Enantiospecific first total synthesis of (-)-4-thiocyanatoneopupukeanane

The first total synthesis of (-)-4-thiocyanatoneopupukeanane starting from (R)-carvone has been achieved, establishing the relative as well as absolute structure of the natural product.

First donor-acceptor interaction promoted gelation of organic fluids

In recent years there has been considerable interest in developing new types of gelators of organic solvents.1 Despite the recent advances, a priori design of a gelator for gelling a given solvent has remained a challenging task. Various noncovalent interactions like hydrogen-bonding,2 metal coordination3 etc. have been used as the driving force for the gelation process. A special class of cholesterol-based gelators were reported by Weiss,4 and by Shinkai.5 Gels derived from these molecules have been used for chiral recognition/sensing,6 for studying photo- and metal-responsive functions,7 and as templates to make hollow fiber silica.8 Other types of organogels have been used for designing polymerized 9 and reverse aerogels,10 and in molecular imprinting.11 Hanabusa’s group has recently reported organogels with a bile acid derivative.12 This has prompted us to disclose our results on a novel electron donor–acceptor (EDA) interaction mediated two-component13 gelator system based on the bile acid14 backbone.

First principles study of magnetism in divalent Eu perovskites

A comparative first principles study has been carried out for EuLiH3 (ELH) and EuTiO3 (ETO) using the generalized gradient approximation +U approach. While ELH exhibits ferromagnetic ground state for all volumes, the magnetic ground state of ETO has the tendency to switch from G-type antiferromagnetic to a ferromagnetic state with change in volume. The marked difference in magnetic behavior and magnitude of the nearest neighbors exchange interaction of both the compounds are shown to be related to the difference in their respective electronic structure near the Fermi level. The Ti 3d states are shown to play predominant role in weakening the strength of the exchange interaction in ETO.

The first observation of a Na2TiS2 related structure in a 2-D anionic manganese trimesate intercalated by cationic imidazole

A hydrothermal reaction of Mn(OAc)2·4H2O, trimesic acid, imidazole, KOH and water at 75 °C for 24 h gave rise to a 2-D compound, [HImd][Mn(BTC)(H2O)] (Imd = imidazole; BTC = trimesate), with protonated imidazole molecules occupying the inter-lamellar space, and the structure resembles the classic inorganic compound, the sodium intercalated TiS2 (Na2TiS2).

Quantum first-passage problem

Formulation of quantum first passage problem is attempted in terms of a restricted Feynman path integral that simulates an absorbing barrier as in the corresponding classical case. The positivity of the resulting probability density, however, remains to be demonstrated.

First hyperpolarizability of bacteriorhodopsin, retinal and related molecules revisited

The previously reported beta values of BR and retinal based chromophores were very high but subsequent measurements found them to be much less. We have found that the beta values of these compounds do not vary so much with experimental conditions as with the method of analysis. Hyper-Rayleigh scattering measurements at 1543 and 1907 nm produce more realistic beta values close to the intrinsic (static) hyperpolarizability, beta(0) which for BR is still very high (275 x 10 (30) esu). The optical nonlinearity of BR arises entirely due to the protonated retinal Schiff Base (PRSB) which in its isolated form has the same intrinsic hyperpolarizability as that of the rotein.

X-ray absorption spectra of niobium dichalcogenides and their first-row transition-metal intercalates

X-ra!. K-absorption spectra of niobium in niobium dichalcogenides. namely NbS, and NbSe, and their first-row transition-metal intercalates Mi P 3N bSz (M = Cr. Mn. Fe. Co. Ni) and Ml#,NbSe2 (M = Fe. CO). have been measured together with those in niobium metal. The spectra of these materials are \er? similar to one another. They reflect the transitions to the partially filled niobium d band with some p character. A bariety of x-ray absorption nearedge structures (XASES) associated with the K edges of intercalated atoms are also presented and discussed.

