Design, synthesis, evaluation, and structure of vitamin D analogues with furan side chains

Based on the crystal structures of human vitamin D receptor (hVDR) bound to 1α,25-dihydroxy-vitamin D(3) (1,25 D) and superagonist ligands, we previously designed new superagonist ligands with a tetrahydrofuran ring at the side chain that optimize the aliphatic side-chain conformation through an entropy benefit. Following a similar strategy, four novel vitamin D analogues with aromatic furan side chains (3a, 3b, 4a, 4b) have now been developed. The triene system has been constructed by an efficient stereoselective intramolecular cyclization of an enol triflate (A-ring precursor) followed by a Suzuki-Miyaura coupling of the resulting intermediate with an alkenyl boronic ester (CD-side chain, upper fragment). The furan side chains have been constructed by gold chemistry. These analogues exhibit significant pro-differentiation effects and transactivation potency. The crystal structure of 3a in a complex with the ligand-binding domain of hVDR revealed that the side-chain furanic ring adopts two conformations.     

Rigid, specific, and discrete gold nanoparticle/antibody conjugates

A general method of rigid, specific labeling of proteins with gold clusters has been devised. The method relies on the conjugation of a glutathione monolayer-protected gold cluster (MPC) with a single chain Fv antibody fragment (scFv), mutated to present an exposed cysteine residue. Efficient formation of a gold-thiolate bond between the MPC and scFv depends on activation of the gold cluster by chemical oxidation. Once formed, the MPC-scFv conjugate is treated with a reductant to quench cluster reactivity. The procedure has been performed with an MPC with an average Au(71) core and an scFv directed against a tetrameric protein, the influenza neuraminidase. A complex of the MPC-scFv conjugate with the neuraminidase was isolated, and the presence of four gold clusters was verified by cryoelectron microscopy.     

Silicon-silica nanowires, nanotubes, and biaxial nanowires: inside, outside, and side-by-side growth of silicon versus silica on zeolite

It was demonstrated that zeolite can be used as a pseudo-template to grow very fine and uniform silicon nanostructures via disproportionation reaction of SiO by thermal evaporation. Three distinct types of composite nanowires and nanotubes of silicon and silica were grown on the surfaces of zeolite Y pellets. The first type is formed by an ultrafine crystalline silicon nanowire sheathed by an amorphous silica tube (a silicon nanowire inside a silica nanotube). The second type is formed by a crystalline silicon nanotube filled with amorphous silica (a silicon nanotube outside a silica nanowire). The third type is a biaxial silicon-silica nanowire structure with side-by-side growth of crystalline silicon and amorphous silica. These silicon nanostructures exhibit unusually intense photoluminescence (in comparison to ordinary silicon nanowires).     

Spectrochemical determination of trace As, Fe, Hg, Mn, and Pb by an argon-stabilized U-shaped DC arc

Argon-stabilized U-shaped DC arc with a system for aerosol introduction was used for the determination of As, Fe, Hg, Mn, and Pb. By applying a computer program performing a time integration of the registered signals and by optimizing the working conditions of an U-shaped arc plasma, the detection capability for As, Fe, Hg, Mn, and Pb was improved, which contributed to the lowering of the detection limits. The lowest detection limits for Fe, Mn, and Pb were achieved during an integration time of 20 s, and for As and Hg during an integration time of 30 s, and their values were 1.1, 0.1, 0.9, 15, and 2.6 ng/mL, respectively. The detection limits obtained by our method with optimal integration times were compared with the detection limits obtained using other methods: inductively coupled plasma-atomic emission spectrometry (ICP-AES), directly coupled plasma-atomic emission spectrometry (DCP-AES), microwave-induced plasma-atomic emission spectrometry (MIP-AES), inductively coupled plasma-mass spectrometry (ICP-MS), and an improved thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). The text was submitted by the authors in English.     

