Morphology-to-properties correlations in anodic porous InP layers

In this paper, we investigate the properties of porous structures anodically grown onto n-InP (100) in HCl. In situ electrochemical characterizations show the pore morphology strongly influences the properties of the InP surfaces. Both dc- and ac-electrochemical measurements reveal an enhancement of the capacitive current and a modification of the electronic distribution at the interface. Photocurrent spectra performed during the pore growth are also strongly modified. For low anodic charges, an increase of the photocurrent with a redshift of the absorption edge is measured. These evolutions can be respectively ascribed (i) to a reflection decrease due to a surface roughening and (ii) to the creation of surface states within the band gap. For higher anodic charges, the photocurrent drops with a narrowing of the spectrum. Using a model based on the “dead” layer, the porous layer is considered as an absorbent film that progressively attenuates the photocurrent of the bulk semiconductor.     

Phosphorus dendrimers as viewed by 31P NMR spectroscopy; synthesis and characterization

This review emphasizes the role of phosphorus for the elaboration of dendrimers and of various highly sophisticated dendritic structures, and the invaluable role played by ³¹P NMR for their characterization and to ascertain their purity. A few properties, highlighting the importance of phosphorus are reported at the end of this review.     

Symmetric Groups and Lattices

This paper deals with various problems in lattice theory involving local extrema. In particular, we construct infinite series of highly symmetric spherical 3-designs which include some of the examples constructed in [9] in dimensions 5 and 7. We also construct new types of dual-extreme lattices.Received June 29, 2002; in final form January 14, 2003 Published online May 16, 2003     

First carbohydrate liquid crystals of columnar structure

S, S-Dialkylacetals of aldoses, tripodal in structure and recently synthesized in large numbers by three groups, do not exhibit thermotropically a smectic, but a columnar hexagonal mesophase (Hx) as we have proved by X-ray diffraction. The molecular organization in this mesophase is comparable with a similar one known for phasmidic molecules. These various multiols, although different in stereo-chemistry, form only one type of hydrogen-bonded disc-shaped multimer. Its mesophase structure is made up of about five molecules placed in columns with a skeleton of hydrogen-bridged sugar parts surrounded by thioalkyl groups in the periphery. Since three 6-deoxy sugar dithioacetals were shown to be non-thermomesomorphic the terminal hydroxyl function is essential for this molecular arrangement which seems not to be true for missing ones in the inner part of a sugar chain, as we have found in one case.     

Protamine neutralisation of low molecular weight heparins and their oligosaccharide components

Protamine sulphate is an effective inhibitor of heparin and is used clinically to neutralise both low molecular weight heparins (LMWH) and unfractionated heparin (UFH). However, protamine sulphate does not fully counter the anti-Xa effect of LMWH, even in excess (>40 μg to 1 IU/ml). To investigate the molecular basis for this observation, the residual potencies in the presence and absence of plasma as well as the molecular weight profiles of commercial LMWH neutralised with increasing amounts of protamine were measured. Materials over 5000 Da are preferentially neutralised by protamine. To further investigate this molecular weight dependence, monodisperse oligosaccharides were prepared from three commercial LMWHs. The specific anti-Xa activity for the fractions increased with molecular weight, and was found to vary between the three preparations for oligosaccharides of the same molecular weight. Our results indicate that protamine sulphate neutralisation is largely dependent on molecular weight, leading to the implication that LMWHs containing a larger proportion of small oligosaccharides will not be as effectively neutralised. Protamine sulphate neutralisation of any given LMWH is also affected by the specific anticoagulant activities of its low molecular weight components, which varies between LMWH products, presumably with the method of manufacture.     

Electrochemical and spectrophotometrical investigation of the electron-accepting strength of organic superelectrophiles: X-ray structure of their charge transfer complexes with tetrathiafulvalene

Nitro Benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles are ranked amongst the strongest electrophiles known to date. In the past twenty years, their propensity to act as electron organic acceptors has been less studied. In this paper, we report on the study of their electrochemical behavior and on the structural characterization of charge transfer complexes (CTC) deriving from their interaction with tetrathiafulvalene (TTF) derivatives, both in solution and in the solid state. The first half wave reduction potentials (E(1/2)(I)) associated with a reversible monoelectronic transfer process of a large set of nitro substituted benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles have been determined through a detailed electrochemical approach in acetonitrile with a microelectrode network using the ferrocene as an internal reference potential in this electrochemical study. Determination of the electron affinity (EA(CT)) of this series of substituted electrodeficient heteroaromatics as well as their LUMO energy was performed using the Charge Transfer Spectroscopic (CTS) method in solution and by DFT calculations, respectively. The use of the correlation EA(CT) versus the reversible half wave potential (E(1/2)(I)) appears to be a useful tool to estimate readily the E(1/2)(I) or EA(CT) values when they cannot be experimentally determined. The diffusion coefficient of these electrophiles has, for the first time, been determined in acetonitrile. These air stable electrodeficient heteroaromatics have been explored as potential new organic acceptors in the formation of charge transfer (CT) complexes with TTF derivatives. Crystallographic data of two CT complexes with TTF (especially the C-C and C-S bond lengths of the TTF moieties) indicate that these complexes exhibit weak electron delocalization and that both molecules remain neutral. Their resulting levels of charge transfer were probed using UV-visible, IR spectroscopy and by DFT calculations.     

