Application of High Temperature High Resolution Gas Chromatography to Crude Extracts of Propolis

The underivatized acetone and hexane fractions from propolis samples (predominant flora Citrus spp. and Vernonia polyanthes) were analyzed by HT-HRGC (high temperature high resolution gas chromatography) and HT-HRGC coupled to mass spectrometry (HT-HRGC-MS). Several compounds, including flavonoid aglycones, phenolic acids, and high molecular weight compounds were characterized in crude extracts by HT-HRGC-MS. HT-HRGC and HT-HRGC-MS were shown to be quick and informative tools for rapid analysis of crude extracts without need for prior derivatization and purification.     

13C, 15N and 113Cd NMR and Molecular Orbital Studies of Novel Bile Acid N-(2-aminoethyl)amides and Their Cd2+-complexes

Lithocholic acid N-(2-aminoethyl)amide (1) and deoxycholic acid N-(2-aminoethyl)amide(2) have been prepared and characterized by¹H, ¹³C and ¹⁵N NMR. The accurate molecular masses of 1 and 2 have been determined by ESI MS. The formation of the Cd²⁺-complexes (1+Cd and 2+Cd) in CD₃OD solution have been detected by ¹H,¹³C, ¹⁵N and ¹¹³Cd NMR. The ¹³C NMR chemical shift assignments of 1 and 2 and their Cd²⁺-complexes are based on DEPT-135 and z-GS ¹H,¹³C HMQC experiments as well as comparison with the assignments of the related structures. The ¹⁵N NMR chemical shiftassignments of the ligands and theirCd²⁺-complexes are based on z-GS¹H,¹⁵N HMBC experiments. ¹³C NMR chemical shift differences between 1and its 1:1 Cd²⁺-complex based on ab initiocalculations at Hartree-Fock SCI-PCM level using3-21G(d) basis set are in agreement with theexperimental shift changes observed onCd²⁺-complexation.     

Transverse and longitudinal periodicities in fields produced by polarization gratings

The spatial periodicities in Fresnel diffraction patterns produced by polarization gratings [Opt. Lett. 24 (1999) 584] and their generalizations are investigated, with particular attention to the state of polarization of the diffracted field. It is shown, e.g., that in certain planes the polarization vector can rotate periodically, while being constant in certain other parallel planes.     

Equilibrium polymerization in two dimensions

A mean-field theory of equilibrium polymerization on a square lattice is presented. A novel feature of the model is the treatment of the whole range of rigidity of polymers (from flexible to stiff) as well as a simultaneous account of both polymer rings and excluded volume. As a result a line of tricritical points is found.     

Synthesis and structural characterisation of 4H‐1,3‐benzothiazine derivatives

The ring‐closure reactions of N‐arylthiomethylaroylamide derivatives ( 1a‐g ) in the presence of phospho ‐rus oxychloride gave 2‐aryl‐4H‐1,3‐benzo‐thiazines (2a‐g). 2‐(3‐Chlorophenyl)‐6‐methyl‐4H‐1,3‐benzoth‐iazine ( 2b ) was reduced with Zn to obtain the corresponding 2,3‐dihydro derivative ( 3b ). Potassium permanganate oxidation of 2‐(4‐chlorophenyl)‐2,3‐diethoxy‐4H‐ ( 2e ) and 2‐(2‐fluorophenyl)‐6,7‐diefhoxy‐4H‐1,3‐benzo‐thiazines ( 2g ) gave the corresponding 4‐ones ( 4e,g ). The reactions of 2‐(4‐chlorophenyl)‐6‐mefhyl‐4H‐1,3‐benzofhiazine ( 2c ) with substituted acetyl chlorides led to linearly condensed ß‐lactams ( 5a,b ). The structures of the compounds studied were confirmed by ¹H and ¹³C NMR and by their characteristic mass spectrometric fragmentations.     

