Effect of maltodextrins on the surface activity of small-molecule surfactants

We report on the effect of commercially important polysaccharides (maltodextrins with variable dextrose equivalent (Paselli SA-2, MD-6 and MD-10) on the surface activity at the air–water interface of small-molecule surfactants (sms), possessing different hydrophobic–lipophilic balance ((SSL (Na⁺), the main component is a sodium salt of stearol–lactoyl lactic acid, and PGE (080), polyglycerol ester of C18 fatty acid), and widely used in food products. A marked change of the surface activity of sms was found in the presence of maltodextrins by tensiometry. The combined data of laser multiangle light scattering and mixing calorimetry have suggested that this result is governed by specific complex formation between maltodextrins and sms in aqueous medium. Measurements have been made of the molar mass, the second virial coefficient and the enthalpy of intermolecular interactions in aqueous solutions. The implication of a degree of polymerization of maltodextrins in this phenomenon was shown. The interrelation between the molecular parameters of the formed complexes and their surface activity at the air–water interface has been revealed and discussed.     

Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine

Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.     

Atomic Absorption Spectrometry of Silver with Absorption Tube Having Nebulization Chamber

In the atomic absorption spectrometry with the long absorption tube using a hydrogen-air flame, only the total consumption type of the burners, e.g., Beckman¹ or ring burners², have been used for the input of a sample solution to the flame. The use of the indirect input method with nebulization chamber has never been attempted, though, by use of a commercially available apparatus with nebulization chamber, the large increase of the sensitivity has been easily obtained by heating the chamber and nebulizing air^3–5.     

Influences of laser remelting on microstructure of nanostructured Al2O3-13 wt.% TiO2 coatings fabricated by plasma spraying

The effects of laser remelting on microstructure of nanostructured Al₂O₃-13 wt.% TiO₂ ceramic coatings prepared by plasma spraying with agglomerated powders were studied. The microstructure of the feedstock, as-sprayed and laser-remelted coatings were investigated by using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffractometry (XRD). The results indicate that the plasma-sprayed ceramic coating consists of both fully melted regions and partially melted regions. The totally ceramic coating, especially the fully melted regions, has a typical plasma-sprayed lamellar-like structure as the conventional coating, and has some pores. According to the difference of microstructures, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The lamellar defect of the as-sprayed coating is erased, and the compactness of the coating is improved significantly after laser remelting. The laser-remelted region composed of fine equiaxed grains, which are different from the conventional column-like crystals along the direction of the heat current. Due to the rapid solidification of laser remelting process, there are still some nanoparticles in the remelted region because of an insufficient time for grains growth.     

Total Synthesis of α-Elvucitabine

Total synthesis of α-elvucitabine was achieved in 26% overall yield by a concise nine-step procedure starting from L-lyxose, with trimethylsilyl trifluoromethaneoulfonate (TMSOTf)–mediated stereocontrolled α-N-glycosidation and olefination through Barton–McCombie deoxygenation being the key steps, and the stereochemistry of the product was determined by nuclear Overhauser effect spectroscopy.     

3-Oxodapagliflozin as a Potent and Highly Selective SGLT2 Inhibitor for the Treatment of Type 2 Diabetes

Structural modifications of 3-OH in the glucose moiety of dapagliflozin（1）, an approved potent sodium-dependent glucose transporter 2（SGLT2） inhibitor, led to 3-oxodapagliflozin（16）, a highly potent and more selective SGLT2 inhibitor[IC50（hSGLT1）/IC50（hSGLT2）=2851 for compound 16 vs. 843 for compound 1]. 3-Oxodapagliflozin（16） exhibited in vitro（IC50=1.0nmol/L against hSGLT2 for compound 16 vs. 1.3 nmol/L for compound 1） and in vivo activities comparable to those of dapagliflozin（1）. The bioactivities of 3-oxodapagliflozin （16） warrant its further evaluation as a promising SGLT2 inhibitor for the treatment of type 2 diabetes.     

