Novel NLO-phores with proaromatic donor and acceptor groups

[reaction: see text] Novel D-pi-A NLO-phores based on the 1,3-dithiol-2-ylidene donor and the thiobarbituric acceptor moieties have been prepared. Modification of the length and rigidity of the pi-spacer allows the first systematic study of the second-order nonlinear optical properties of doubly proaromatic merocyanines. The pi-electron donor efficiency of the 1,3-dithiol-2-ylidene group is superior to that of the tetrathiafulvalenyl group.     

Unprecedented gold-tellurolate clusters [Au(8)(mu-TeR)(8)(PR'(3))(4)

The reaction of [AuCl(PR'3)] with KTeR, prepared from RTeTeR and K-selectride, gives the gold-tellurolate clusters [Au8(mu-TeR)8(PR'3)4] (R = Ph, Tol; PR'3 = PPh3, PPh2py) in high yield. This result contrasts with the one obtained from the reaction with thiolates or selenolates, from which mononuclear complexes are synthesized. The structures of these species have been determined and consist on three layers of gold and tellurium atoms in the ratio Au3Te2:Au2Te4:Au3Te2. There are short gold...gold interactions ranging from 2.9463(7) to 3.31132(7) A, and the clusters are composed of di- and tri-coordinated gold centers. The result is unprecedented in gold-chalcogenolate chemistry from which mononuclear species are expected and represents one of the few examples of gold-tellurolate derivatives. These species show an interesting luminescent behavior in the solid state (at 77 K) and in solution (both at 298 and 77 K).     

Highly luminescent gold(I)-silver(I) and gold(I)-copper(I) chalcogenide clusters

The reactions of [AuClL] with Ag(2)O, where L represents the heterofunctional ligands PPh(2)py and PPh(2)CH(2)CH(2)py, give the trigoldoxonium complexes [O(AuL)(3)]BF(4). Treatment of these compounds with thio- or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL)(3)]BF(4) (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe)(4)]PF(6) to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh(2)py)(3)]BF(4) with silver or copper salts give [E(AuPPh(2)py)(3)M](2+) (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au(3)Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh(2)py)(3)](+) units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh(2)CH(2)CH(2)py)(3)]BF(4) with silver and copper salts give complexes with [E(AuPPh(2)CH(2)CH(2)py)(3)M](2+) stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of AuM interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal.     

Structure and thermodynamics of polystyrene-block-poly(ethylene/propene) micelles in selective solvents

The concentration and temperature dependencies of micelle formation by a polystyrene-block-poly(ethylene/propene) copolymer in several ketones (2-butanone, 3-pentanone, 4-methyl-2-pentanone, 4-heptanone, 5-methyl-2-hexanone and 5-methyl-3-heptanone) were studied by static and dynamic light scattering, viscometry and size exclusion chromatography. No micelles were detected in solutions of 5-methyl-3-heptanone. The standard Gibbs energy, ΔG°, the standard enthalpy, ΔH°, and the standard entropy, ΔS°, of micellization were estimated. The values of ΔG° and ΔH° were negative for all ketones studied and depended on the polar character of the ketone. The micelles showed larger association numbers and densities independent of the ketone. Micelle dimensions hardly depended on the ketone.     

Synthesis, structural characterization, and theoretical studies of gold(I) and gold(I)-gold(III) thiolate complexes: quenching of gold(I) thiolate luminescence

