A dual-phase oscillatory behavior in Belousov–Zhabotinsky system with vanillin as the substrate

Dual-phase oscillations are observed in Belousov–Zhabotinsky system with 4-hydroxy-3-methoxybenzaldehyde (vanillin) as the substrate and manganous sulphate or ammonium Ce(IV) sulphate as the catalyst. The nonoscillatory period of time between the two phases decreases with increase in the concentration of the catalyst and the substrate. Under uncatalyzed and ferroin catalyzed conditions the system exhibits single-phase oscillations. The first-phase oscillations are due to vanillin whereas the second-phase oscillations are brought about by 4-hydroxy-3-methoxybenzoic acid (vanillic acid) formed during the course of the first-phase reactions. The reactions are explained with relevant steps of the FKN mechanism. © 1998 John Wiley & Sons, Inc. Int J. Chem. Kinet 30: 201–206, 1998.     

Lithium garnet based free-standing solid polymer composite membrane for rechargeable lithium battery

Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (W_avg ~?5?×?10⁶) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO₄) and lithium garnet oxide Li_6.28Al_0.24La₃Zr₂O₁₂ (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li⁺ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li⁺ conductivity of 4.40?×?10^?4 S cm^?1 and wide electrochemical window (4.5 V) is observed for PEO₈/LiClO₄?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO₂ as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g^?1/142 mAh g^?1 at 25 °C with 0.06 C-rate.     

Stabilization of p-block organoelement terminal hydroxides, thiols, and selenols requires newer synthetic strategies

Metal hydroxides represent a very interesting and highly useful class of compounds that have been known to chemists for a very long time. While alkali and alkaline earth metal hydroxides (s‐block) are commonplace chemicals in terms of their abundance and their use in a chemical laboratory as bases, the interest in Brønsted acidic molecular terminal hydroxides of p‐block elements, such as aluminum and silicon, has been of recent origin, with respect to the variety of applications these compounds can offer both in materials science and catalysis. Moreover, these systems are environmentally friendly, relative to the metal halides, owing to their ‐OH functionality (resembling that of water). Design and conceptualization of the corresponding terminal thiols, selenols, and tellurols (M? SH, M? SeH, and M? TeH) offer even more challenging problems to synthetic inorganic chemists. This concept summarizes some of the recent strategies developed to stabilize these otherwise very unstable species. The successful preparation of a number of silicon trihydroxides a few years back resulted in the generation of several model compounds for metal–silicates. The recent synthesis of unusual aluminum compounds such as RAl(OH)₂, RAl(SH)₂, and RAl(SeH)₂ with terminal EH (E=O, Se, or Se) groups is likely to change the ways in which some of the well‐known catalytic conversions are being carried out. The need for very flexible and innovative synthetic strategies to achieve these unusual compounds is emphasized in this concept.     

Physical insights from a penetration depth model of optically pumped NMR

A model of optically pumped NMR (OPNMR) behavior in GaAs that connects the photon energy dependence of the OPNMR signal intensity for (69)Ga with different polarizations of light has been developed. Inputs to this model include experimental conditions--external magnetic field (B(0)), temperature (T), and optical pumping parameters (tau(L), laser helicity)--as well as parameters that arise from sample-specific characteristics--electron spin lifetime (T(1e)), electron lifetime (tau(e)), electron-nuclear correlation time (tau(c)), and sample thickness (z). These various inputs affect the profile of the OPNMR signal intensity as a function of photon energy (E) in a predictable manner. Therefore, the profile can serve as a composite fingerprint by which individual parameters can be inferred when not known. Characteristics of the profile include the photon energy for maximum OPNMR signal intensity and the intensity ratio between sigma(+) and sigma(-) light.     

Optically pumped nuclear magnetic resonance of semiconductors

Optically pumped NMR (OPNMR) of direct gap and indirect gap semiconductors has been an area of active research interest, motivated by both basic science and technological perspectives. Proposals to enhance and to spatially localize nuclear polarization have stimulated interest in this area. Recent progress in OPNMR has focused on exploring the experimental parameter space in order to elucidate details of the underlying photophysics of optical pumping phenomena. The focus of this review is on recent studies of bulk samples of GaAs and InP, namely, the photon energy dependence, the magnetic field dependence, and the phase dependence of OPNMR resonances. Models for the development of nuclear polarization are discussed.     

Designer ribozymes: programming the tRNA specificity into flexizyme

Fx3 is an artificial ribozyme with the ability to aminoacylate various tRNAs with phenylalanine and its nonnatural derivatives. Herein we report a simple strategy to build tRNA specificity into the generic Fx3, by appending to its 3'-end a tRNA-specific sequence (TSS), which is complementary to the acceptor stem of the cognate tRNA. This new designer ribozyme, referred to as Fx10, is able to recognize its cognate tRNA via a 10-base-pair interaction that is formed after the invasion of the tRNA acceptor stem by the TSS. We have demonstrated that Fx10 can aminoacylate its cognate tRNA with a high degree of specificity and also discriminate against the noncognate tRNAs. Because the tRNA specificity can be easily programmed into Fx10, it is a custom-made catalyst to generate nonnatural aminoacyl-tRNAs.     

