(x,Q^2)$ . This function is given by the sum of a conformal term and of a contribution due to quark confinement, depending on IR hard-wall parameter $z_0$ and on the mean square distances, related to a parameter $Q^\prime $ , among quarks and gluons in the target. The holographic structure function per nucleon in a nucleus $A$ is evaluated showing that a rescaling of the typical nucleon size, $z_0$ and $Q^\prime $ , due to nuclear binding, can be reabsorbed in a $Q^2$ -rescaling scheme. The difference between neutron and proton structure functions and the effects of the longitudinal structure functions can also be taken into account. The obtained theoretical results favorably compare with the experimental data.     

Multiferroics by rational design: implementing ferroelectricity in molecule-based magnets

Multiferroic materials: A novel class of multiferroics based on organic-inorganic hybrid materials is synthesized. The ferromagnetic properties originate from the coordination network, whereas the ferroelectricity results from the polar organic ions (see picture, M=magnetization and P=polarization).