Bidimensional near-field sampling spectrometry

We report on a concept of compact optical Fourier-transform spectrometer based on bidimensional (2D) spatial sampling of a confined interferogram. The spectrometer consists of a nanostructured glass surface on which two light beams interfere in total internal reflection. Subwavelength spatial sampling of the interferogram near field is achieved by introducing a tilt angle between a 2D array of optical nanoantennas and the interferogram pattern. The intensity distribution of the scattered light is recorded on a 2D CCD camera, and a one-dimensional Fourier transform of the interferogram is used to recover the input light spectrum. Experimental results show a wide spectral bandwidth in the visible range, down to 380 nm, with spectral resolution of 1.6 nm around 780 nm.     

Effects of ions clustering in Nd3+/Al3+-codoped double-clad fiber laser operating near 930 nm

We report experimental and theoretical investigations on the presence and the detrimental effect of neodymium clusters on the three-level transition at near 930 nm in aluminosilicate double-clad fibers. A series of fibers with a W-type refractive index core profile to filter out the competing strong transition at 1060 nm were fabricated to study the impact of clusters on laser efficiency at near 930 nm using different core compositions. Percentage of clustered Nd ions have been evaluated using two methods based either on the saturation of the pump absorption or on laser efficiencies. Laser characterizations and numerical modeling have shown that clustering effect has a strong impact on the laser efficiency at 930 nm and fractions of clustered ions higher than 50% have been found in the most doped fiber.     

Synthesis, Characterization and Electrochemical Behavior of CoII, NiII and CdII Complexes with N2O2 Donor Ligands Derived from 4,4′-Diaminobiphenyl and?2-Hydroxybenzaldehyde or?2,4-Dihydroxybenzaldehyde

The condensation of 2-hydroxybenzaldehyde or 2,4-dihydroxybenzaldehyde with 4,4′-diaminobiphenyl in absolute EtOH in a molar ratio 2:1 gave, respectively, the Schiff base ligands H₂L1 or H₂L2. The bases served as tetradentate ligands to coordinate Co^II, Ni^II and Cd^II chlorides, leading to complexes where the metal:ligand ratio is 2:1. All of the compounds were characterized by elemental analysis, infrared, electronic and mass spectroscopy, ¹H-n.m.r. and d.s.c. The cyclic voltammograms of the ligands and their complexes in DMF are discussed.     

NIR lanthanide luminescence by energy transfer from appended terpyridine-boradiazaindacene dyes

Mononuclear trivalent lanthanide complexes with formula [Ln(L)(NO(3))(3)] [in which L=4,4-difluoro-8-(2':2';6':2'-terpyridin-4'-yl)-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (Boditerpy)] are reported for Ln=Yb, Nd, Er, La and Gd. According to the crystal structure of the Yb complex, the lanthanide ion is bound to the terdentate terpyridine and the inner coordination sphere of the nine-coordinate lanthanide ion is completed by three bidentate nitrate anions. The coordination polyhedron can be described as a distorted tricapped antiprism. The terpyridine chelate is almost planar and tilted by nearly 60 degrees from the indacene subunit. FT-IR spectra confirm the bidentate binding mode of the nitrate anions for the other complexes. NMR and ES-MS spectra (through characteristic isotopic patterns) confirm the chemical formulation. The complexes have high molar absorption coefficients in the visible spectral region (65,000 M(-1) cm(-1) at 529 nm) and display sizeable NIR luminescence (900 to 1600 nm, for Ln=Yb, Nd and Er), upon irradiation through the electronic state of the indacene moiety at 514 nm. Crystal-field splitting was analysed at low temperature. The quantum yield of the Yb solution (10(-4) M) in dichloromethane amounts to 0.31 %, corresponding to a sensitisation efficacy of the ligand of ca. 63 %.     

Toward a reversible isolation of a C20 fullerene inside a tetraureacalix[4]arene dimer. A theoretical study

The potential stabilization of normally unstable C20, the smallest fullerene, via its encapsulation inside a tetraureacalix[4]arene dimer has been analyzed using molecular mechanics calculations with different force fields, the self-consistent-charge density-functional tight-binding with dispersion correction (SCC-DFTB-D) model, and standard density-functional-theory (DFT) calculations. The interaction energies obtained for the C20 complex have been compared with analogous values calculated for numerous complexes of the tetraureacalix[4]arene dimer with other guests. Results of the calculations with all force fields and SCC-DFTB-D predict that the binding of C20 occurs with the highest selectivity. On the other hand, standard DFT calculations fail to correctly describe the stabilization of the complexes under study as standard DFT generally does not treat dispersion interactions properly. Predicted relative stabilities of the complexes are discussed in conjunction with available experimental data. Molecular dynamics simulations reveal the instability of the guest-free capsular dimer, which decomposes on a 1-ns time scale, while dimeric complexes with guests remained intact during the 5-ns simulation time, indicating the guest-driven formation of the molecular capsule.     