Mackay,Anti-Mackay,Double-Mackay,Pseudo-Mackay,and Related Icosahedral Shell Clusters

Mackay introduced two important crystallographic concepts in a short paper published 40 years ago. One is the icosahedral shell structure (iss) consisting of concentric icosahedra displaying fivefold rotational symmetry. The number of atoms contained within these icosahedral shells and subshells agrees well with the magic numbers in rare gas clusters, (C₆₀) _N molecules, and some metal clusters determined by mass spectroscopy or simulated on energy considerations. The cluster of 55 atoms within the second icosahedral shell occurs frequently and has been called Mackay icosahedron, or simply MI, which occurs not only in various clusters, but also in intermetallic compounds and quasicrystals. The second concept is the hierarchic icosahedral structures caused by the presence of a stacking fault in the fcc packing of the successive triangular faces in the iss. For instance, a fault occurs after the ABC layers resulting an ABCB packing. This is, in fact, a hierarchic icosahedral structure of a core icosahedron connected to 12 outer icosahedra by vertex sharing, or an icosahedron of icosahedra (double MI. Contrary to Mackay's iss, a faulted hierarchic icosahedral shell is, in fact, a twinlike face capping of the underlying triangles; it is, therefore, called an anti-Mackay cluster. The hierarchic icosahedral structure in an Al-Mn-Pd icosahedral quasicrystal has a core of body-centered cube rather than an icosahedron and, therefore, is called a pseudo-Mackay cluster. The hierarchic icosahedral structures have been studied separately in the past in the fields of clusters, nanoparticles, intermetallic compounds, and quasicrystals, but the underlying geometry should be the same. In the following a unified geometrical analysis is presented.     

Protonation constants of 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriamino-N,N,N',N',N'-penta-acetic trans-1,2-diaminocyclohexane-N,N,N',N'-tetra-acetic acid

The stepwise stability constants for the protonation of hydroxyethylidenediphosphonic acid (HEDP), diethylenetriaminopenta-acetic acid (DTPA) and diaminocyclohexanetetra-acetic acid (DCTA) have been determined potentiometrically with a hydrogen electrode at an ionic strength of 1 (KCl) and at 10-35 degrees . The data were treated by a least-squares method for estimation of DeltaH and DeltaS values.     

Determination of zirconium, barium, lanthanum, aluminium, sodium, hafnium and fluorine in fluorozirconate glasses

Summary A procedure is described for the determination of the cationic and anionic components in fluorozirconate glasses. Zirconium, barium, aluminium, lanthanum, sodium and hafnium were determined by inductively coupled plasma atomic emission spectrometry (ICP/AES) after dissolution of the sample with an acid mixture in a microwave oven. The fluorine content was evaluated with two different techniques, namely potentiometry with a fluoride ion-selective electrode (FISE) and ion chromatography (IC). In this case the sample was solubilized by fusion with sodium carbonate.     

Synthesis,characterization, and application of helical polymers

This review mainly describes the asymmetric synthesis of optically active polymers with helical conformation. Bulky methacrylates such as triphenylmethyl methacrylate and 1-phenyldibenzosuberyl methacrylate give one-handed helical and optically active polymers with almost perfectly isotactic main chain conformation by polymerization with chiral anionic initiators. The radical polymerization and copolymerization of these monomers under chiral conditions also afford optically active polymers with prevailing one-handed helicity. N, N-Disubstituted acrylamides also give optically active, helical polymers in the asymmetric anionic polymerization. Optically active polyisocyanates with a prevailing one-handed helical structure have been prepared in the copolymerization of an achiral isocyanate with a small amount of an optically active isocyanate and also in the polymerization of alkyl and aromatic isocyanates with optically active lithium alkoxide or amide compounds. The existence of a stable helical structure for polychloral has been successfully proved with the helical oligomers of chloral. One-handed helical polyisocyanides have been prepared by helix-sense-selective polymerization of bulky isocyanides and also by the cyclopolymerization of a 1, 2-diisocyanobenzene derivative with the Pd complex of a one-handed helical oligomer.     

