Polymorphism of Anhydrous Cadmium Iodate Structure of ε‐Cd(IO3)2

The investigation of CdCl₂‐HIO₃ system, in aqueous and HNO₃ solutions, revealed that anhydrous cadmium iodate presents a marked polymorphism. No less than four new Cd(IO₃)₂polymorphs have been isolated and characterized, two of which showing second harmonic generation activity. Single crystals of ε‐Cd(IO₃)₂ are obtained by slowly evaporating, at 60 °C, a saturated solution of γ‐Cd(IO₃)₂ in 30 % nitric acid. This compound crystallizes in the orthorhombic space group Pca2₁ [a = 17.581(2), b = 5.495(2), c = 11.163(2) Å]. The basic structural unit can be described as the connection of two cadmium polyhedrons with a short metal – metal distance of 3.88Å. These units are further linked through two other iodate bridges resulting in layers parallel to the (100) plane. The 3D linkage is ensured by short bonds of the fourth iodate group.     

PHOTOTHERMAL DEFLECTION SPECTROSCOPY OF PHOTOSYNTHETIC PIGMENTS in vivo and in vitro

Abstract— This Technical Note describes the design of a photothermal beam deflection apparatus which allows the easy and rapid measurement of thermal dissipation of absorbed light energy in various photosynthetic materials including whole plant leaves. This system is based on the "mirage effect" in which the refractive index gradient induced in a fluid in contact with the sample, irradiated with an intensity-modulated light, causes the periodic deflection of a laser beam parallel to the sample surface. The deflection of the probe laser beam is detected by a position sensor, the output of which is processed by a lock-in amplifier. Photothermal deflection signals can be monitored in vivo in intact leaves placed in various (liquid or gaseous) environments with a satisfactory signal-to-noise ratio between 100 (in water) and 50 (in air) at low modulation frequencies (ca 30 Hz). It is shown that this new and simple photothermal technique is a very sensitive tool for the measurement of absorption spectra of photosynthetic pigments both in vivo (leaves, algae or chloroplasts) and in model systems (Langmuir-Blodgett and solid films of chlorophyll).     

Semiclassical dynamics of Dirac particles interacting with a static gravitational field

The semiclassical limit for Dirac particles interacting with a static gravitational field is investigated. A Foldy–Wouthuysen transformation which diagonalizes at the semiclassical order the Dirac equation for an arbitrary static spacetime metric is realized. In this representation the Hamiltonian provides for a coupling between spin and gravity through the torsion of the gravitational field. In the specific case of a symmetric gravitational field we retrieve the Hamiltonian previously found by other authors. But our formalism provides for another effect, namely, the spin hall effect, which was not predicted before in this context.     

General Adiabatic Evolution with a Gap Condition

We consider the adiabatic regime of two parameters evolution semigroups generated by linear operators that are analytic in time and satisfy the following gap condition for all times: the spectrum of the generator consists in finitely many isolated eigenvalues of finite algebraic multiplicity, away from the rest of the spectrum. The restriction of the generator to the spectral subspace corresponding to the distinguished eigenvalues is not assumed to be diagonalizable. The presence of eigenilpotents in the spectral decomposition of the generator typically leads to solutions which grow exponentially fast in some inverse power of the adiabaticity parameter, even for real spectrum. In turn, this forbids the evolution to follow all instantaneous eigenprojectors of the generator in the adiabatic limit. Making use of superadiabatic renormalization, we construct a different set of time-dependent projectors, close to the instantaneous eigenprojectors of the generator in the adiabatic limit, and an approximation of the evolution semigroup which intertwines exactly between the values of these projectors at the initial and final times. Hence, the evolution semigroup follows the constructed set of projectors in the adiabatic regime, modulo error terms we control.     

