Ruthenium-Oxygen Coordination-Driven Self-Assembly of a Ru-8(II) Incomplete Prism: Synthesis, Structure, and Shape-Selective Molecular Recognition Study

Coordination-driven self-assembly of 1,3,5-benzenetricarboxylate (tma; 1) and oxalato-bridged p-cymeneruthenium(II) building block Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (2) affords an unusual octanuclear incomplete prism Ru-8(eta(6)-p-cymene)(8)(tma)(2)(mu-eta(4)-C2O4)(2)(OMe)(4)](O3SCF3)( 2) (3), which exhibits a remarkable shape-selective binding affinity for neutral phenolic compounds via hydrogen-bonding interactions (p-cymene = p-(PrC6H4Me)-Pr-i). Such a binding was confirmed by single-crystal X-ray diffraction analysis using 1,3,5-trihydroxybenzene as an analyte.

A Series of Cu-II-Azide Polymers of Cu-6 Building Units and the Role of Chelating Diamine in Controlling their Dimensionality: Synthesis, Structures, and Magnetic Behavior

Four new neutral copper-azido polymers Cu-6(N-3)(12)(aem)(2)](n)(1), Cu-6(N-3)(12)(dmeen)(2)(H2O)(2)](n) (2), Cu-6(N-3)(12)(N,N'-dmen)(2)](n) (3), and Cu-6(N-3)(12)(hmpz)(2)](n) (4) aem = 4-(2-aminoethyl)morpholine; dmeen = N,N-dimethyl-N'-ethylethylenediamine; N,N'-dmen = N,N'-dimethylethylenediamine and hmpz = homopiperazine] have been synthesized by using 0.33 mol equiv of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O/CuCl2 center dot 2H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-6(II) building blocks. But the overall structures of these complexes vary widely in dimensionality. While 1 is three-dimensional (3D) in nature, 2 and 3 have a two-dimensional (2D) arrangement (with different connectivity) and 4 has a one-dimensional (1D) structure. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all the four complexes. The experimental susceptibility data have been analyzed by some theoretical model equations.

Room-temperature synthesis of gold nanoparticles - Size-control by slow addition

We report a simple and rapid process for the room-temperature synthesis of gold nanoparticles using tannic acid, a green reagent, as both the reducing and stabilising agent. We systematically investigated the effect of pH on the size distribution of nanoparticles synthesized. Based on induction time and zeta- potential measurements, we show that particle size distribution is controlled by a fine balance between the rates of reduction (determined by the initial pH of reactants) and coalescence (determined by the pH of the reaction mixture) in the initial period of growth. This insight led to the optimal batch process for size-controlled synthesis of 2-10 nm gold nanoparticles - slow addition (within 10 minutes) of chloroauric acid into tannic acid.

Synthesis and characterization of flexible epoxy nanocomposites reinforced with amine functionalized alumina nanoparticles: a potential encapsulant for organic devices

Research on conducting polymers, organic light emitting diodes and organic solar cells has been an exciting field for the past decade. The challenge with these organic devices is the long term stability of the active material. Organic materials are susceptible to chemical degradation in the presence of oxygen and moisture. The sensitivity of these materials towards oxygen and moisture makes it imperative to protect them by encapsulation. Polymer nanocomposites can be used as encapsulation materials in order to prevent material degradation. In the present work, amine functionalized alumina was used as a cross-linking and reinforcing material for the polymer matrix in order to fabricate the composites to be used for encapsulation of devices. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to elucidate the surface chemistry. Thermogravimetric analysis techniques and CHN analysis were used to quantify grafting density of amine groups over the surface of the nanoparticles. Mechanical characterizations of the composites with various loadings were carried out with dynamic mechanical analyzer. It was observed that the composites have good thermal stability and mechanical flexibility, which are important for an encapsulant. The morphology of the composites was evaluated using scanning electron microscopy and atomic force microscopy.