Biarylic biscarbazole alkaloids: occurrence,stereochemistry, synthesis,and bioactivity

The structurally and pharmacologically intriguing but stereochemically initially disregarded small class of biarylic biscarbazole alkaloids is presented, starting with an introduction of the different structural patterns found in nature. For the construction of the biaryl bond, mainly biomimetic oxidative coupling reactions were used, as shown for the natural products bismurrayaquinone-A, bis-2-hydroxy-3-methylcarbazole, clausenamine-A, and murrastifoline-F. For most of these compounds, a resolution of the respective atropo-enantiomers succeeded either directly, by high-performance liquid chromatography by HPLC on a chiral phase, or via atropo-diastereomers, after derivatization with a chiral auxiliary. The absolute configurations of the pure enantiomers were assigned by comparison of experimental (CD) spectra with those quantum chemi-cally calculated, or, for atropo-diastereomeric derivatives, by means of ROESY investigations and X-ray crystallography. Ullmann-type coupling conditions were also found to be feasible for the construction of the 2,2'-biscarbazole core, necessitating a completely regioselective 2-bromination protocol. The first atroposelective synthesis of such a basic target structure was achieved by application of the "lactone methodology," giving rise to an atropisomeric ratio of 85 : 15. Some of the biscarbazole alkaloids and their derivatives were found to have interesting bioactivities, and for the first time, the natural atropo-enantiomeric ratio in the plants was determined for one of these compounds, murrastifoline-F.     

Azidocryptands-synthesis, structure, and complexation properties

Cryptands bearing an intraannular azido substituent have been synthesized and characterized spectroscopically. Their complexation properties were investigated by picrate extraction analysis. The oxygen-containing cryptands were found to be good ligands for alkali cations, with a preference for Li(+) and Na(+). The molecular structure of the complex with KBr was determined by X-ray crystallography. In this, the first structurally characterized complex of an aryl azide bound to a metal cation, the potassium cation was found to show ninefold coordination to four oxygen atoms and two nitrogen atoms of the crown ether moiety, to the bromide anion and to N1 of the azido group, as well as C1 of the benzene ring.     

Division and fusion, extension, adhesion, and retraction of vesicles created through Langmuir monolayer collapse: cell-like behavior

The motion of vesicles created through Langmuir monolayer collapse has been investigated. The vesicles grow only in a narrow molecular area range, and they exhibit remarkable, various biological cell-like behaviors such as division (cell division in cell biology, cytokinesis) and self-propulsion (motility). The vesicle division includes some dynamic modes: (i) an expulsion of a single satellite vesicle from an initial vesicle, (ii) a hierarchical and a sequential expulsion of a satellite vesicle, and (iii) a successive expulsion of two satellite vesicles from an initial vesicle. Two neighboring vesicles often show alternate fusion and division between them. Strong shape fluctuations dominate through vesicle division. The vesicles created exhibit distinct motions depending on the molecular area. At a large molecular area where most initial vesicles are created, they show a continuous, random motion on a few tens of micrometers length scale with a strong shape fluctuation and a constant velocity fluctuation profile. At a small molecular area they cease to move and shape fluctuations also become suppressed. At an intermediate molecular area there coexist vesicles with different dynamic modes: some vesicles show random motion similar to that at a large molecular area, but in a less fluctuating manner, while others exhibit a directional motion with an intermittent velocity jump. The directional motion is characterized by three distinct steps, i.e., extension, adhesion, and retraction. The characteristic motion is discussed from the viewpoint of haptotaxis, or the motion driven by adhesion gradients on the monolayer created by the local transfer of charged surfactant molecules between the vesicle and the monolayer, which the vesicle adheres to.     

