A New, Convenient Reductive Procedure For The Deprotection Of 4-Methoxybenzyl (Mpm) Ethers To Alcohols

Selective introduction and removal of protecting groups is of great significance in organic synthesis.l The benzyl ether function is one of the most common protecting groups for alcohols. Selective oxidative removal of the 4-methoxybenzyl (MPM) ethers in the presence of benzyl ethers made the MPM moiety an alternative protecting group, and its utility in carbohydrate chemistry is well established. Several procedures have been developed for the cleavage of the 4-methoxybenzyl moiety, e.g. DDQ oxidation (eq 1),2e lectrochemical ~xidationh,~om ogeneous electron t r a n~f e rp,~ho toinduced single electron t r an~f e rb,o~ro n trichloride-dimethyl sulfide,6e tc. However, in all these methods isolation of the alcohol from the inevitable byproduct, 4-methoxybenzaldehyde [also dichlorodicyanohydroquinone (DDHQ) in the most commonly used method employing DDQI can be troublesome. Recently Wallace and Hedgetts7 discovered that acetic acid at 90 "C cleaves the aromatic MPM ethers into the corresponding phenols and 4-methoxybenzyl acetate (eq 21, whereas the aliphatic MPM ethers generated, instead of alcohols, the corresponding acetates (eq 3). Complimentary to this methodology, herein we report that sodium cyanoborohydride and boron trifluoride etherate reductively cleaves, cleanly and efficiently, the aliphatic MPM ethers to an easily separable mixture of the corresponding alcohols and 4-methylanisole

Void Geometry Driven Spin Crossover in Zeolite-Encapsulated Cobalt Tris(bipyridyl) Complex Ion

The cobalt(II) tris(bipyridyl) complex ion encapsulated in zeolite-Y supercages exhibits a thermally driven interconversion between a low-spin and a high-spin state-a phenomenon not observed for this ion either in solid state or in solution. From a comparative study of the magnetism and optical spectroscopy of the encapsulated and unencapsulated complex ion, supported by molecular modeling, such spin behavior is shown to be intramolecular in origin. In the unencapsulated or free state, the [Co(bipy)(3)](2+) ion exhibits a marked trigonal prismatic distortion, but on encapsulation, the topology of the supercage forces it to adopt a near-octahedral geometry. An analysis using the angular overlap ligand field model with spectroscopically derived parameters shows that the geometry does indeed give rise to a low-spin ground state, and suggests a possible scenario for the spin state interconversion.

Crossover from Ising to mean-field critical behavior in an aqueous electrolyte solution

The near-critical behavior of the susceptibility deduced from light-scattering measurements in a ternary liquid mixture of 3-methylpyridine, water, and sodium bromide has been determined. The measurements have been performed in the one-phase region near the lower consolute points of samples with different concentrations of sodium bromide. A crossover from Ising asymptotic behavior to mean-field behavior has been observed. As the concentration of sodium bromide increases, the crossover becomes more pronounced, and the crossover temperature shifts closer to the critical temperature. The data are well described by a model that contains two independent crossover parameters. The crossover of the susceptibility critical exponent γ from its Ising value γ=1.24 to the mean-field value γ=1 is sharp and nonmonotonic. We conclude that there exists an additional length scale in the system due to the presence of the electrolyte which competes with the correlation length of the concentration fluctuations. An analogy with crossover phenomena in polymer solutions and a possible connection with multicritical phenomena is discussed.

Concept of "Crossover Point" and its Application on Threshold Voltage Definition for Undoped-Body Transistors

As the conventional MOSFET's scaling is approaching the limit imposed by short channel effects, Double Gate (DG) MOS transistors are appearing as the most feasible candidate in terms of technology in sub-45nm technology nodes. As the short channel effect in DG transistor is controlled by the device geometry, undoped or lightly doped body is used to sustain the channel. There exits a disparity in threshold voltage calculation criteria of undoped-body symmetric double gate transistors which uses two definitions, one is potential based and the another is charge based definition. In this paper, a novel concept of "crossover point'' is introduced, which proves that the charge-based definition is more accurate than the potential based definition.The change in threshold voltage with body thickness variation for a fixed channel length is anomalous as predicted by potential based definition while it is monotonous for charge based definition.The threshold voltage is then extracted from drain currant versus gate voltage characteristics using linear extrapolation and "Third Derivative of Drain-Source Current'' method or simply "TD'' method. The trend of threshold voltage variation is found same in both the cases which support charge-based definition.

Concept of Crossover point and its application on Threshold Voltage definition for Undoped-Body Transistors

As the conventional MOSFETs scaling is approaching the limit imposed by short channel effects, Double Gate (DG) MOS transistors are appearing as the most feasible andidate in terms of technology in sub-45nm technology nodes. As the short channel effect in DG transistor is controlled by the device geometry, undoped or lightly doped body, is used to sustain the channel. There exits a disparity in threshold voltage calculation criteria of undoped-body symmetric double gate transistors which uses two definitions, one is potential based and the another is charge based definition. In this paper, a novel concept of "crossover point" is introduced, which proves that the charge-based definition is more accurate than the potential based definition. The change in threshold voltage with body thickness variation for a fixed channel length is anomalous as predicted by, potential based definition while it is monotonous for change based definition. The threshold voltage is then extracted from drain currant versus gate voltage characteristics using linear extrapolation and "Third Derivative of Drain-Source Current" method or simply "TD" method. The trend of threshold voltage variation is found some in both the cases which support charge-based definition.