Total synthesis of substituted (±)-6,6-dimethyl-B-norestra-1,3,5(10)-trien-17?-ols and their 9?-isomers

Total syntheses of (±)-1,4-dimethoxy-6,6-dimethyl-B-norestra-1,3,5(10)-trien-17?-ol(11a), (±)-2,3-dimethoxy-6,6-dimethyl-B-norestra-1,3,5(10)-trien-17?-ol (11b), and (±)-3-methoxy-6,6-dimethyl-B-norestra-1,3,5(10)trien-17?-ol (11c), have been carried out starting from 4,7-dimethoxy-3,3-dimethylindan-1-one (1), 5,6-dimethoxy-3,3-dimethylindan-1-one (2), and 4?-methoxy-3-methylbut-2-enophenone (4), respectively. Generally, it is found that the intermediate 6,6-dimethyl-B-norestra-1,3,5(10),8-tetraen-17?-ols (10), on lithium�liquid ammonia reduction, yield a mixture of 8?,9?- and 8?,9?-trienols, (11) and (12) respectively, in the ratio 1 : 1. This is due to the comparable stabilities of these two isomers. However, the reduction carried out in presence of aniline affords a higher percentage of the 8?,9?-trienol (11). The assignment of configurations is made by chemical and 1H n.m.r. analysis. Catalytic hydrogenation of the tetraenols (10) is shown to proceed via initial isomerisation to the corresponding 6,6-dimethyl-B-norestra-1,3,5(10),9(11)-tetraen-17?-ols (26), followed by hydrogenation from the ?-side to give, exclusively, the 8?,9?-trienols (12).

A Heat and Light Mediated Synthetic Sequence Serendipitous Synthesis of Methyl Ester of Tris-Norpterosin-E

Synthesis of methyl ester of 3-oxo-indan-5-acetic acid (3), an analogue of the natura1 product pterosin-E (4), starting from cyclopentadiene (1) and p-benzoquinone (2) using a sequence of six ground and excited state reactions, is described.

Synthesis of Reduced Metabolites of Isoflavonoids, and their Enantiomeric Forms

Isoflavonoids are naturally occurring plant derived biochemicals, which act as phytoalexins. Isoflavonoids are of interest due to their estrogenic and other potential physiological properties, particularly in mammals that typically consume isoflavonoid rich nutrients such as soy and red clover. The literature review of this thesis mainly focuses on the reduced metabolites of hydroxy and/or methoxy substituted isoflavones with four groups: isoflavan-4-ols, isoflav-3-enes, isoflavans and α-methyldeoxybenzoins (1,2-diarylpropan-1-ones), which are all reduced metabolites of food derived isoflavones in mammals. Related isoflavan-4-ones are briefly discussed. Results of an extensive survey of the literature concerning the synthesis of polyhydroxy- or methoxysubstituted isoflavonoids and especially asymmetric approaches are discussed. The experimental section describes new synthetic methods to prepare polyphenolic reduced isoflavonoid structures such as isoflav-3-enes, isoflavan-4-ones, cis- and trans-isoflavan-4-ols, 1,2-diarylpropan-1-ones and isoflavans by various hydride reagents and hydrogenations. The specific reactivity differences of various hydride reagents toward isoflavonoids are discussed. The first enantioselective synthesis of natural (S)-(-)-equol and the opposite enantiomer (R)-(+)-equol is also described by the asymmetric iridium PHOX catalysed hydrogenation of isoflav-3-enes. Both of these equol enantiomers are found to possess biological activity in mammals due to estrogen receptor binding activity. The natural enantiomer prefers estrogen receptor β and the R-enantiomer prefers the estrogen receptor α. Also the precursor, isoflav-3-ene, is found to possess positive biological effects on mammals. In connection with the synthetic work, the (S)-(-)-equol was discovered from serum of ewes after isoflavone rich red clover feeding. The chiral HPLC method was developed to identify natural equol enantiomer for the first time in this species. The first synthesis of natural isoflavonoid (R)-(-)-angolensin and its enantiomer (S)-(+)-angolensin is desribed by the use of recyclable chiral auxiliaries (chiral pseudoephedrines). The method offers a general approach also to other natural polyphenolic 1,2-diarylpropan-1-ones and to further study isoflavonoid metabolism in human and other mammals. The absolute configurations of these new chiral isoflavonoid metabolites were determined by X-ray spectroscopy. Also thorough NMR and MS analysis of synthesised structures are presented.