“Spectroscopic” Calculations of CH Bond Dissociation Energies for Ethane, Propane, Butane, Isobutane, Pentane, Hexane, and Neopentane Using Fundamental Vibration Frequencies

The fundamental spectrum and the parameters of the potential function of a number of saturated hydrocarbon molecules are calculated in an anharmonic approximation. The calculation is performed by the variational technique using a minimal Morse-harmonic basis. The potential function is taken as the sum of the Morse function for CH bonds and the harmonic function for the skeletal and deformation vibrations. The initial approximation for the potential function is found by ab initio calculations in a 6-31G basis and refined by solving the inverse problem. The calculated CH bond dissociation energies depend significantly on the molecular structure and on the position of CH bonds in the molecule. These energies correlate well with the experimental cleavage energies of these bonds. The changes in the dipole moment of the molecule induced by vibrations were found by ab initio calculations in a 6-31G basis. The calculated IR transmission curves are in good agreement with the experimental curves.     

Synthesis of diazadibenzoperylenes and characterization of their structural, optical, redox, and coordination properties

Tetraphenoxy-substituted diazadibenzoperylenes 5a,b were synthesized from tetrachloroperylene tetracarboxylic acid bisanhydride 1 through imidization with benzylamine, nucleophilic displacement of the four chlorine atoms by phenolates, carbonyl group reduction by LiAlH(4)/AlCl(3), and subsequent Pd/C-promoted debenzylation-dehydrogenation. The structural properties of these extended diazaarenes are discussed on the basis of a X-ray crystal structure of the N,N'-dibutylated diazadibenzoperylenium dication 6, which revealed a 25 degrees twist of the central six-membered ring leading to an atropisomeric pi-conjugated backbone. The chromophoric systems of 5 and 6 were characterized by optical absorption and fluorescence spectroscopy, which revealed an intense fluorescence with a quantum yield of 75% for 5 and 50% for 6. Cyclic voltammetry showed reversible oxidation and reduction waves for 6, whereas the oxidation of 5 afforded the irreversible deposition of a conductive film on the electrode surface. Finally, the potential use of ligands 5 in supramolecular chemistry has been evaluated by complexation experiments with carboxylic acids and zinc tetraphenylporphyrin (ZnTPP).     

Synthesis, spectroscopy, and reactivity of meso-unsubstituted azuliporphyrins and their heteroanalogues. Oxidative ring contractions to carba-, oxacarba-, thiacarba-, and selenacarbaporphyrins

This paper reports the first detailed study on meso-unsubstituted azuliporphyrins, an important family of porphyrin-like molecules where one of the usual pyrrole rings has been replaced by an azulene subunit. Although the azulene moiety introduces an element of cross-conjugation, zwitterionic resonance contributors with tropylium and carbaporphyrin substructures give azuliporphyrins diatropic character that falls midway between true carbaporphyrins and nonaromatic benziporphyrins. Protonation affords an aromatic dication where this type of resonance interaction is favored due to the associated charge delocalization. Two different "3 + 1" syntheses of meso-unsubstituted azuliporphyrins have been developed. Acid-catalyzed reaction of readily available tripyrrane dicarboxylic acids with 1,3-azulenedicarbaldehyde, followed by oxidation with DDQ or FeCl(3), affords good yields of azuliporphyrins. Alternatively, azulene reacted with acetoxymethylpyrroles (2 equiv) in refluxing acetic acid/2-propanol to give tripyrrane analogues, and following a deprotection step, condensation with a pyrrole dialdehyde in TFA-CH(2)Cl(2) gave the azuliporphyrin system. The latter approach was also used to prepare 23-thia- and 23-selenaazuliporphyrins. However, reaction of the azulitripyrrane with 2,5-furandicarbaldehyde produced a mixture of three oxacarbaporphyrins in moderate yield. The free base forms of thia- and selenaazuliporphyrins both showed intermediary aromatic character that was considerably enhanced upon protonation. The UV-vis spectra for azuliporphyrins and their heteroanalogues showed four bands between 350 and 500 nm and broad absorptions at higher wavelengths. Addition of TFA gave dications that showed porphyrin-like spectra with Soret bands between 460 and 500 nm. In the presence of pyrrolidine, azuliporphyrins and their heteroanalogues undergo nucleophilic attack on the seven-membered ring to give carbaporphyrin adducts. These systems also undergo oxidative rearrangements under basic conditions with t-BuOOH to give benzocarbaporphyrins. The selenaazuliporphyrin afforded two benzoselenacarbaporphyrins, a previously unknown core-modified carbaporphyrin system. The proton NMR spectra for these compounds showed strong diatropic ring currents with the internal CH resonance upfield above -5 ppm, while the meso-protons resonated downfield near 10 ppm. The UV-vis spectra were also porphyrin-like and gave strong Soret bands at ca. 440 nm.     

