Parametric generation of twin photons in vertical triple microcavities

We report the realization of a monolithic vertical-cavity, surface emitting micro-optical parametric conversion nanostructure, triply resonant with the parametric frequencies, allowing parametric oscillation with ultra-low pump power threshold. The photonic phase-space naturally provides triple resonance for the parametric frequencies, together with built-in cavity phase-matching for the pump wave at normal incidence. Parametric oscillation is observed in both the strong and weak exciton–photon coupling regime, allowing a high operating temperature. Signal and idler beams can be collected at 0° or at finite angles. The OPO threshold is low enough to envisage the realization of an all-semiconductor electrically-pumped micro-parametric oscillator. To cite this article: C. Diederichs et al., C. R. Physique 8 (2007).     

An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene

The first N-donor-stabilized phosphasilene LSi(SiMe(3))═PSiMe(3) (L = PhC(NtBu)(2)) has been synthesized in 87% yield through 1,2-silyl migration of the (Me(3)Si)(2)P-substituted, N-heterocyclic silylene [LSi-P(SiMe(3))(2)]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph(3)PCl(2) to give the unprecedented 4π-electron Si(2)P(2)-cycloheterobutadiene [(LSi)(2)P(2)] with two-coordinate phosphorus atoms. The striking molecular structures as well as the (29)Si and (31)P NMR spectroscopic features of both products indicate the presence of zwitterionic Si═P bonds which is also in accordance with results by DFT calculations.     

Pyridazines 92. Synthesis of dialkyldipyridazinodiazepinones as potential HIV‐1 reverse transcriptase inhibitors

Two methods for the preparation of dialkylsubstituted dipyridazino[4,3‐b:3′,4′‐e][1,4]diazepinones and dipyridazino[3,4‐b:3′,4′‐e][1,4]diazepinones are reported. The new compounds were evaluated for their inhibitory effects against the replication of human immunodeficiency virus [HIV‐1(III_B) and HIV‐2(ROD)] in MT‐4 cells.     

Zur Theorie der Chiralitätsfunktionen

The Algebraic Theory of Chirality Functions is derived by means of exclusively qualitative considerations. Hence, the significance of quantitative results is questionable. Moreover the construction of “Näherungsansätze” (”Approximation-Ansatz”), which may be interpreted as semiempirical methods, is achieved on the basis of plausibility and mathematical simplicity. Since physical arguments are not included, the consistency or inconsistency of “Näherungsansätze” with experimental results do not justify direct physical conclusions.     

The impact of chemical composition on the degradation kinetics of poly(lactic-co-glycolic) acid copolymers cast films in phosphate buffer solution

We have investigated the in vitro degradation of poly(lactic-co-glycolic) acid copolymer with different lactic to glycolic ratio: 50:50, 65:35, 75:25, 95:05 and 100:00 (mol. %). The degradation studies were performed on solvent cast films of controlled thickness and shape. The samples were incubated at 37 °C in phosphate buffered saline solution. The degradation was followed using potentiometry, light microscopy, gravimetry, size exclusion chromatography and differential scanning calorimetry. The same degradation process, as discussed in detail in our previous article for PLGA 50:50 (E. Vey et al., J. of Polym. Deg. and Stab. 2008, 93, 1896-1876), was observed for all the samples investigated, however the time scale over which the different events/degradation steps were observed increased with increasing lactic content of the polymer. The glass transition temperatures of the films increase with lactic content and are thought to have a significant impact on the rate of diffusion of water into the films - the higher the glass transition the slower the diffusion of water - and therefore on the degradation dynamics of the films. Kinetic parameters were extracted from the acid release, molecular weight and mass loss data. In each case linear correlations between the rate constants extracted and the lactic content of the polymer were found. The overall degradation rate of the films was found to decrease with increasing lactic content.     

Electrokinetic characterization of poly(dimethylsiloxane) microchannels

This paper characterizes the basic electrokinetic phenomena occurring within native poly(dimethylsiloxane) (PDMS) microchannels. Using simple buffers and current measurements, current density and electroosmosis data were determined in trapezoidal, reversibly sealed PDMS/PDMS and hybrid PDMS/glass channels with a cross-sectional area of 1035.5 microm(2) and about 6 cm length. This data was then compared to that obtained in an air-thermostated 50 microm inner diameter (1963.5 microm(2) cross-sectional area) fused-silica (FS) capillary of 70 cm length. Having a pH 7.8 buffer with an ionic strength (I) of 90 mM, Ohms's law was observed in the microchannels with electric field strengths of up to about 420 V/cm, which is about twice as high as for the FS capillary. The electroosmotic mobility (micro(EO)) in PDMS and FS is shown to exhibit the same general dependences on I and pH. For all configurations tested, the experimentally determined micro(EO) values were found to correlate well with the relationship micro(EO) = a + b log(I), where a and b are coefficients that are determined via nonlinear regression analysis. Electroosmotic fluid pumping in native PDMS also follows a pH dependence that can be estimated with a model based upon the ionization of silanol. Compared to FS, however, the magnitude of the electroosmotic flow in native PDMS is 50-70% smaller over the entire pH range and is difficult to maintain at acidic pH values. Thus, the origin of the negative charge at the inner wall of PDMS, glass, and FS appears to be similar but the density is lower for PDMS than for glass and FS.     

Enhanced selectivity in Novozym 435 catalyzed kinetic resolution of secondary alcohols and butanoates caused by the (R)-alcohols

In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced.