A Novel Chiral Auxiliary for Enantioselective Synthesis of Tertiary Alcohol

The use of 1-menthyl ester of 1,3-dithiane-2-carboxylic acid as a chiral auxilary for the conversion of acetophenone, propiophenone and butyrophenone to the corresponding optically active tertiary alcohols 2-phenylhexan-2-ol, 3-phenylheptan-3-ol and 4-phenyloctan-4-ol, has been demonstrated.     

Total synthesis of asimicin and bullatacin

The efficient total synthesis of asimicin, 1, and bullatacin, 2, has demonstrated the advantages of three different strategies for the synthesis of the tricyclic intermediates 6 and 7, which represent the key fragment of the bis-THF Annonaceous acetogenins. The naked carbon skeleton strategy is based on the production of all asymmetric centers by selective placement of the oxygen functions onto an unsaturated, nonfunctionalized carbon skeleton. Diversity in this approach arises from the relative timing of highly stereoselective reactions, such as the Sharpless asymmetric dihydroxylation (AD) reaction, the Kennedy oxidative cyclization (OC) with rhenium(VII) oxide, the Mitsunobu-type alcohol epimerization reaction, and the Williamson etherification reaction. The convergent strategy, which is based on the combinatorial coupling of two series of diastereomeric fragments, to produce intermediates such as 11 and 12, enjoys the advantages of both efficiency and versatility. The third approach, which is based on partially functionalized intermediates, such as 13, combines the advantages of both the linear and the convergent strategies-synthetic efficiency and diversity.     

Phase separation in asymmetrical fermion superfluids

Motivated by recent developments on cold atom traps and high density QCD we consider fermionic systems composed of two particle species with different densities. We argue that a mixed phase composed of normal and superfluid components is the energetically favored ground state. We suggest how this phase separation can be used as a probe of fermion superfluidity in atomic traps.     

Coupling of spontaneous emission from GaN-AlN quantum dots into silver surface plasmons

We have demonstrated the decay of spontaneous emission (SE) from AlN-GaN quantum dots (QDs) into silver surface plasmon (SP) modes in the ultraviolet at approximately 375-380 nm. Using time-resolved photoluminescence (PL), we show that the electron-hole recombination rate in AlN-GaN QDs is enhanced when SE is resonantly coupled to a metal SP mode, corresponding to the dip in the continuous-wave PL spectrum. Exciton recombination by means of silver SP modes is as much as 3-7 times faster than in normal QD SE and depends strongly on emission wavelength and thickness of the silver.     

High-energy and high-peak-power nanosecond pulse generation with beam quality control in 200-microm core highly multimode Yb-doped fiber amplifiers

We explored high-energy and high-peak-power pulse generation in large-core multimode fiber amplifiers, achieving what is to our knowledge the highest reported energies, up to 82 mJ for 500-ns pulses, 27 mJ for 50-ns pulses, and 2.4-MW peak power for 4-ns pulses at 1064 nm, using 200-microm-diameter and 0.062-N.A. core Yb-doped double-clad fiber amplifiers. The highly multimode nature of the fiber core was mitigated by use of a coiling-induced mode-filtering effect to yield a significant improvement in output-beam quality from M2 = 25 from an uncoiled fiber to M2 = 6.5 from a properly coiled fiber, with the corresponding reduction in number of propagating transverse modes from > or = 200 to < or = 20.     

Studies in nickel(IV) chemistry. Part 6. Kinetics of electron transfer from phenylhydrazine to tris-(dimethylglyoximato) nickelate(IV) in aqueous medium

The kinetics of electron transfer from phenylhydrazine(S) to tris-(dimethylglyoximato) nickelate(IV), Ni(dmg) (dmg^2? = dimethylglyoximate dianion), have been studied in aqueous medium in the range of 6.21 ? pH ? 12.2. The kinetics exhibit a pseudo-first-order disappearance of Ni(dmg) when excess S is present. The pseudo-first-order rate constants k_obs are almost linearly dependent on [S]₀ for varying concentrations of the reductant. At constant [S]₀, the k_obs?pH profile is U shaped. The k_obs values register a decrease as the [H⁺] is increased in the pH range of ∽12.2–9.5, remain almost constant (minimum) in the range of ∽9–8, and then again linearly increase as [H⁺] is increased in the pH range of ∽7–6.21. Results are interpreted in terms of a probable mechanism involving outer-sphere electron transfer from the phenylhydrazine and phenylhydrazinium cation species to the unprotonated and one-protonated species of the Ni(IV) complex. The reduction rate appears to be dependent on the nature of the species (unprotonated and one-protonated) of the oxidant Ni(IV) complex. The phenylhydrazinium cation reduces the Ni(IV) complex at least one order of magnitude faster than does the neutral reductant species. The major product of the oxidation of phenylhydrazine by the Ni(IV) complex is 4-hydroxyazobenzene with a small amount of phenol.     