The gold(I) thiolate complexes [Au(2-SC6H4NH2)(PPh3)] (1), [PPN][Au(2-SC6H4NH2)2] (2) (PPN = PPh3=N=PPh3), and [{Au(2-SC6H4NH2)}2(mu-dppm)] (3) (dppm = PPh2CH2PPh2) have been prepared by reaction of acetylacetonato gold(I) precursors with 2-aminobenzenethiol in the appropriate molar ratio. All products are intensely photoluminescent at 77 K. The molecular structure of the dinuclear derivative 3 displays a gold-gold intramolecular contact of 3.1346(4) A. Further reaction with the organometallic gold(III) complex [Au(C6F5)3(tht)] affords dinuclear or tetranuclear mixed gold(I)-gold(III) derivatives with a thiolate bridge, namely, [(AuPPh3){Au(C6F5)3}(mu2-2-SC6H4NH2)] (4) and [(C6F5)3Au(mu2-2-SC6H4NH2)(AudppmAu)(mu2-2-SC(6)H4NH2)Au(C6F5)3] (5). X-ray diffraction studies of the latter show a shortening of the intramolecular gold(I)-gold(I) contact [2.9353(7) or 2.9332(7) A for a second independent molecule], and short gold(I)-gold(III) distances of 3.2812(7) and 3.3822(7) A [or 3.2923(7) and 3.4052(7) A] are also displayed. Despite the gold-gold interactions, the mixed derivatives are nonemissive compounds. Therefore, the complexes were studied by DFT methods. The HOMOs and LUMOs for gold(I) derivatives 1 and 3 are mainly centered on the thiolate and phosphine (or the second thiolate for complex 2), respectively, with some gold contributions, whereas the LUMO for derivative 4 is more centered on the gold(III) fragment. TD-DFT results show a good agreement with the experimental UV-vis absorption and excitation spectra. The excitations can be assigned as a S --> Au-P charge transfer with some mixture of LLCT for derivative 1, an LLCT mixed with ILCT for derivative 2, and a S --> Au...Au-P charge transfer with LLCT and MC for derivative 3. An LMCT (thiolate --> Au(III) mixed with thiolate --> Au-P) excitation was found for derivative 4. The differing nature of the excited states [participation of the gold(III) fragment and the small contribution of sulfur] is proposed to be responsible for quenching the luminescence.     

A tandem synthesis of 3-aroylcoumarinoflavones catalyzed by <Emphasis Type="SmallCaps">l</Emphasis>-proline and their antioxidant activity

A facile, convenient, efficient and high-yielding synthesis of 3-aroylcoumarinoflavones has been developed by the condensation of easily synthesized 7-hydroxy-8-formylflavones and benzoyl acetonitriles in the presence of catalytic amount of l-proline in ethanol reflux. All the synthesized compounds were evaluated for their antioxidant activity. Some of the compounds showed very good activity compared to standard BHT.     

Coefficient estimates of negative powers and inverse coefficients for certain starlike functions

For ?1≤B<A≤1, let \(\mathcal {S}^{*}(A,B)\) denote the class of normalized analytic functions \(f(z)= z+{\sum }_{n=2}^{\infty }a_{n} z^{n}\) in |z|<1 which satisfy the subordination relation z f ^′(z)/f(z)?(1 + A z)/(1 + B z) and Σ^?(A,B) be the corresponding class of meromorphic functions in |z|>1. For \(f\in \mathcal {S}^{*}(A,B)\) and λ>0, we shall estimate the absolute value of the Taylor coefficients a _n (?λ,f) of the analytic function (f(z)/z)^?λ . Using this we shall determine the coefficient estimate for inverses of functions in the classes \(\mathcal {S}^{*}(A,B)\) and Σ^?(A,B).     

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (T_NTBN) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of T_NTBN was estimated for CBO3OCB and T_NTBN was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of T_NTBN on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.     

The Prevalence of Helicobacter Pylori Infection in Benign Laryngeal Disorders

Helicobacter pylori (HP) is an accepted cause of chronic active gastritis and has a major causative role in peptic ulcers. It is a gastric carcinogen. Its role in nonulcer dyspepsia (NUD) is less clear, yet 50% of patients with NUD are infected with HP, and some recent literature demonstrates long-term improvement of symptoms following eradication. HP has been investigated in several other organ systems, but has not been investigated to any major degree in laryngeal disorders, a region that could be directly exposed to the bacterium from pharyngolaryngeal reflux. This study represents one arm of a larger study designed to investigate such a relationship. Of 101 patients with nonmalignant voice disorders presenting to our voice clinics, 54.5% tested positive for the H. pylori organism. Of the controls, 47.1% tested positive. When striated into age groups of < 45 years, 46–61 years, and > 62 years, and then age-matched with the controls, the likelihood of infection with the H. pylori organism was greater in both the experimental middle group, and in the middle group when combined with the elder group, than in the matched controls, and this difference demonstrated a trend approaching statistical significance. This finding is discussed in the light of other studies on HP and on gastroesophageal reflex (GER).