Lithium diisopropylamide-mediated reactions of imines, unsaturated esters, epoxides, and aryl carbamates: influence of hexamethylphosphoramide and ethereal cosolvents on reaction mechanisms

Several reactions mediated by lithium diisopropylamide (LDA) with added hexamethylphosphoramide (HMPA) are described. The N-isopropylimine of cyclohexanone lithiates via an ensemble of monomer-based pathways. Conjugate addition of LDA/HMPA to an unsaturated ester proceeds via di- and tetra-HMPA-solvated dimers. Deprotonation of norbornene epoxide by LDA/HMPA proceeds via an intermediate metalated epoxide as a mixed dimer with LDA. Ortholithiation of an aryl carbamate proceeds via a mono-HMPA-solvated monomer-based pathway. Dependencies on THF and other ethereal cosolvents suggest that secondary-shell solvation effects are important in some instances. The origins of the inordinate mechanistic complexity are discussed.     

Phase Behavior, Structure, and Physical Properties of the Quaternary System Tetradecyldimethylamine Oxide, HCl, 1-Hexanol, and Water

The phase diagram of the ternary surfactant system tetradecyldimethylamine oxide (TDMAO)/HCl/1-hexanol/water shows with increasing cosurfactant concentration an L(1) phase, two L(alpha) phases (a vesicle phase L(alpha1) and a stacked bilayer phase L(alphah)), and an L(3) phase, which are separated by the corresponding two-phase regions L(1)/L(alpha) and L(alpha)/L(3). In this investigation, the system was studied where some of the TDMAO was substituted by the protonated TDMAO. Under these conditions, one finds for constant surfactant concentration of 100 mM TDMAO a micellar L(1) phase, an L(alpha1) phase (consisting of multilamellar vesicles), and an interesting isotropic L(1)(*) phase in the middle of the L(1)/L(alpha) two-phase region. The L(1)(*) phase exists at intermediate degrees of charging of 30-60% and for 40-120 mM TDMAO and 70-140 mM hexanol concentration. At surfactant concentrations less than 80 mM the L(1)(*)-phase borders directly on the L(1) phase. The phase transition between the L(1) phase and the L(1)(*) phase was detected by electric conductivity and rheological measurements. The conductivity values show a sharp drop at the L(1)/L(1)(*) transition, and the zero shear viscosity of the L(1)(*) phase is much lower than in L(1) phase. The form and size of the aggregates in L(1)(*) were detected with FF-TEM and SANS. This phase contains small unilamellar vesicles (SUV) of about 10 nm and some large multilamellar vesicles with diameters up to 500 nm. The system exhibits another peculiarity. For 100 mM surfactant, the clear L(alpha1)-phase exists only at chargings below 30%. With oscillating rheological measurements a parallel development of the storage modulus G' and the loss modulus G" was observed. Both moduli are frequency independent and the system possesses a yield stress. The storage modulus is a magnitude larger than the loss modulus. Copyright 2000 Academic Press.     