Mimicking helical antibacterial peptides with nonpeptidic folding oligomers

Unnatural oligomeric scaffolds designed to adopt defined secondary structures (e.g., helices), while retaining the chemical diversity of amino acid side chains, are of practical value to elaborate functional mimetics of bioactive alpha-polypeptides. Enantiopure N,N'-linked oligoureas as short as seven residues long have been previously shown to fold into a stable helical structure, stabilized by 12- and 14-membered H-bonded rings. We now report that eight-residue oligoureas designed to mimic globally amphiphilic alpha-helical host-defense peptides are effective against both gram-negative and gram-positive bacteria (including methicillin-resistant Staphylococcus aureus [MRSA]) and exhibit selectivity for bacterial versus mammalian cells. Circular dichroism (CD) spectroscopy studies suggest enhanced helical propensity of oligoureas in the presence of phospholipid vesicles. The utility of this new class of nonpeptidic foldamers for biological applications is highlighted by high resistance to proteolytic degradation.     

New tetrazine-based fluoroelectrochromic window; modulation of the fluorescence through applied potential

A new electrofluorescent switch was prepared with an electroactive fluorescent tetrazine blend of polymer electrolyte; the cells contain four layers: the tetrazine polymer film, a photocured polymer electrolyte film, and two indium-tin oxide plates as the two contact electrodes.     

Lifts of - and -morphisms to -morphisms

Let be the Hochschild complex of cochains on and let be the space of multivector fields on . In this paper we prove that given any -structure (i.e. Gerstenhaber algebra up to homotopy structure) on , and any -morphism (i.e. morphism of a commutative, associative algebra up to homotopy) between and , there exists a -morphism between and that restricts to . We also show that any -morphism (i.e. morphism of a Lie algebra up to homotopy), in particular the one constructed by Kontsevich, can be deformed into a -morphism, using Tamarkin's method for any -structure on . We also show that any two of such -morphisms are homotopic.

     

Revisiting the reactivity of oximate alpha-nucleophiles with electrophilic phosphorus centers. Relevance to detoxification of sarin, soman and DFP under mild conditions

Following a potentiometric determination of the relevant pKa values of the (R1R2)C=NOH functionality, the second order rate constants (k(Ox)) for reaction of a large set of oximate bases with two model organophosphorus esters, i.e. bis-(4-nitrophenyl)phenylphosphonate (BNPPP) and bis-(4-nitrophenyl)methylphosphonate (BNPMP), and three toxic compounds, i.e., sarin (GB), soman (GD) and diisopropylphosphorofluoridate (DFP), in aqueous as well as a 30 : 70 (v/v) H2O-Me2SO mixture have been measured. The corresponding Br?nsted-type nucleophilicity plots of log k(Ox)vs. pKa(Ox) reveal a clear tendency of the reactivity of the oximates to suffer a saturation effect with increasing basicity in aqueous solution. In the case of BNPMP and the three toxic esters, this behaviour is reflected in a levelling off at pKa approximately 9 but a more dramatic situation prevails in the BNPPP system where the attainment of maximum reactivity at pKa approximately 9 is followed by a clear decrease in rate at higher pKa's. Interestingly, a number of data reported previously by different authors for the sarin, soman and DFP systems are found to conform rather well to the curvilinear Br?nsted correlations built with our data. Based on this and previous results obtained for reactions at carbon centers, it can be concluded that the observed saturation effect is the reflection of an intrinsic property of the oximate functionality. An explanation of this behavior in terms of an especially strong requirement for desolvation of the oximates prior to nucleophilic attack which becomes more and more difficult with increasing basicity is suggested. This proposal is supported by the observed changes in pKa(Ox) and k(Ox) brought about by a transfer from H2O to a 30 : 70 H2O-Me2SO mixture. The implications of the saturation effect on the efficiency of oximates as nucleophilic catalysts for smooth decontamination are emphasized. Also discussed is the effect of basicity on the exalted (alpha-effect) reactivity of these bases.