Anion radicals of some fluorobiphenyls

Potassium 4,4′-difluorobiphenylide, 4-fluorobiphenylide and potassium 3,3′-difluorobiphenylide are stable at −80° in the tetrahydrofuran. 4-Chlorobiphenyl, 4-bromobiphenyl and 4,4′-dibromobiphenyl apparently react with potassium at low temperatures to form radicals which decompose immediately by halide elimination. The ESR spectra of the 4,4′-difluorobiphenylide and 3,3′-difluorobiphenylide radicals and the polarographic behaviour, p-band positions, and results of LCAO---MO calculations for the parent, neutral compounds are reported.     

High-sensitivity atomic magnetometer unaffected by spin-exchange relaxation

Alkali-metal magnetometers compete with SQUID detectors as the most sensitive magnetic field sensors. Their sensitivity is limited by relaxation due to spin-exchange collisions. We demonstrate a K magnetometer in which spin-exchange relaxation is completely eliminated by operating at high K density and low magnetic field. Direct measurements of the signal-to-noise ratio give a magnetometer sensitivity of 10 fT Hz(-1/2), limited by magnetic noise produced by Johnson currents in the magnetic shields. We extend a previous theoretical analysis of spin exchange in low magnetic fields to arbitrary spin polarizations and estimate the shot-noise limit of the magnetometer to be 2x10(-18) T Hz(-1/2).     

Modeling substrate- and inhibitor-bound forms of liver alcohol dehydrogenase: chemistry of mononuclear nitrogen/sulfur-ligated zinc alcohol,formamide, and sulfoxide complexes

Using a mixed nitrogen/sulfur ligand possessing a single internal hydrogen bond donor (N,N-bis-2-(methylthio)ethyl-N-(6-amino-2-pyridylmethyl)amine (bmapa)), we prepared and structurally and spectroscopically characterized a series of zinc complexes possessing a single alcohol ([(bmapa)Zn(MeOH)](ClO(4))(2) (1)), formamide ([(bmapa)Zn(DMF)](ClO(4))(2) (3), [(bmapa)Zn(NMF)](ClO(4))(2) (4)), or sulfoxide ([(bmapa)Zn(DMSO)](ClO(4))(2) (7), [(bmapa)Zn(TMSO)](ClO(4))(2) (8)) ligand. X-ray crystallographic characterization was obtained for 1.MeOH, 3, 4, 7.DMSO, and 8. To enable studies of the influence of the single hydrogen bond donor amino group of the bmapa ligand on the chemistry of zinc/neutral oxygen donor binding interactions, analogous alcohol ([(bmpa)Zn(MeOH)](ClO(4))(2) (2)), formamide ([(bmpa)Zn(DMF)](ClO(4))(2) (5), [(bmpa)Zn(NMF)](ClO(4))(2) (6)), and sulfoxide ([(bmpa)Zn(DMSO)](ClO(4))(2) (9), [(bmpa)Zn(TMSO)](ClO(4))(2) (10)) complexes of the bmpa (N,N-bis-2-(methylthio)ethyl-N-(2-pyridylmethyl)amine) ligand system were generated and characterized. Of these, 2, 5, 6, and 9.2DMSO were characterized by X-ray crystallography. Solution spectroscopic methods ((1)H and (13)C NMR, FTIR) were utilized to examine the formamide binding properties of 3-6 in CH(3)CN and CH(3)NO(2) solutions. Conclusions derived from this work include the following: (1) the increased donicity of formamide and sulfoxide donors (versus alcohols) makes these competitive ligands for a cationic N/S-ligated zinc center, even in alcohol solution, (2) the inclusion of a single internal hydrogen bond donor, characterized by a heteroatom distance of approximately 2.80-2.95 A, produces subtle structural perturbations in N/S-ligated zinc alcohol, formamide, or sulfoxide complexes, (3) the heteroatom distance of a secondary hydrogen-bonding interaction involving the oxygen atom of a zinc-coordinated alcohol, formamide, and sulfoxide ligand is reduced with increasing donicity of the exogenous ligand, and (4) formamide displacement on a N/S-ligated zinc center is rapid, regardless of the presence of an internal hydrogen bond donor. These results provide initial insight into the chemical factors governing the binding of a neutral oxygen donor to a N/S-ligated zinc center.     

Dimethylsilyl- and methylene-bridged aromatic groups : II. Phosphorescent triplet states

The zero-field splitting parameters D and E, or D, were measured by electron spin spectroscopy for the triplet states of bis(4-biphenylyl)dimethylsilane, 4,4′-bis-(4-biphenylyldimethylsilyl)biphenyl, 1,2-diphenyltetramethyldisilane, several monosilanes, bis(4-biphenylyl)methane, 4,4′-bis(4-phenylbenzyl)biphenyl, and dimethyldiphenylmethane. The zero-field splitting values of compounds having biphenyl subunits bridged with either SiMe₂- or CH₂-groups, compared with those of mono- and disubstituted biphenyls, show that the triplet electrons are localized mainly on one biphenyl group in each of the bridged compounds on the time scale of the ESR observations.     

