Conformational transitions of calixphyrin derivatives monitored by temperature-dependent NMR spectroscopy. Ab initio interpretation of the spectra

Eight meso-aryl calixphyrin derivatives were synthesized and their conformational equilibria and transitions studied with temperature-dependent NMR spectroscopy. On the basis of density functional computations, several conformer species could be identified and observed changes in chemical shifts explained. In some compounds, the aryl group rotation and porphyrin ring flipping could be monitored independently, as their NMR coalescence temperatures were well-separated. Calculated relative conformer energies, transition barriers, and isotropic shieldings agree well with the experimental data. In the meso-substituted porhyrins (calixphyrins) the sp3 carbon atoms perturb their pi-electron system and significantly modify the molecular shape and the flexibility. Even when the conjugation of the pi-electron system was destroyed by the nonplanarity, far-range electronic induction effects still exist and influence chemical shielding and molecular geometry. The aryl functional groups moderately modify the structure of the calixphyrin ring and thus can be used for fine-tuning of the mechanical and chemical properties of these compounds.     

Synthesis, nuclear, and magnetic structures and magnetic properties of [Mn3(OH)2(SO4)2(H2O)2

[Mn(3)(OH)(2)(SO(4))(2)(H(2)O)(2)] and its deuterated analogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single-crystal X-ray analysis and Rietveld analysis of neutron powder-diffraction data, consists of a 3D network of chains of edge-sharing Mn(1)O(6), running along the c axis, connected by the apices of Mn(2)O(6) and SO(4) units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long-range ordering (LRO) and short-range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54 degrees towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn(3) trimer, the LRO is achieved by antiparallel alignment of the four symmetry-related trimers within the magnetic unit cell. A spin-flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.     

Synthesis of Bridged Tetrahydrobenzo[b]azepines and Derivatives through an Aza‐Piancatelli Cyclization/Michael Addition Sequence

Herein, we report the preparation of bridged tetrahydrobenzo[b]azepines, which was accomplished through an aza‐Piancatelli cyclization/Michael addition sequence in a one‐pot fashion from readily available precursors. It is noteworthy that a general method to access these scaffolds was hitherto unprecedented. Additionally, the multifaceted aspects of this process have been exemplified through its application to the synthesis of 2‐azabicyclo[3.2.1]octanes and bridged tetrahydrobenzo[b]oxepines, along with post‐derivatizations.     

Organometallic vapor phase epitaxial growth of (AlxGa1-x)0.5In0.5P and its heterostructures

Low pressure organometallic vapor-phase epitaxial growth of Ga_0.5In_0.5P and (Al_xGa_1-x) _0.5In_0.5P is examined. Epitaxial layers of bulk materials are characterized using photoluminescence, electroreflectance, Raman scattering spectroscopy, and surface morphology studies to determine lattice match and optimum growth conditions. Lattice matching at the growth temperature produces featureless growth surfaces, while lattice matching at room temperatures results in minimum photoluminescence linewidth but cracked surfaces due to tensile strain during growth. Raman scattering spectra of the quaternary reveal a three mode structure, with spectral peaks due to GaP-like, InP-like, and AIP-like LO phonons. Heterostructures are investigated including quantum shifts from a series of superlattices. These materials are incorporated in double-heterostructure lasers and single-quantum-well laser with graded-index separate confinement heterostructure     

Analyse de la stabilité spectrale d’un laser DFB à trois sauts de phase (3PS-DFB)

The aim of this article is to analyze the spectral stability of the three phase shift distributed feedback (3ps-dfb) laser by using Time domain model (tdm). We have developed a software that simulates static and dynamic properties of distributed feedback (dfb) multi-sections laser at large signal. The best single-mode stability operation up to 18mW of the 3ps-dfb is achieved for three phase shifts at (π, π, π) whatever the phase position. These results showed that the 3ps-dfb laser was a much more suitable structure to realize stable single-mode high-power operation for a coherent optical communication system.     

Spectroscopic detection of DNA quadruplexes by vibrational circular dichroism

The four-stranded G-quadruplex motif is a conformation frequently adopted by guanine-rich nucleic acids that plays an important role in biology, medicine, and nanotechnology. Although vibrational spectroscopy has been widely used to investigate nucleic acid structure, association of particular spectral features with the quadruplex structure has to date been ambiguous. In this work, experimental IR absorption and vibrational circular dichroism (VCD) spectra of the model quadruplex systems d(G)(8) and deoxyguanosine-5'-monophosphate (5'-dGMP) were analyzed using molecular dynamics (MD) and quantum-chemical modeling. The experimental spectra were unambiguously assigned to the quadruplex DNA arrangement, and several IR and VCD bands related to this structural motif were determined. Involvement of MD in the modeling was essential for realistic simulation of the spectra. The VCD signal was found to be more sensitive to dynamical structural variations than the IR signal. The combination of the spectroscopic techniques with multiscale simulations provides extended information about nucleic acid conformations and their dynamics.     

Electron-beam poling in undoped, N- or Ge-doped MDECR H:SiO2 films

Amorphous N- or Ge-doped H:SiO₂ films deposited on silica by the matrix distributed electron cyclotron resonance-PECVD method were irradiated by an electron-beam with different doses in order to pole the material and induce second harmonic generation (SHG). SHG was measured using the Maker-fringe method. When irradiated at an acceleration voltage of 25 kV, an incident current of 5 nA during 480 s, the N-doped H:SiO₂ films exhibited a maximum second harmonic signal in the order of 0.003 pm/V, but when irradiated with an acceleration voltage of 30 kV, at 5 nA during 240 s, the films exhibited a maximum second harmonic signal of 0.006 pm/V. With a smaller current of 0.5 nA during 25 s and 25 kV acceleration voltage, the Ge-doped H:SiO₂ films (3.8 at. % Ge) showed a maximum second-order nonlinearity of 0.0005 pm/V. But an H:SiO₂ films with a smaller Ge content (1.0 at. % Ge), showed a large SHG: d₃₃=0.09 pm/V when irradiated at 25 kV, 0.5 nA during 15 s. PACS 78.66.J; 42.65.K; 68.60.D     

1.3 /spl mu/m InGaAsN vertical cavity surface emitting lasers grown by MOCVD

The first InGaAsN VCSELs grown by MOCVD with CW lasing wavelength longer than 1.3 /spl mu/m are reported. The devices were of conventional p-i-n structure with doped DBR mirrors. CW lasing up to 65/spl deg/C was observed, with a maximum output power at room temperature of 0.8 mW for multimode devices and nearly 0.3 mW for single-mode devices.