Testing approximate theories of first-order phase transitions on the two-dimensional Potts model

The two-dimensional,q-state (q>4) Potts model is used as a testing ground for approximate theories of first-order phase transitions. In particular, the predictions of a theory analogous to the Ramakrishnan-Yussouff theory of freezing are compared with those of ordinary mean-field (Curie-Wiess) theory. It is found that the Curie-Weiss theory is a better approximation than the Ramakrishnan-Yussouff theory, even though the former neglects all fluctuations. It is shown that the Ramakrishnan-Yussouff theory overestimates the effects of fluctuations in this system. The reasons behind the failure of the Ramakrishnan-Yussouff approximation and the suitability of using the two-dimensional Potts model as a testing ground for these theories are discussed.

Size dependence and dispersion behavior of the first hyperpolarizability of copper nanoparticles

We have probed the size dependency of the first hyperpolarizability (b) of copper nanoparticles by hyper-Rayleigh scattering (HRS). Our results indicate that second harmonic generation (SHG) originates predominantly at the surface of the nanoparticles as long as the size (d) remains small compared to the wavelength (k). However, volume contribution to the SH response due to the retardation effect becomes important when particle size grows beyond the `small particle limit'. There is a significant dispersion in the b values of copper nanoparticles owing tothe presence of the strong surface plasmon resonance (SPR) band.

An investigation of bond formation in the weakly bound first excited 1Σ and lowest 3Σ states of HeH+

The role of the electronic kinetic energy and its Cartesian components is examined during the formation of the first excited 1�£ and the lowest 3�£ states of HeH+ employing wavefunctions of multi-configuration type with basis orbitals in elliptic coordinates. Results show that the bond formation in these states is preceded primarily by a charge transfer from H to He+ rather than by polarisation of the H-orbital by He+

Pressure-induced first-order transition in layered crystalline semiconductor GeSe to a metallic phase

The electrical resistivity of layerd crystalline GeSe has been investigated up to a pressure of 100 kbar and down to liquid-nitrogen temperature by use of a Bridgman anvil device. A pressure-induced first-order phase transition has been observed in single-crystal GeSe near 6 GPa. The high-pressure phase is found to be quenchable and an x-ray diffraction study of the quenched material reveals that it has the face-centered-cubic structure. Resistivity measurements as a function of pressure and temperature suggest that the high-pressure phase is metallic.

Realization of first order optical systems using thin lensest

A first order optical system is investigated in full generality within the context of wave optics. The problem is reduced to a study of the ray transfer matrices. The simplest such systems correspond to axially symmetric propagation. Realization of such systems by centrally located lenses separated by finite distances is studied. It is shown that, contrary to the commonly held view, the set of first order systems that can be realized using axially symmetric thin lenses exhausts the entire SL(2, R) group; at most three lenses are needed to realize any element of this group. In particular, the inverse of free propagation can be so realized. Among anisotropic systems it is again shown that every element of the lens group Sp(4, R) can be realized using a finite number of thin lenses.

Study of Structural Stability and Electronic Structure of Nonstoichiometric CdS Nano Clusters from First Principles

Structural stability of small sized nonstoichiometric CdS nano clusters between zincblende and wurtzite structures has been investigated using first-principles density functional calculations. Our study shows that the relative stability of these two structures depends sensitively on whether the surface is S-terminated or Cd-terminated. The associated band gap also exhibits non-monotonic behavior as a function of cluster size. Our findings may shed light on contradictory reports of experimentally observed structures of CdS nano clusters found in the literature.

Townsend's First Ionization Coefficients and Sparking Potentials in Crossed Electric and Magnetic Fields

Townsend's first ionization coefficients have been measured in corssed electric and magnetic fields for values of B/p ranging from 0.013 TESLA. TORR-1 to 0.064 TESLA.TORR-1 and for 103 x 102¿ E/p 331 x 102 V.M-1. TORR-1 in oxygen and for 122 x 102¿ E/pÂ488 x 102 V.M-1.TORR-1 for dry air. The values of effective collision frequencies determined from the equivalent pressure (pe) concept generally increase with E/p at constant B/p and decrease with increasing B/p at constant E/p. Effective collision frequencies determined from measured sparking potentials at high values of E/p increase with decreasing E/pe. The drift velocity and mean energy of electrons in oxygen in crossed electric and magnetic fields have been derived.