Synthetic studies towards complex diterpenoids—VII : Stereoselective synthesis and conformational analysis of all four possible racemates of 1,2,3,4,4a,9a-hexadydro-1-methylfluorene-1-carboxylic acids

Synthesis of the unsaturated acid 3 through H₂SO_4? catalysed cyclodehydration of the keto-ester 1 and its conversion to lactone 4 are described. The PPA induced cyclization of the keto-acid 9, on the other hand resulted in a stereoisomeric mixture of the octahydroanthracene derivatives 10a and 10b. The four possible racemates of the hydrofluorene derivatives 5, 6, 7, and 8 have been synthesized by chemical and catalytic reduction of 3 and 4. Li-liquid ammonia induced reductive cleavage of the lactone 4 proceeds with 65% retention and 35% inversion of configuration at the benzylic C-4a asymmetric centre to afford the trans and cis acids 5 and 8 respectively, while catalytic hydrogenolysis of 4 proceeds with inversion to give the cis acid 8. Li-liquid ammonia reduction of 3 gives trans acid 6 and cis7 in 23% and 53% yields respectively, whereas catalytic hydrogenation of 3 affords 81% of cis acid 8 and 13% of cis acid 7. Some conformational properties of the methyl esters 17, 18, 19, and 20 have been deduced from chemical and NMR spectral data.     

On the gate capacitance of MOS structures of kane-type semiconductors under magnetic quantization

An attempt is made to formulate the gate capacitance of MOS structures of Kane-type semiconductors under magnetic quantization, without any approximations of weak or strong electric field limits, on the basis of the fourth-order effective mass theory and taking into account the interactions of the conduction, light-hole, heavy-hole, and split-off bands. It is found, taking n-channel Hg_1–x Cd _x Te as an example, that the gate capacitance exhibits spiky oscillations with changing magnetic field, which is in qualitative agreement with experimental observations, reported elsewhere, in MOS structures of the same semiconductor. The corresponding results for n-channel inversion layers on parabolic semiconductors are also obtained from the expressions derived.     

Reduction of Sulfur Dioxide to Sulfur Monoxide by Ferrous Porphyrin**

The reduction of SO₂ to fixed forms of sulfur can address the growing concerns regarding its detrimental effect on health and the environment as well as enable its valorization into valuable chemicals. The naturally occurring heme enzyme sulfite reductase (SiR) is known to reduce SO₂ to H₂S and is an integral part of the global sulfur cycle. However, its action has not yet been mimicked in artificial systems outside of the protein matrix even after several decades of structural elucidation of the enzyme. While the coordination of SO₂ to transition metals is documented, its reduction using molecular catalysts has remained elusive. Herein reduction of SO₂ by iron(II) tetraphenylporphyrin is demonstrated. A combination of spectroscopic data backed up by theoretical calculations indicate that Fe^IITPP reduces SO₂ by 2e⁻/2H⁺ to form an intermediate [Fe^III−SO]⁺ species, also proposed for SiR, which releases SO. The SO obtained from the chemical reduction of SO₂ could be evidenced in the form of a cheletropic adduct of butadiene resulting in an organic sulfoxide.     

Perturbation theory of optical fibres with power-law core profile

The characteristics of graded-index optical fibres with power-law core profile and homogeneous cladding have been studied using perturbation theory. Analytical expressions are derived for the cut-off frequency, propagation constant and, in the case of leaky modes, the attenuation coefficient of an arbitrary mode on such a fibre. For the case of monomode fibres, excellent agreement is found with existing theoretical results for the propagation constant of the HE₁₁ mode and cut-off frequency of the TE₀₁ mode.On leave from Department of Physics, IIT, New Delhi, India.     

