Wafer and epilayer improvement for integrated optics devices on InP: the ESPRIT project 2518

Ga _x In_1–x As _y P_1–y alloys lattice matched to InP substrates are currently used to fabricate optoelectronic and integrated optics devices. To achieve devices with high performances and high fabrication yield, the uniformity and reproducibility of the Ga _x In_1–x As _y P_1–y epitaxial layers (composition, thickness, doping, etc.) have become key parameters. These problems have been addressed in the frame of ESPRIT project 2518 and are presented in this paper. Several aspects have been considered starting from the optimization of InP substrates, the MOVPE growth of uniform GalnAsP layers, the material characterization to the validation of material uniformity on passive optical waveguides. Both scanning photoluminescence analysis and waveguide losses measurements performed on 2 inch wafers with a high lateral resolution have shown that high quality uniform GalnAsP layers can be obtained reproducibly on 2 InP substrates using a commercially available LP-MOCVD growth process. In particular, more than 60% of 36 mm long, 3m wide and 100m spaced rib waveguides exhibit losses below 0.8dBcm^–1.     

Magnetic properties on holmium iron garnet in high magnetic field. Optical absorption spectra in the infra-red region

On single crystals of holmium iron garnet (HoIG), magnetic properties have been studied in magnetic field up to 150kOe applied parallel to the main crystallographic directions in the 4.2–300K temperature range. Above 130 K, the magnetization is isotropic and linear magnetic field dependent as previously found in polycrystals and predicted by Néel's ferrimagnetic theory. Nevertheless the paramagnetic Curie temperature is much higher than the polycrystal value. Below 130K, due to the onset of the umbrella structure, the ferrite magnetization presents a non linear field variation with [111] as easy direction. The field evolutions of the anisotropy constants (K ₁ andK ₂) were calculated. Optical absorption measurements of both 5₈5I ₆ and 5I ₈5I ₇ transitions are reported and compared to the results of the literature in terms of inequivalent magnetic sites.     

Evaluation of a high-performance thin-layer chromatographic technique for the determination of salbutamol serum levels in clinical trials.

Salbutamol concentrations were determined by high-performance thin-layer chromatography in the sera of two sets of ten volunteers at hourly intervals for 6 h after taking one 8-mg slow-release tablet. The influence of time lapse in processing of serum samples, i.e. centrifugation, extraction and chromatography, was studied. A statistical significant instability of salbutamol in the sera of patients was found which was not present in standard drug-free serum samples spiked with salbutamol and used for construction of standard curves.     

Redox,transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin,nickel, and palladium compounds

Here we report that capping the molecule TTFtt (TTFtt = tetrathiafulvalene-2,3,6,7-tetrathiolate) with dialkyl tin groups enables the isolation of a stable series of redox congeners and facile transmetalation to Ni and Pd. TTFtt has been proposed as an attractive building block for molecular materials for two decades as it combines the redox chemistry of TTF and dithiolene units. TTFttH₄, however, is inherently unstable and the incorporation of TTFtt units into complexes or materials typically proceeds through the in situ generation of the tetraanion TTFtt⁴⁻. Capping of TTFtt⁴⁻ with Bu₂Sn²⁺ units dramatically improves the stability of the TTFtt moiety and furthermore enables the isolation of a redox series where the TTF core carries the formal charges of 0, +1, and +2. All of these redox congeners show efficient and clean transmetalation to Ni and Pd resulting in an analogous series of bimetallic complexes capped by 1,2-bis(diphenylphosphino)ethane (dppe) ligands. Furthermore, by using the same transmetalation method, we synthesized analogous palladium complexes capped by 1,1′-bis(diphenylphosphino)ferrocene (dppf) which had been previously reported. All of these species have been thoroughly characterized through a systematic survey of chemical and electronic properties by techniques including cyclic voltammetry (CV), ultraviolet-visible-near infrared spectroscopy (UV-vis-NIR), electron paramagnetic resonance spectroscopy (EPR), nuclear magnetic resonance spectroscopy (NMR) and X-ray diffraction (XRD). These detailed synthetic and spectroscopic studies highlight important differences between the transmetalation strategy presented here and previously reported synthetic methods for the installation of TTFtt. In addition, the utility of this stabilization strategy can be illustrated by the observation of unusual TTF radical–radical packing in the solid state and dimerization in the solution state. Theoretical calculations based on variational 2-electron reduced density matrix methods have been used to investigate these unusual interactions and illustrate fundamentally different levels of covalency and overlap depending on the orientations of the TTF cores. Taken together, this work demonstrates that tin-capped TTFtt units are ideal reagents for the installation of redox-tunable TTFtt ligands enabling the generation of entirely new geometric and electronic structures.