Proteomic analysis of protein oxidation in Alzheimer's disease brain

There is a growing body of evidence that oxidative stress plays a major role in Alzheimer's disease (AD) pathogenesis. Identification of oxidatively altered proteins in AD is important for understanding the relationship between protein oxidation, protein aggregation and neurodegeneration. In this communication, we report a method that can be applied to study oxidative changes of individual proteins in brain. In order to analyze protein oxidation by detection of protein-bound carbonyls, cytosolic protein extracts were derivatized with 2,4-dinitrophenylhydrazine (DNPH) and then separated by two-dimensional (2-D) gel electrophoresis. After electrotransfer to polyvinylidene difluoride (PVDF) membranes, proteins were first stained with Sypro Ruby protein stain, and then the oxidized proteins were detected with anti-dinitrophenyl (DNP) antibody. About 150 proteins and more than 100 oxidized proteins were detected and quantified in both AD and control cases by 2-D image analysis. The amount of protein-bound carbonyls was decreased for six and increased for one protein in AD. The amount of protein was increased for three proteins in AD. Furthermore, the degree of oxidation was calculated as the ratio of protein-bound carbonyls to the total amount of an individual protein. Two proteins showed a significant decrease in the degree of oxidation in AD. Our results suggest that the balance of protein oxidation and degradation is altered in AD.     

Silver(I) Cation Complexation with 3α,3'α-Bis(pyridine-n-carboxy) Lithocholic Acid 1,2-Ethanediol Diesters (n = 2–4): 1H, 13C and 15N NMR Spectral Studies and Molecular Orbital Calculations

Three isomeric molecular clefts: 3,3'-bis(pyridine-n-carboxy) lithocholic acid 1,2-ethanediol diesters (n = 2–4) 1–3 have been synthesized and their structures ascertained by ¹H, ¹³C NMR and MALDI TOF MS. Their complex formation with Ag⁺-cation (added as AgO₃ SCF₃) have been investigated by means of NMR and molecular orbital calculations. The coordination behaviour of the silver(I) cation is dependent on the isomerism of the pyridine-n-carboxy moiety. In 1 (pyridine-2-carboxylato = picolinato) both NMR and theoretical calculations strongly suggest that the coordination occurs with the lone electron pairs of the pyridine nitrogen and carbonyl oxygen in both of the arms of the molecular cleft separately. In 2 and 3 (pyridine-3-carboxylato = nicotinato and pyridine-4-carboxylato = isonicotinato) where the distance between the pyridine nitrogen and carbonyl oxygen is too large to allow the same type of coordination as in 1, ₃-complexation with the pyridine ring and carbonyl oxygen of the different arms of the molecular cleft simultaneously is suggested by molecular orbital calculations and supported also by NMR. No Ag⁺-cation coordination was observed with the 1,2-ethanediol oxygens in 1–3.     

Synthesis of 4′-substituted 2,2′:6′,2″-terpyridines via a Mitsunobu reaction

Treatment of 2,6-di(pyridin-2-yl)pyridin-4(1H)-one with various appropriately protected ω-substituted primary alcohols or a nucleoside (3,3′-O-diBz-dUrd) in dry THF in the presence of triphenylphosphine and diisopropylazodicarboxylate gives the corresponding 4′-substituted terpyridines in high yield.     

Time-dependent simulation of Czochralski silicon crystal growth

We have developed a detailed mathematical model and numerical simulation tools based on the streamline upwind/Petrov-Galerkin (SUPG) finite element formulation for the Czochralski silicon crystal growth. In this paper we consider the mathematical modeling and numerical simulation of the time-dependent melt flow and temperature field in a rotationally symmetric crystal growth environment. Heat inside the Czochralski furnace is transferred by conduction, convection and radiation, Radiating surfaces are assumed to be opaque, diffuse and gray. Hence the radiative heat exchange can be modeled with a non-local boundary condition on the radiating part of the surface. The position of the crystal-melt interface is solved by the enthalpy method. The melt flow is assumed to be laminar and governed by the cylindrically symmetric and incompressible Navier-Stokes equations coupled with the calculation of temperature.     

Tosylation and acylation of cellulose in 1-allyl-3-methylimidazolium chloride

Tosylation and acylation of cellulose were performed under mild reaction conditions using imidazolium based ionic liquids (ILs) as solvents. The non-degradative nature, lower viscosity, as well as higher solubility of cellulose in [amim]Cl encouraged us to carry out the reactions in this media. The reactions described here were optimised for this particular solvent in order to obtain different cellulose derivatives with high yields, homogeneity and degree of substitution (DS). Two reagents employed for the in situ activation of carboxylic acids were N,N′-carbonyldiimidazole (CDI) and 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide hydrochloride (EDCI). Final products were characterised by solution and solid-state NMR techniques. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.