Complexes of HArF and AuX (X = F,Cl, Br,I). Comparison of H-bonds,halogen bonds,F-shared bonds and covalent bonds

The various sorts of complexes in which HArF and AuX (X = F, Cl, Br, I) can engage are probed by MP2/aug-cc-pVTZ calculations. The most weakly bound are those containing a halogen bond (XB) of the AuX⋯FArH sort, with binding energies less than 8 kcal/mol. H-bonded dimers FArH⋯XAu are a little stronger, held together by some 12 kcal/mol. Being the most strongly bound places the F atom of HArF roughly midway between Ar and Au in an F-shaped structure, bound by some 43–54 kcal/mol. The last sort of product involves atomic rearrangements wherein the H atom migrates from Ar to Au, followed by formation of a covalent Ar–Au bond. The resulting molecular unit is stabilized by 30–40 kcal/mol relative to the original HArF and AuX reactants. The H-bonded dimers are held together by an unusually large polarization component, surpassing electrostatic attraction, while dispersion predominates for the halogen bonds. Perturbations of the geometries and stretching frequencies offer a ready means of distinguishing the different types of complexes by spectroscopic techniques.     

Highly site, regio-, and stereoselective multicomponent reaction of benzimidazole carbenes, isothiocyanates, and allenoates

The novel three-component reaction of benzimidazole carbenes with isothiocyanates and allenoates proceeded efficiently in a highly site, regio-, and stereoselective manner to produce predominantly spiro[benzimidazoline-2,3′-tetrahydrothiophene] derivatives. The reaction was proposed to occur via a tandem nucleophilic addition of carbenes to isothiocyanates followed by an unusual [3+2] cycloaddition to the less activated carbon-carbon double bond of allenoates.     

Synthesis,characterization, processability,mechanical properties,flame retardant,and oil resistance of chlorinated acrylonitrile butadiene rubber

Novel chlorinated acrylonitrile butadiene rubber (Cl‐NBR) was prepared from NBR by the alkaline hydrolysis of chloroform by using phase‐transfer catalysis. The formation of Cl‐NBR was monitored by ¹H‐NMR, UV‐Vis, and Fourier transform infrared spectroscopic techniques. The percentage of chlorine attached to the rubber chain was estimated by Volhard method. The effect of polar groups on the structural and thermal properties of Cl‐NBR was analyzed by scanning electron microscopy, X‐ray diffraction analysis, differential scanning calorimetry, and thermogravimetric analysis studies. The flame retardant, oil resistance, cure behavior, and mechanical properties of chlorinated elastomer were also analyzed. The proton NMR revealed the attachment of chlorine in the backbone of NBR with new chemical shift values. The C‐Cl stretching of chlorinated NBR was confirmed from Fourier transform infrared. The UV spectrum also supported the formation of chlorinated unit in the NBR chain through the shifts and broadening of absorption peaks. The X‐ray diffraction analysis pattern indicated a decrease in the amorphous domain of NBR with an increase in the level of chemical modification. The increased glass transition temperature obtained from differential scanning calorimetry confirms the increased molecular rigidity of the chlorinated NBR and thermal transitions increased with increase in the level of chemical modification. The thermal stability of Cl‐NBR decreased with an increase in chlorine content. The flame and oil resistance of Cl‐NBR was greatly higher than pure NBR due to the increased polarity of modified rubber. The superior tensile strength of Cl‐NBR (4 times higher than pure NBR) and higher oil resistance find applications in pump diaphragms, aircraft hoses, oil‐lined tubing, and gaskets materials with the excellent flame resistant property.     

The determination of nickel,cobalt, iron and zinc in ferrites

An anion exchange technique has been developed for the determination of iron, nickel, cobalt and zinc in a ferrite type material. The constituents are separated by utilizing the difference in the adsorption of the chloride complexes on a strongly basic anion exchange resin. Each constituent is determined by the back titration of an excess of EDTA with a standard copper solution, using PAN as an indicator.