Capping TTFtt enables facile transmetalation in three different oxidation states.     

Steric hindrance-controlled Pd(0)-catalyzed coupling-cyclization of 2,3-allenamides and organic iodides. An efficient synthesis of iminolactones and gamma-hydroxy-gamma-lactams

Under the catalysis of 1 mol % Pd(PPh3)4, the reaction of 4,4-disubstituted 2,3-allenamides and organic iodides in toluene afforded iminolactones stereospecifically in >90% yields using K2CO3 (2 equiv)-5 mol % TBAB as the base. A similar reaction with 4-monosubstituted 2,3-allenamides afforded gamma-hydroxy-gamma-lactams in relatively lower yields. The N/O-attack selectivity may be determined by the steric effect at the 4-position of 2,3-allenamides.     

Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-

Gas phase vibrational spectra of BrHI- and BrDI- have been measured from 6 to 17 microm (590-1666 cm(-1)) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI-.Ar and BrDI-.Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI- and BrDI- were dissociated into HBr (DBr) and I- via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI- and BrDI- due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated.     

An Upper Bound for the w-Weak Global Dimension of Pullbacks

Let R be a commutative ring with identity and I0 an ideal of R.We introduce and study the c-weak global dimension c-w.gl.dim(R/I0) of the factor ring R/I0.Let T be a w-linked extension of R,and we also introduce the wR-weak global dimension wR-w.gl.dim(T) of T.We show that the ring T with wR-w.gl.dim(T) =0 is exactly a field and the ring T with wR-w.gl.dim(T) ≤ 1 is exactly a PwRMD.As an application,we give an upper bound for the w-weak global dimension of a Cartesian square (RDTF,M).More precisely,if T is w-linked over R,then w-w.gl.dim(R) ≤ max{wR-w.gl.dim(T) + w-fdR T,c-w.gl.dim(D) + w-fdn D}.Furthermore,for a Milnor square (RDTF,M),we obtain w-w.gl.dim(R) ≤ max{wR-w.gl.dim(T) + w-fdR T,w-w.gl.dim(D) + w-fdR D}.     

Screening an In-House Isoquinoline Alkaloids Library for New Blockers of Voltage-Gated Na+ Channels Using Voltage Sensor Fluorescent Probes: Hits and Biases

Voltage-gated Na⁺ (Na_V) channels are significant therapeutic targets for the treatment of cardiac and neurological disorders, thus promoting the search for novel Na_V channel ligands. With the objective of discovering new blockers of Na_V channel ligands, we screened an In-House vegetal alkaloid library using fluorescence cell-based assays. We screened 62 isoquinoline alkaloids (IA) for their ability to decrease the FRET signal of voltage sensor probes (VSP), which were induced by the activation of Na_V channels with batrachotoxin (BTX) in GH3b6 cells. This led to the selection of five IA: liriodenine, oxostephanine, thalmiculine, protopine, and bebeerine, inhibiting the BTX-induced VSP signal with micromolar IC₅₀. These five alkaloids were then assayed using the Na⁺ fluorescent probe ANG-2 and the patch-clamp technique. Only oxostephanine and liriodenine were able to inhibit the BTX-induced ANG-2 signal in HEK293-hNa_V1.3 cells. Indeed, liriodenine and oxostephanine decreased the effects of BTX on Na⁺ currents elicited by the hNa_V1.3 channel, suggesting that conformation change induced by BTX binding could induce a bias in fluorescent assays. However, among the five IA selected in the VSP assay, only bebeerine exhibited strong inhibitory effects against Na⁺ currents elicited by the hNav1.2 and hNav1.6 channels, with IC₅₀ values below 10 µM. So far, bebeerine is the first BBIQ to have been reported to block Na_V channels, with promising therapeutical applications.