Studies in nickel(IV) chemistry. Kinetics of the Cu(II) ion-mediated acid decomposition of tris(dimethylglyoximato) nickelate(IV) in aqueous acidic medium

Kinetics of the Cu(II) ion-mediated acid decomposition of tris (dimethylglyoximato)nickelate(IV), Ni(dmg)₃^2? (dmg^2? = dimethylglyoximate dianion), are reported in aqueous medium in the range of 3.6 ? pH ? 6.6 at 35°C and μ = 0.57 M. The pseudo-first-order rate constants of the disappearance of Ni(IV) k_obs(M) satisfy the equation where k_ad refers to the pseudo-first-order rate constants for the proton-assisted decomposition of the Ni(IV) complex determined independently and is a function of [H⁺], and k_dec(M) to that for the Cu(II) ion-mediated route and is a function of [H⁺] and [Cu²⁺]. Both k_obs(M) and k_dec(M) are found to increase with increasing [Cu(II)]₀, tending to attain limiting values at higher relative [Cu(II)]₀. At low [Cu(II)]₀ the k_dec(M) is found to register a decrease with increasing pH in the pH range of 3.6–4.4, then an increase in the range of 4.4–5.76, and again a decrease in the range of 5.76–6.6. Results on the Cu(II) ion-mediated acid decomposition are interpreted in terms of a probable mechanism involving pH-dependent adduct formation equilibria involving the one-protonated and the two-protonated species of Ni(IV) and the various species of Cu(II) ion in the media, followed by rate-determining acid decomposition of the adduct(s) to give Ni(II) aq. and Cu(dmgH)₂. While the two-protonated Ni(IV) complex apparently reacts about five orders of magnitude faster than the one-protonated species, the aquacopper(II) reacts about two orders of magnitude slower than the hydroxoaquacopper(II).     

Stable drop shapes under disjoining pressure. I. A hierarchical approach and application

The contact line region as affected by the disjoining pressure has been analyzed under the assumption that it can sustain only two types of profiles. Disjoining pressure represents the extra potential in thin films that always exists in the contact angle region where a liquid drop or a wedge thins to meet the solid substrate and in turn affects the contact angle as well as the film profile. It is shown here that the integration of the augmented Young-Laplace equation to yield the above types of drop profiles under the action of disjoining pressure leads to the usual conditions of equilibrium as well as the condition of stability in the same analysis. Other inequality constraints are obtained where the stability condition does not apply. The fact that stability condition coexists with the conditions of equilibrium is pursued to show in one case that the stability modifies half of the predicted outcomes in the drop shapes. In addition, exceptions to the rule are found, which are physically meaningful, and a scale-dependent equilibrium is reported for the first time.     

Structural,spectroscopic aspects,and electronic properties of (TiO2)n clusters: A study based on the use of natural algorithms in association with quantum chemical methods

In this article, we propose a stochastic search‐based method, namely genetic algorithm (GA) and simulated annealing (SA) in conjunction with density functional theory (DFT) to evaluate global and local minimum structures of (TiO₂)_n clusters with n = 1–12. Once the structures are established, we evaluate the infrared spectroscopic modes, cluster formation energy, vertical excitation energy, vertical ionization potential, vertical electron affinity, highest occupied molecular orbital (HOMO)‐lowest unoccupied molecular orbital (LUMO) gaps, and so forth. We show that an initial determination of structure using stochastic techniques (GA/SA), also popularly known as natural algorithms as their working principle mimics certain natural processes, and following it up with density functional calculations lead to high‐quality structures for these systems. We have shown that the clusters tend to form three‐dimensional networks. We compare our results with the available experimental and theoretical results. The results obtained from SA/GA‐DFT technique agree well with available theoretical and experimental data of literature. © 2013 Wiley Periodicals, Inc.     

Broad band light emission from Ag-ion implanted silicon nanocrystals

Silicon nanoparticles formed using low energy (<50 keV) silver ion implantation in crystalline Si exhibit broad band light emission from ultraviolet (UV) to green. The formation of nanoparticles is confirmed using high resolution electron microscopy (HRTEM) and the resulting microscopy is used to obtain the size distribution of Si nanoparticles. Photoluminescence (PL) spectra were observed in the range of the UV to the green. The origin of emission is most likely from highly localized defects at the Si/SiO2 which is further confirmed from Photoluminescence Excitation (PLE) and effective mass theory estimation.