Justifying threshold voltage definition for undoped body transistors through ``crossover point'' concept

Two different definitions, one is potential based and the other is charge based, are used in the literatures to define the threshold voltage of undoped body symmetric double gate transistors. This paper, by introducing a novel concept of crossover point, proves that the charge based definition is more accurate than the potential based definition. It is shown that for a given channel length the potential based definition predicts anomalous change in threshold voltage with body thickness variation while the charge based definition results in monotonous change. The threshold voltage is then extracted from drain current versus gate voltage characteristics using linear extrapolation, transconductance and match-point methods. In all the three cases it is found that trend of threshold voltage variation support the charge based definition.

On an analytical-numerical procedure for the analysis of cylindrical shells with arbitrarily oriented cracks

An analytical-numerical procedure for obtaining stress intensity factor solutions for an arbitrarily oriented crack in a long, thin circular cylindrical shell is presented. The method of analysis involves obtaining a series solution to the governing shell equation in terms of Mathieu and modified Mathieu functions by the method of separation of variables and satisfying the crack surface boundary conditions numerically using collocation. The solution is then transformed from elliptic coordinates to polar coordinates with crack tip as the origin through a Taylor series expansion and membrane and bending stress intensity factors are computed. Numerical results are presented and discussed for the pressure loading case.

A new synthetic procedure for the preparation of pyridinium tetrafluoroborate and hexafluorosilicate

Pyridinium tetrafluoroborate (C5H5NHBF4) and pyridinium hexafluorosilicate [(C5H5NH)2SiF6] have been prepared in good yields and high purity by the reaction of pyridinium poly(hydrogen fluoride) with oxides and acids of boron and silicon respectively. The salts have been characterised by melting points, IR, 1H and 19F NMR spectroscopy and chemical analysis.

A rapid procedure for the isolation of spheroplasts from Mycobacterium smegmatis

Abstract is not available.

Optimal Parameter Trajectory Estimation in Parameterized SDEs: An Algorithmic Procedure

We consider the problem of estimating the optimal parameter trajectory over a finite time interval in a parameterized stochastic differential equation (SDE), and propose a simulation-based algorithm for this purpose. Towards this end, we consider a discretization of the SDE over finite time instants and reformulate the problem as one of finding an optimal parameter at each of these instants. A stochastic approximation algorithm based on the smoothed functional technique is adapted to this setting for finding the optimal parameter trajectory. A proof of convergence of the algorithm is presented and results of numerical experiments over two different settings are shown. The algorithm is seen to exhibit good performance. We also present extensions of our framework to the case of finding optimal parameterized feedback policies for controlled SDE and present numerical results in this scenario as well.

A gravimetric procedure for the determination of wet precipitated sulphur, dissolved sulphur, soluble sulphides and hydrogen sulphide

Elemental sulphur (in wet precipitated form or dissolved in organic solvents) and hydrogen sulphide have been determined gravimetrically at room temperature by conversion into copper sulphide by elemental copper in presence of an organic solvent such as benzene or acetonitrile. Any solvent in which sulphur is soluble can be used. The black copper sulphide formed can be weighed or determined iodometrically. Analysis indicates the black compound to be Cu1.8S. This room temperature method is a versatile one-step procedure sensitive to microgram or macro amounts of sulphur. It has been used for determining the solubility of sulphur in tetrahydrofuran and dioxan. The apparent heat of solution indicates that sulphur dissolves in these solvents without any marked solute—solvent interactions.

Self-Organization of n-Alkane Chains in Water: Length Dependent Crossover from Helix and Toroid to Molten Globule

We demonstrate a chain length dependent crossover in the structural properties of linear hydrocarbon (n-alkane) chains using detailed atomistic simulations in explicit water. We identify a number of exotic structures of the polymer chain through energy minimization of representative snapshots collected from molecular dynamics trajectory. While the collapsed state is ring-like (circular) for small chains (CnH2n+2; n <= 20) and spherical for very long ones (n = 100), we find the emergence of ordered helical structures at intermediate lengths (n similar to 40). We find different types of disordered helices and toroid-like structures at n = 60. We also report a sharp transition in the stability of the collapsed state as a function of the chain length through relevant free energy calculations. While the collapsed state is only marginally metastable for C20H42, a clear bistable free energy surface emerges only when the chain is about 30 monomers long. For n = 30, the polymer exhibits an intermittent oscillation between the collapsed and the coil structures, characteristic of two stable states separated by a small barrier.

A simple procedure for purification of N-carbamoylputrescine: Application to assays of putrescine transcarbamoylase and agmatine iminohydrolase activities

The observation that N-carbamoylputrescine is quantitatively excluded on O-(carboxymethyl)-cellulose columns with simultaneous retention of putrescine and agmatine has been utilized to develop a sensitive radiometric assay for putrescine transcarbamoylase and a colorimetric assay for agmatine iminohydrolase. A simple procedure for obtaining bulk amounts of pure synthetic N-carbamoylputrescine by separation from putrescine and dicarbamoylputrescine on Dowex 50 (Na+) resin is described.

On an analytical-numerical procedure for the analysis of cylindrical-shells with arbitrarily oriented cracks

An analytical-numerical procedure for obtaining stress intensity factor solutions for an arbitrarily oriented crack in a long, thin circular cylindrical shell is presented. The method of analysis involves obtaining a series solution to the governing shell equation in terms of Mathieu and modified Mathieu functions by the method of separation of variables and satisfying the crack surface boundary conditions numerically using collocation. The solution is then transformed from elliptic coordinates to polar coordinates with crack tip as the origin through a Taylor series expansion and membrane and bending stress intensity factors are computed. Numerical results are presented and discussed for the pressure loading case.