Ultrafast electron-phonon coupling in hollow gold nanospheres

Electronic energy relaxation in hollow gold nanospheres (HGNs) was studied using femtosecond time-resolved transient absorption spectroscopy. A range of HGNs having outer diameter-to-shell thickness aspect ratios of 3.5 to 9.5 were synthesized by a galvanic replacement method. The HGNs exhibited electron-phonon relaxation times that decreased from 1.18 ± 0.16 to 0.59 ± 0.08 ps as the aspect ratio increased over this range. The corresponding electron-phonon coupling constants, G, ranged from (1.67 ± 0.22) to (3.33 ± 0.45) × 10(16) W m(-3) K(-1). Electron-phonon coupling was also determined for solid gold nanospheres (SGNs) with diameters spanning 20 nm to 83 nm; no size dependence was observed for these structures. The HGNs with high aspect ratios exhibited larger electron-phonon coupling constants than the SGNs, whose average G value was (1.9 ± 0.2) × 10(16) W m(-3) K(-1). By comparison, low-aspect ratio HGNs exhibited values comparable to SGNs. The electron-phonon coupling of high-aspect ratio HGNs was also influenced by the surrounding fluid dielectric; slightly smaller G values were obtained when methanol was the solvent as opposed to water. This coupling enhancement observed for high-aspect ratio HGNs was attributed to the large surface to volume ratio of these structures, which results in non-negligible contributions from the environment.     

GC-MS Analysis of Methadone and EDDP in Addicted Patients under Methadone Substitution Treatment: Comparison of Urine and Plasma as Biological Samples

(1) Background: Methadone, along with buprenorphine, is the most commonly used drug for the treatment of opioid dependence. This study aimed to analyze methadone and its major metabolite, 2-ethylidene-1,5-dimethyl-3,3-diphenyl pyrrolidine (EDDP), in the urine and plasma of opiate addicts. The study group consisted of drug users voluntarily admitted to the detoxification center C.E.T.T.T. “St. Stelian” of Bucharest. Secondly, the study aimed to identify whether urine or plasma provides better results for the proposed method. (2) Methods: A GC-MS method, using an internal standard (diphenylamine) in the FULL-SCAN and SIM modes of operation and using the m/z = 72 ion for methadone and the m/z = 277 ion for EDDP, combined with a liquid–liquid extraction procedure was performed. (3) Results: The applied procedure allows the detection and quantification of methadone in both urine and plasma samples. EDDP was identified in patients with higher levels of methadone. Higher levels of methadone were detected in urine than in plasma samples. (4) Conclusions: This procedure can be used in clinical laboratories for the rapid determination of methadone levels in urine rather than in plasma. The procedure can be applied for the monitoring of methadone substitution treatment.     

Bacterial iron transport: coordination properties of azotobactin, the highly fluorescent siderophore of Azotobacter vinelandii

Azotobacter vinelandii, a nitrogen-fixing soil bacterium, secretes in iron deficiency azotobactin delta, a highly fluorescent pyoverdin-like chromopeptidic hexadentate siderophore. The chromophore, derived from 2,3-diamino-6,7 dihydroxyquinoline, is bound to a peptide chain of 10 amino acids: (L)-Asp-(D)-Ser-(L)-Hse-Gly-(D)-beta-threo-HOAsp-(L)-Ser-(D)-Cit-(L)-Hse-(L)-Hse lactone-(D)-N(delta)-Acetyl, N(delta)-HOOrn. Azotobactin delta has three different iron(III) binding sites which are one hydroxamate group at the C-terminal end of the peptidic chain (N(delta)-Acetyl, N(delta)-HOOrn), one alpha-hydroxycarboxylic function in the middle of the chain (beta-threo-hydroxyaspartic acid), and one catechol group on the chromophore. The coordination properties of its iron(III) and iron(II) complexes were measured by spectrophotometry, potentiometry, and voltammetry after the determination of the acid-base functions of the uncomplexed free siderophore. Strongly negatively charged ferric species were observed at neutral p[H]'s corresponding to a predominant absolute configuration Lambda of the ferric complex in solution as deduced from CD measurements. The presence of an alpha-hydroxycarboxylic chelating group does not decrease the stability of the iron(III) complex when compared to the main trishydroxamate siderophores or to pyoverdins. The value of the redox potential of ferric azotobactin is highly consistent with a reductive step by physiological reductants for the iron release. Formation and dissociation kinetics of the azotobactin delta ferric complex point out that both ends of this long siderophore chain get coordinated to Fe(III) before the middle. The most striking result provided by fluorescence measurements is the lasting quenching of the fluorophore in the course of the protonation of the ferric azotobactin delta complex. Despite the release of the hydroxyacid and of the catechol, the fluorescence remains indeed quenched, when iron(III) is bound only to the hydroxamic acid, suggesting a folded conformation at this stage, around the metal ion, in contrast to the unfolded species observed for other siderophores such as ferrioxamine or pyoverdin PaA.