A simple route to enantiopure bis-lactones: synthesis of both enantiomers of epi-nor-canadensolide, nor-canadensolide, and canadensolide

A simple strategy has been developed for the synthesis of both enantiomers of nor-canadensolide, epi-nor-canadensolide, and an intermediate to canadensolide. An orthoester Claisen rearrangement of an appropriately constructed allyl alcohol derivative prepared from R-(+)-2,3-di-O-cyclohexylidine glyceraldehyde followed by epoxidation of the resulting unsaturated esters produced hydroxy-lactones, which on oxidation gave keto-lactones. Stereoselective reduction of the keto-carbonyl using either a chelation controlled or a non-chelation controlled process led to the natural or the epi-series, respectively. The interplay of the electronic effect between the polar groups and the steric effect of the β-substituent during reduction of the keto-lactones turned out to be the key factors in deciding the stereochemical outcome. Regeneration of the aldehyde functionality latent in the ketal moiety of the hydroxy-lactones provided the lactols, which on oxidation gave the bis-lactones.     

Dielectric relaxation,ac and dc conductivities in the fullerenes C60 and C70

The complex conductivity in polycrystalline C₆₀ and C₇₀ has been investigated for frequencies 20 Hz≤ν≤10⁶ Hz and temperatures 10 K≤T≤750 K. The high-frequency dielectric constants ε_α= 2.6±0.1(C₆₀) and ε_∞= 4.6±0.1 (C₇₀) were deduced from these experiments. The observed low temperature relaxation process in C₆₀ fits well into the relaxation dynamics of the C₆₀ molecules as determined by many other experimental techniques operating on very different time scales. In addition to the study of the dipolar relaxation process, the dc and ac conductivities were determined. From the temperature dependence of the dc conductivities energy barriers of E_G=1.75±0.1 eV (C₆₀) and E_G=1.7±0.1 eV (C₇₀) were estimated. In C₇₀ we found indications for small polaron tunneling.     

Theoretical study of the effective electron mass in ternary chalcopyrite semiconductors in the presence of crossed electric and magnetic fields

An attempt is made to investigate theoretically the effective electron mass in ternary chalcopyrite semiconductors at low temperatures on the basis of a newly derived dispersion relation of the conduction electrons under cross fields for the more generalized case which occurs from the consideration of the various types of anisotropies in the energy spectrum. It is found, taking degeneraten-CdGeAs₂ as an example, that the effective electron mass at the Fermi level along the direction of magnetic quantization depends on both the Fermi energy and the magnetic quantum number due to the combined influence of the crystal field splitting parameter and the anisotropic spin-orbit splitting parameter respectively, resulting in different effective masses at the Fermi level corresponding to different magnetic sub-bands. It is also observed that the same mass at the Fermi level in the direction normal to both magnetic and electric fields also varies both with Fermi energy and magnetic sub-band index, and the characteristic feature of cross-fields is to introduce the index-dependent oscillatory mass anisotropy. The theoretical results are in good agreement with the experimental observations as reported elsewhere.     

超导纳米线单光子探测器件的制备

超导纳米线单光子探测器件(SNSPD)是超导单光子探测系统的核心器件。文中介绍了成功制备的基于5nm厚的NbN超导超薄薄膜的SNSPD器件。器件核心结构为150nm宽的纳米曲折线结构,纳米线条占空比为75%,面积为20μm×20μm。超导纳米线是利用电子束曝光(EBL)技术和反应离子刻蚀(RIE)等工艺技术制备的。所制备的SNSPD样品,在温度3.5K下的临界电流约12.9μA;在1310nm波长光波辐照,12.5μA的偏置电流下,探测效率约0.016%。     