The synthesis and photolysis mechanisms of 8‐nitroquinoline‐based photolabile caging groups for carboxylic acid

Photolabile protecting groups have been extensively studied and applied for protection of small biological molecules, which make it convenient to detect the biological processes of the caged compounds. In this study, a series of 8‐nitroquinoline‐based photolabile caging groups for carboxylic acid were synthesized with improved photolysis efficiency. Among them, 6‐bromo‐8‐nitro‐1, 2‐dihydroquinolinyl chromophore was proven the best derivative on account of its longest absorption wavelength (345 nm), highest caging ability, and quantum yield (Φ = 0.003). Moreover, density functional theory calculations were performed in order to study the photolysis mechanisms. Theoretical calculations revealed that the reaction was kinetically inert under general mild condition with the high barrier height of 34.3 kcal/mol at carbonyl migration step, while under the photolysis condition, because of the large energy gap (64.5 kcal/mol) between S₀ and S₁ states, the reaction should be accessible in the triplet ground state (T₁) through successive excitation of S₀ → S₁ states, subsequent intersystem crossing of S₁ → T₁ states, and finally returned to the stable S₀ state for product via potential energy surface crossing between T₁ and S₀ states. Copyright © 2014 John Wiley & Sons, Ltd.     

Radical cyclization by ipso substitution of the methoxy group: considerable effect of HMPA on samarium-mediated cyclization

Alkyl radicals generated by treatment of thiocarbamates of conformationally favorable 3-alkyl-3-arylpropan-1-ols with tris(trimethylsilyl)silane and AIBN efficiently undergo intramolecular ipso substitution of the methoxy group, yielding the corresponding cyclized products. In contrast, either conformationally favorable or flexible 1-arylalkan-3- or 4-ones easily cyclize into five- or six-membered condensed rings by treatment with SmI(2) via ketyl radical intermediates. The addition of HMPA as cosolvent dramatically changes the cyclization mode of the SmI(2)-induced reaction, and the para-cyclization products are exclusively formed. This "HMPA effect" can be rationalized by the strong chelating ability of HMPA with the samarium atom.     

Preparation of Fritless Packed Silica Columns for Capillary Electrochromatography

Fritless packed silica gel columns were prepared using sol‐gel technology. A part of a 75 μm i.d. fused silica capillary was filled with a mixture of tetramethoxysilane and poly(ethylene glycol). After gelling at 40°C and heating at 300°C, the resultant silica gel was derivatized with dimethyloctadecylchlorosilane. A scanning electron micrograph of a cross‐section of the capillary column showed that the gel took the form of a spherical particle aggregate and adhered to the column inner wall. The column performance was evaluated for electrochromatography using acetonitrile–50 mM HEPES buffer (pH 6.6) (60/40 or 40/60, v/v) as the mobile phase. An electroosmotic flow of 1.0 mm/s was generated with (60/40, v/v) acetonitrile/HEPES buffer at a field strength of 546 V/cm. Using a sol‐gel‐derived packed column at an electroosmotic flow of 0.5 mm/s, efficiencies of up to 1.1×10⁵ plates/m were obtained for retained solutes.     

A new PVC matrix membrane sensor for determination of praseodymium(III) ion based on bis(salicylaldehyde)thiocarbohydrazone as an ion carrier

The sufficient amounts of bis(salicylaldehyde) thiocarbohydrazone (STCH) as a lipophilic selective element (3%, w/w), sodium nitrobenzene (NB) as a plasticizer (64%, w/w), tetraphenyl borate (NaTPB) as an anionic additive (3%, w/w), and poly vinyl chloride (PVC) as a polymeric matrix (30%, w/w) was employed to form a PVC membrane of a new Pr³⁺ ions selective sensor to apply as an indicator electrode in analytical applications. The best electrode response was observed in the slope (19.5 ± 0.7 mV per decade) over a wide concentrations from lower (1.0 × 10^?6 mol L^–1) to higher (1.0 × 10^?2 mol L^–1) of Pr³⁺ ion solution with a detection limit of 8.5 × 10^–7 mol L^–1. This electrode showed the fast response time about 10 second for praseodymium ion concentration range of 1.0 × 10^–6 to 1.0 × 10^–2 mol L^–1, in the pH range of 2.3–7.9. The matched potential method was applied to study the selectivity of electrode toward Pr³⁺ ions in comparison with many common cations. The results showed the negligible disturbance of all other cations on the proposed praseodymium(III) electrode. The making sensor has been employed successfully as an indicator electrode in the potentiometric titration of praseodymium(III) solution with EDTA at pH 6.0. Moreover the applicability of the sensor was studied in determination of Pr³⁺ ion in mixtures of different ions.