An Improved Total Synthesis of (±) - Podocarpic Acid by a Cyclialkylation Route

A number of total syntheses of (±) - podocarpic acid (i) have been described¹ King, King and Topliss² first identified one of the products from nonstereo-selective cyclization of (4) with polyphosphoric acid as (±)- ethyl-O-methylpodocarpate (2) and correlated that with the corresponding acid (3), prepared in an extremly poor yield (ca 0.4%)³ by Bhattacharyya³, and Haworth and Moore⁴ by cyclization of (5) with a mixture of sulfuric acid and acetic acid. More recently Mancini, Fringuelli and Taticchi⁵ prepared (3) (in 4.8% yield) by repeating Howorth¹ s cyclization of (4). In continuation of our studies on cyclialky-     

Influence of magnetic quantization on the Einstein relation in non-linear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestion for experimental determination

In this paper, we have investigated the Einstein relation for the diffusivity-to-mobility ratio (DMR) under magnetic quantization in non-linear optical materials on the basis of a newly formulated electron dispersion law by considering the crystal field constant, the anisotropies of the momentum-matrix element and the spin-orbit splitting constant, respectively, within the frame work of k·p formalism. The corresponding result for the three-band model of Kane (the conduction electrons of III-V, ternary and quaternary compounds obey this model) forms a special case of our generalized analysis. The DMR under magnetic quantization has also been investigated for II-VI (on the basis of Hopfield model), bismuth (using the models of McClure and Choi, Cohen, Lax and parabolic ellipsoidal, respectively), and stressed materials (on the basis of model of Seiler et al.) by formulating the respective electron statistics under magnetic quantization incorporating the respective energy band constants. It has been found, taking n-CdGeAs₂, n-Hg_1−xCd_xTe, p-CdS, and stressed n-InSb as examples of the aforementioned compounds, that the DMR exhibits oscillatory dependence with the inverse quantizing magnetic field due to Subhnikov de Haas (SdH) effect with different numerical values. The DMR also increases with increasing carrier degeneracy and the nature of oscillations are totally dependent on their respective band structures in various cases. The classical expression of the DMR has been obtained as a special case from the results of all the materials as considered here under certain limiting conditions, and this compatibility is the indirect test of our generalized formalism. In addition, we have suggested an experimental method of determining the DMR for degenerate materials under magnetic quantization having arbitrary dispersion laws. The three applications of our results in the presence of magneto-transport have further been suggested.     

Temperature dependence of the Debye screening length in heavily doped semiconductors having Gaussian band-tails

In the present work, a generalized expression is derived for the Debye screening length of the carriers in heavily doped semiconductors having Gaussian band-tails. The temperature dependence of the screening length is also computed for such semiconductors, taking n-type GaAs as an example.On leave of absence fromthe Department of Physics, B. N. College, University of Patna, India.     

MeV Au ion induced modifications at Co/Si interface

We report on room temperature MeV Au ion induced modifications at the Co/Si interfaces. Nanometers size thin film of Co and Si were grown by ultra high vacuum (UHV) electron beam evaporation technique on Si(1 1 1) surface and were irradiated by 1.5 MeV Au²⁺ ions at a fluence of 5 × 10¹⁴ ions cm⁻². High-resolution transmission electron microscopy (HRTEM) along with energy filter imaging technique has been employed to study the formation of Co-Si alloy at the interface. Formation of such surface alloy has been discussed in the light of ion-matter interaction in nanometer scale regime.     

Three-dimensional multihelical microfluidic mixers for rapid mixing of liquids

Rapid mixing of liquids is important for most microfluidic applications. However, mixing is slow in conventional micromixers, because, in the absence of turbulence, mixing here occurs by molecular diffusion. Recent experiments show that mixing can be enhanced by generating transient flow resulting in chaotic advection. While these are planar microchannels, here we show that three-dimensional orientations of fluidic vessels and channels can enhance significantly mixing of liquids. In particular, we present a novel, multihelical microchannel system built in soft gels, for which the helix angle, helix radius, axial length, and even the asymmetry of the channel cross section are easily tailored to achieve the desired mixing. Mixing efficiency increases with helix angle and asymmetry of channel cross section, which leads to orders of magnitude reduction in mixing length over conventional mixers. This new scheme of generating 3D microchannels will help in miniaturization of devices, process intensification, and generation of multifunctional process units for microfluidic applications.