Self‐association in {2‐[3,4‐alkylenedioxy‐5‐(3‐pyridyl)]‐thienyl}alkanols: an NMR,IR, and single‐crystal X‐ray study

syn‐2,2,4,4‐Tetramethyl‐3‐{2‐[3,4‐alkylenedioxy‐5‐(3‐pyridyl)]thienyl}pentan‐3‐ols self‐associate both in the solid state and in solution. Single‐crystal X‐ray diffraction study of the 3,4‐ethylenedioxythiophene (EDOT) derivative shows that it exists as a centrosymmetric head‐to‐tail, syn dimer in the solid state. The IR spectra of the solids display only a broad OH absorption around 3300 cm^?1, corresponding to a hydrogen‐bonded species. ¹H Nuclear Overhauser Effect Spectroscopy (NOESY) NMR experiments in benzene reveal interactions between the tert‐butyl groups and the H2 and H6 protons of the pyridyl group. Two approaches have been used to determine association constants of the EDOT derivative by NMR titration, based on the concentration dependence of (i) the syn/anti ratio and (ii) the OH proton shift of the syn rotamer. Reasonably concordant results are obtained from 298 to 323 K (3.6 and 3.9 M^?1, respectively, at 298 K). Similar values are obtained from the syn OH proton shift variation for the 3,4‐methylenedioxythiophene (MDOT) derivative. Concentration‐dependent variation of the anti OH proton shift in the latter suggests that the anti isomer associates in the form of an open, singly hydrogen‐bonded dimer, with a much smaller association constant than the syn rotamer. Self‐association constants for 3‐pyridyl‐EDOT‐alkanols with smaller substituents vary by a factor of 4 from (i‐Pr)₂ up to (CD₃)₂, while the hetero‐association constants for the same compounds with pyridine vary slightly less. Copyright © 2007 John Wiley & Sons, Ltd.     

Constrained nucleic acids (CNA). Part 2. Synthesis of conformationally restricted dinucleotide units featuring noncanonical alpha/beta/gamma or delta/epsilon/zeta torsion angle combinations

Four dinucleotide building units of nucleic acids in which three out of six backbone torsion angles are included in a dioxaphosphorinane ring structure (D-CNA family) have been synthesized: two diastereoisomeric alpha,beta,gamma-D-CNA {cis and trans} and two diastereoisomeric delta,epsilon,zeta-D-CNA {(S(C4'),R(P)) and (S(C4'),S(P))}. The structural analysis of these conformationally restricted dinucleotides, using NMR spectroscopy and X-ray crystallography, shows that these D-CNA structural elements allow the stabilization of torsion angle combinations, alpha/beta/gamma and delta/epsilon/zeta, that are significantly different from those typically observed in canonical A- or B-form duplexes.     

Regioselective N-functionalization of tetraazacycloalkanes

[reaction: see text] Bisaminal type compounds obtained by condensation of pyruvic aldehyde with the suitable open-chain tetraamine followed by cyclization with either dibromoethane or dibromopropane can be regioselectively quaternized by a wide range of alkylating agents. Removal of the bisaminal bridge yields the monosubstituted tetraazamacrocycle or bismacrocycle. Further functionalization allows the preparation of bifunctional ligands or trisubstituted macrocycles. The structure of six compounds was solved by X-ray diffraction, and the unexpected results are rationalized according to the molecular modeling calculations.     

Calculation of ionization potentials of small molecules: a comparative study of different methods

With the help of various theoretical methods, ionization potentials (IPs) have been computed for a panel of small molecules containing atoms of group 14, 15, or 16 and representing different singly, doubly, or triply bonded systems with or without an interacting heteroatom lone pair. Comparison of experimental IP values to theoretical results indicates that (i) the standard outer valence green function (OVGF), density functional theory (DFT), and DeltaSCF methods lead to rather accurate values, (ii) the CASPT2 method systematically underestimates IPs, (iii) the method of deducing IPs from a shift of some standard DFT eigenvalue spectrum is a straightforward approach leading to rather accurate IPs, (iv) the eigenvalue spectrum obtained with the so-called statistical average of different orbital model potential (SAOP) exchange-correlation model potential is an efficient approach leading directly to quite accurate IPs, and (v) a good prediction of the IP spectrum can be obtained from the shifted excitation spectra of the system calculated by the time-dependent DFT (TD-DFT) method. It is also shown that the TD-DFT calculations of the ionized species bring a significant improvement over the calculations of the neutral molecules, indicating that a great part of the electronic relaxation is already taken into account (in a similar way for all ionizations). Finally, in the case of TD-DFT calculations of neutral molecules, the statistical average of different orbital model potential (SAOP) functional does not lead to significantly better results than the B3LYP functional.     

Synthesis of primary-alkyl selenols and selenides from primary-alkyl thiols involving diphenyl sulfonium salts

Hexyl thiol has been transformed to hexyl selenol and related selenides and selenocyanate by substitution of the corresponding hexyldiphenylsulfonium tetrafluoroborate with selenium nucleophiles.