Biocatalytically oligomerized epicatechin with potent and specific anti-proliferative activity for human breast cancer cells

Catechins, naturally occurring flavonoids derived from wine and green tea, are known to exhibit multiple health benefits. Epigallocatechin gallate (EGCG) is one of the most widely investigated catechins, but its efficacy in cancer therapy is still inconsistent and limited. The poor stability of EGCG has contributed to the disparity in the reported anti-cancer activity and other beneficial properties. Here we report an innovative enzymatic strategy for the oligomerization of catechins (specifically epicatechin) that yields stable, water-soluble oligomerized epicatechins with enhanced and highly specific anti-proliferative activity for human breast cancer cells. This one-pot oxidative oligomerization is carried out in ambient conditions using Horseradish Peroxidase (HRP) as a catalyst yielding water-soluble oligo(epicatechins). The oligomerized epicatechins obtained exhibit excellent growth inhibitory effects against human breast cancer cells with greater specificity towards growth-inhibiting cancer cells as opposed to normal cells, achieving a high therapeutic differential. Our studies indicate that water-soluble oligomeric epicatechins surpass EGCG in stability, selectivity and efficacy at lower doses.     

Assembling metal phosphonates in the presence of monodentate-terminal and bidentate-bridging pyridine ligands. Use of non-covalent and covalent-coordinate interactions to build polymeric metal-phosphonate architectures

The cubic transition metal phosphonates [(t)BuPO3M(2-apy)]4 (M= Zn (1), Co (2)), whose core resembles the D4R SBU of zeolites, have been synthesized from a reaction between the corresponding metal acetate, tert-butylphosphonic acid and 2-aminopyridine (2-apy) at room temperature. X-Ray structure determination reveals that the molecules of 1 and 2, which crystallize in the tetragonal I4(1)/a space group with crystallographically imposed 4 symmetry, form a 3-D supramolecular assembly aided by N-H...O hydrogen bonding. When the same reaction was carried out by using a bridging bidentate Lewis base such as 4,4'-bipyridine, insoluble precipitate is obtained for both zinc and cobalt. In the case of other metal salts such as copper, manganese and nickel, however, one-dimensional polymeric compounds such as [M((t)BuPO3H)2(4,4'-bipy)(H2O)2]n (M= Cu (3), Mn (4)), [(Ni(4,4'-bipy)(H2O)4)((t)BuPO3H)2(H2O)]n (5) have been isolated. The solid-state structures of 3-5 have been determined by single crystal X-ray diffraction studies. Compounds 3 and 4 are isostructural and crystallize in the triclinic P1 space group with two phosphonate ligands coordinated to the metal centers in a [1.100] fashion, whereas in the case of compound 5, the polymeric backbone is formed by Ni-4,4'-bipy units and the phosphonate anions show no bonding interaction to the metal. The 1-D polymeric chains of 3-5 organize in the solid-state as 3-D supramolecular assemblies with the aid of extensive hydrogen bonding interaction between coordinated water molecules and P-OH or P=O groups of the phosphonate ligands.     

Determination of 77Se-77Se and 77Se-13C J-coupling parameters for the clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2-

We have investigated rarely observed 77Se J-couplings (spin-spin couplings) in the mixed-metal face-capped octahedral clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2- at natural abundance. To the best of our knowledge, these are the first observations of Se-Se spin-spin interactions between mu3-Se sites, important for stereochemical assignments in hexarhenium analogues, Chevrel phase materials, and similar cluster materials. NMR techniques such as COSY, INADEQUATE, and 2D J-resolved spectroscopy have been used in conjunction to study these interactions. The two isomers (cis and trans) of [Re4Os2Se8(CN)6]2- were distinguishable, and selective isotopic labeling of [Re5OsSe8(CN)6]3- with 13CN ligands enabled resonances to be assigned by observing the 2J (Se-M-C) couplings. For [Re5OsSe8(CN)6]3-, two different 2J (Se-M-Se) couplings were measurable on a single cluster, and these are related to one another through spin-spin interactions across a face diagonal or along an edge of the cube of inner selenium ligands. A rigorous analysis based on combinatorial math has been invoked to assign the couplings on the basis of the probability of multiple-spin interactions. The face diagonal association is found to result in a J-coupling interaction larger in magnitude than that from coupling along an edge of the cube-information critical for making stereochemical assignments of selenium sites.