Chemistry of a binuclear cadmium(II) hydroxide complex: formation from water,CO(2) reactivity,and comparison to a zinc analog

Treatment of the bmnpa (N,N-bis-2-(methylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine) ligand with equimolar amounts of Cd(ClO(4))(2).5H(2)O and Me(4)NOH.5H(2)O in CH(3)CN yielded the binuclear cadmium hydroxide complex [((bmnpa)Cd)(2)(mu-OH)(2)](ClO(4))(2).CH(3)CN (1). Complex 1 may also be prepared (a) by treatment of a CH(3)CN solution of (bmnpa)Cd(ClO(4))(2) (2) with 1 equiv of n-BuLi, followed by treatment with water or (b) from 2 in the presence of 1 equiv each of water and NEt(3). The hydroxide derivative 1 is not produced from 2 and water in the absence of an added base. Complex 1 possesses a binuclear structure in the solid state with hydrogen-bonding and CH/pi interactions involving the bmnpa ligand. The overall structural features of 1 differ from the halide derivative [((bmnpa)Cd)(2)(mu-Cl)(2)](ClO(4))(2) (3), particularly in that the Cd(2)(mu-OH)(2) core of 1 is symmetric whereas the Cd(2)(mu-Cl)(2) core of 3 is asymmetric. In acetonitrile solution, 1 behaves as a 1:2 electrolyte and retains a binuclear structure and secondary hydrogen-bonding and CH/pi interactions, whereas 3 is a 1:1 electrolyte, indicating formation of a mononuclear [(bmnpa)CdCl]ClO(4) species in solution. Treatment of 1 with CO(2) in anhydrous CH(3)CN yields the bridging carbonate complex [((bmnpa)Cd)(2)(mu-CO(3))](ClO(4))(2).CH(3)CN (4). Treatment of a chemically similar zinc hydroxide complex, [((benpa)Zn)(2)(mu-OH)(2)](ClO(4))(2) (benpa = N,N-bis-2-(ethylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine, with CO(2) also results in the formation of a carbonate derivative, [((benpa)Zn)(2)(mu-CO(3))](ClO(4))(2) (5), albeit the coordination mode of the bridging carbonate moiety is different. Treatment of 4 with added water results in no reaction, whereas 5 under identical conditions will undergo reaction to yield the zinc hydroxide complex [((benpa)Zn)(2)(mu-OH)(2)](ClO(4))(2).     

A cadmium hydroxide complex of a N3S-donor ligand containing two hydrogen bond donors: synthesis, characterization, and CO2 reactivity

Treatment of the ebnpa (N-2-(ethylthio)ethyl-N,N-bis((6-neopentylamino-2-pyridyl)methyl)amine) ligand with a molar equivalent amount of Cd(ClO(4))(2).5H(2)O in CH(3)CN followed by the addition of [Me(4)N]OH.5H(2)O yielded the cadmium hydroxide complex [(ebnpaCd)(2)(mu-OH)(2)](ClO(4))(2) (1). Complex 1 has a binuclear cation in the solid-state with secondary hydrogen-bonding and CH/pi interactions involving the ebnpa ligand. In acetonitrile, 1 forms a binuclear/mononuclear equilibrium mixture. The formation of a mononuclear species has been confirmed by conductance measurements of 1 at low concentrations. Variable temperature studies of the binuclear/mononuclear equilibrium provided the standard enthalpy and entropy associated with the formation of the monomer as DeltaH degrees = +31(2) kJ mol(-1) and DeltaS degrees = +108(8) J mol(-1) K(-1), respectively. Enhanced secondary hydrogen-bonding interactions involving the terminal Cd-OH moiety may help to stabilize the mononuclear complex. Treatment of 1 with CO(2) in acetonitrile results in the formation of a binuclear cadmium carbonate complex, [(ebnpaCd)(2)(mu-CO(3))](ClO(4))(2) (2).     

Elastic constants of B-A1 composites by ultrasonic velocity measurements

The complete orthotropic elastic-stiffness matrix of unidirectional, Borsic-filament-reinforced aluminum composites was experimentally evaluated for three different volume fractions by ultrasonic velocity measurements on thin plates. Longitudinal- and shear-velocity measurements were made in appropriate symmetry directions by direct contact or liquid-immersion techniques. The elastic constants determined by this pulsed through-transmission method were in agreement with micromechanical theories based on the properties of the constituent materials. Agreement was also found between engineering constants determined by mechanical testing and those calculated from the ultrasonic data. Finally, measurement of the ultrasonic-wave velocity has also been shown to be a rapid nondestructive-test method for determining filament-volume fraction in a fabricated part.     

Antidiabetic Potential of Volatile Cinnamon Oil: A Review and Exploration of Mechanisms Using In Silico Molecular Docking Simulations

Cinnamon has been used as a flavoring and medicinal agent for centuries. Much research has focused on cinnamon bark powder, which contains antioxidants, flavonoids, carotenoids, vitamins, minerals, fiber, and small amounts of essential oil. However, isolated and concentrated cinnamon essential oil may also have important medicinal qualities, particularly in antidiabetic therapy. Some of the most common essential oil constituents identified in the literature include cinnamaldehyde, eugenol, and beta-caryophyllene. Due to their high concentration in cinnamon essential oil, these constituents are hypothesized to have the most significant physiological activity. Here, we present a brief review of literature on cinnamon oil and its constituents as they relate to glucose metabolism and diabetic pathogenesis. We also present molecular docking simulations of these cinnamon essential oil constituents (cinnamaldehyde, eugenol, beta-caryophyllene) that suggest interaction with several key enzymes in glucometabolic pathways.