Twisting dynamics in the excited singlet state of Michler's ketone

Ultrafast relaxation dynamics of the excited singlet (S(1)) state of Michler's ketone (MK) has been investigated in different kinds of solvents using a time-resolved absorption spectroscopic technique with 120 fs time resolution. This technique reveals that conversion of the locally excited (LE) state to the twisted intramolecular charge transfer (TICT) state because of twisting of the N,N-dimethylanilino groups with respect to the central carbonyl group is the major relaxation process responsible for the multi-exponential and probe-wavelength-dependent transient absorption dynamics of the S1 state of MK, but solvation dynamics does not have a significant role in this process. Theoretical optimization of the ground-state geometry of MK shows that the dimethylanilino groups attached to the central carbonyl group are at a dihedral angle of about 51 degrees with respect to each other because of steric interaction between the phenyl rings. Following photoexcitation of MK to its S1 state, two kinds of twisting motions have been resolved. Immediately after photoexcitation, an ultrafast "anti-twisting" motion of the dimethylanilino groups brings back the pretwisted molecule to a near-planar geometry with high mesomeric interaction and intramolecular charge transfer (ICT) character. This motion is observed in all kinds of solvents. Additionally, in solvents of large polarity, the dimethylamino groups undergo further twisting to about 90 degrees with respect to the phenyl ring, to which it is attached, leading to the conversion of the ICT state to the TICT state. Similar characteristics of the absorption spectra of the TICT state and the anion radical of MK establish the nearly pure electron transfer (ET) character of the TICT state. In aprotic solvents, because of the steep slope of the potential energy surface near the Franck-Condon (FC) or LE state region, the LE state is nearly nonemissive at room temperature and fluorescence emission is observed from only the ICT and TICT states. Alternatively, in protic solvents, because of an intermolecular hydrogen-bonding interaction between MK and the solvent, the LE region is more flat and stimulated emission from this state is also observed. However, a stronger hydrogen-bonding interaction between the TICT state and the solvent as well as the closeness between the two potential energy surfaces due to the TICT and the ground states cause the nonradiative coupling between these states to be very effective and, hence, cause the TICT state to be weakly emissive. The multi-exponentiality and strong wavelength-dependence of the kinetics of the relaxation process taking place in the S1 state of MK have arisen for several reasons, such as strong overlapping of transient absorption and stimulated emission spectra of the LE, ICT, and TICT states, which are formed consecutively following photoexcitation of the molecule, as well as the fact that different probe wavelengths monitor different regions of the potential energy surface representing the twisting motion of the excited molecule.     

Nucleation efficiency of R134a as a sensitive liquid for superheated drop emulsion detector

Superheated emulsion detector is known to detect neutrons, γ-rays and other charged particles. The present work includes the study of nucleation efficiency of superheated drops of one of the CFC-free liquids, R134a (C₂H₂F₄), to fast neutrons, its response to γ-rays from ²⁴¹Am and ¹³⁷Cs and compare its nucleation efficiency with that of R12. The observation indicates that because of the presence of hydrogen, the nucleation efficiency is less in R134a than in R12 in the present neutron energy range of consideration. R134a is one of the most environment-friendly, commercially available liquid that is suitable for superheated drop detector, specially in neutron dosimetry and one needs to investigate it in detail.     

Design of medium energy beam transport line between the RFQ and the Linac in the radioactive ion beam facility at VECC,Kolkata

The design of a medium energy beam transport (MEBT) line comprising of a re-buncher and four quadrupoles, two upstream and the other two downstream of the re-buncher, has been presented. The design was done to ensure almost 100% transport of heavy-ion beams of about 99 keV/u energy from RFQ having a q/A not less than 1/14 through the re-buncher and then through IH Linac of about 0.6 m length in which beam would be accelerated to about 185 keV/u. The re-buncher has been designed to operate at 37.8 MHz, the resonating frequency of both the RFQ and the IH Linac. The entire beam line has been installed and recently O⁵⁺ beam from RFQ has been transported through the re-buncher and subsequently accelerated in the IH Linac successfully.     

On decompositions of semirings via <Emphasis Type="Italic">k</Emphasis>-radicals of some relations

We generalize the notion of k-radical of Green’s \({\overline{\mathcal{J}}}\)-relation, study the decompositions of semirings and investigate the semirings on which the powers and transitive closures of k-radicals are distributive lattice congruences.     

Problems on matchings and independent sets of a graph

Let $G$ be a finite simple graph. For $X?V\left(G\right)$, the difference of $X$, $d\left(X\right)?\left|X\right|?\left|N\left(X\right)\right|$ where $N\left(X\right)$ is the neighborhood of $X$ and $max\{d\left(X\right):X?V\left(G\right)\}$ is called the critical difference of $G$. $X$ is called a critical set if $d\left(X\right)$ equals the critical difference and $\ker \left(G\right)$ is the intersection of all critical sets. $\mathrm{diadem}\left(G\right)$ is the union of all critical independent sets. An independent set $S$ is an inclusion minimal set with$d\left(S\right)>0$ if no proper subset of $S$ has positive difference.A graph $G$ is called a König–Egerváry graph if the sum of its independence number $\alpha \left(G\right)$ and matching number $\mu \left(G\right)$ equals $\left|V\left(G\right)\right|$.In this paper, we prove a conjecture which states that for any graph the number of inclusion minimal independent set $S$ with $d\left(S\right)>0$ is at least the critical difference of the graph.We also give a new short proof of the inequality $\left|\ker \left(G\right)\right|+\left|\mathrm{diadem}\left(G\right)\right|\le 2\alpha \left(G\right)$.A characterization of unicyclic non-König–Egerváry graphs is also presented and a conjecture which states that for such a graph $G$, the critical difference equals $\alpha \left(G\right)?\mu \left(G\right)$, is proved.We also make an observation about $\ker \left(G\right)$ using Edmonds–Gallai Structure Theorem as a concluding remark.