Control of Chemical Reactions by Using Molecules that Buffer Non-aqueous Solutions

Control of chemical reactions is necessary to obtain designer chemical transformation products and for preventing decomposition and isomerization reactions of compounds of interest. For the control of chemical events in aqueous solutions, the use of aqueous buffers is a common practice. However, no molecules that buffer non-aqueous solutions were commonly used. Herein, we demonstrate that 1,3-cyclohexanedione derivatives have buffering functions in non-aqueous solutions. It was also shown that these molecules can be utilized to alter and control chemical reactions. 1,3-Cyclohexanedione derivatives inhibited both acid- and base-catalyzed isomerizations and decompositions in organic solvents. The reaction products obtained in the presence of the buffering molecule 2-methyl-1,3-cyclohexanedione differed from those obtained in the absence of the buffering molecule. The use of buffering molecules that work in organic solvents provides a strategy to control chemical reactions and expands the range of compounds that can be synthesized.     

DNA scaffold supports long-lived vibronic coherence in an indodicarbocyanine (Cy5) dimer

Vibronic coupling between pigment molecules is believed to prolong coherences in photosynthetic pigment–protein complexes. Reproducing long-lived coherences using vibronically coupled chromophores in synthetic DNA constructs presents a biomimetic route to efficient artificial light harvesting. Here, we present two-dimensional (2D) electronic spectra of one monomeric Cy5 construct and two dimeric Cy5 constructs (0 bp and 1 bp between dyes) on a DNA scaffold and perform beating frequency analysis to interpret observed coherences. Power spectra of quantum beating signals of the dimers reveal high frequency oscillations that correspond to coherences between vibronic exciton states. Beating frequency maps confirm that these oscillations, 1270 cm⁻¹ and 1545 cm⁻¹ for the 0-bp dimer and 1100 cm⁻¹ for the 1-bp dimer, are coherences between vibronic exciton states and that these coherences persist for ∼300 fs. Our observations are well described by a vibronic exciton model, which predicts the excitonic coupling strength in the dimers and the resulting molecular exciton states. The energy spacing between those states closely corresponds to the observed beat frequencies. MD simulations indicate that the dyes in our constructs lie largely internal to the DNA base stacking region, similar to the native design of biological light harvesting complexes. Observed coherences persist on the timescale of photosynthetic energy transfer yielding further parallels to observed biological coherences, establishing DNA as an attractive scaffold for synthetic light harvesting applications.

Dyes coupled to DNA display distance-dependent vibronic couplings that prolongs quantum coherences detected with 2D spectroscopy.     

Materials analysis using confocal Raman microscopy

The recent development of Raman microscopes with high optical throughput and very sensitive CCD cameras has led to Raman spectroscopy again competing effectively with FTIR methods for materials analysis. Modern Raman instruments, designed to operate confocally without serious alignment or energy trade-off problems, allow depth profiling of optically transparent polymers and polymer matrices to be routinely obtained with a spatial resolution of 1–2 μm. The use of such an instrument is illustrated by describing recent work on polymeric material problems including, 1 The distribution and redistribution of small molecules in polymeric matrices. 2 The monitoring of adhesion primer diffusion at a polymer/silica interface. 3 The determination of the extent of interdiffusion and interaction at a polymer/polymer interface. 4 A comparison of confocal and micotoming approaches to polymer laminate analysis. The range of possible applications is increasing rapidly. It is clear that Raman microscopy will become a very important tool for future materials analysis, both in the polymer area and many other areas.     

Simulation of heat and mass transfer on peristaltic flow of hyperbolic tangent fluid in an asymmetric channel

In the present analysis, the influence of heat and mass transfer on the peristaltic flow of a hyperbolic tangent fluid in an asymmetric channel has been discussed. The highly nonlinear equations are simplified under lubrication approach. The perturbation and numerical solutions of the problem are not only discussed but the validity of the results is also being checked. The graphical results of the problem under discussion are also being brought under consideration to see the behavior of various physical parameters. Copyright © 2012 John Wiley & Sons, Ltd.     

Flow due to a plate that applies an accelerated shear to a second grade fluid between two parallel walls perpendicular to the plate

The velocity field and the shear stresses corresponding to the motion of a second grade fluid between two side walls, induced by an infinite plate that applies an accelerated shear stress to the fluid, are determined by means of the integral transforms. The obtained solutions, presented under integral form in term of the solutions corresponding to the flow due to a constant shear on the boundary, satisfy all imposed initial and boundary conditions. In the absence of the side walls, they reduce to the similar solutions over an infinite plate. The Newtonian solutions are obtained as limiting cases of the general solutions. The influence of the side walls on the fluid motion as well as a comparison between the two models is shown by graphical illustrations.     

Asymmetric Synthesis of Octahydrobenzofuran Core Structure with Three Contiguous Stereogenic Centers and Development of the Absolute Configurations

Cyclization of enantiopure (S/R)-1 with halogen-reagent-constructed enantiopure octahydrobenzofuran core structure with contiguous three stereogenic centers of both enantiomers (SRR and RSS). The absolute configurations of all compounds have been established from x-ray analysis of the single crystal of (3aS,7aR,7R)-3. The chiral initiation in diastereoselective mode of 5-exo ring closure across C?C bond of pendant cyclohexene moiety has been proposed.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Cattaneo–Christov heat flux model for stagnation point flow of micropolar nanofluid toward a nonlinear stretching surface with slip effects

Journal of Thermal Analysis and Calorimetry - Cattaneo–Christov with variable thermal relaxation time and entropy generation is the main concern of this study. The micropolar fluid with...     

Physical vapor deposition of SnS:PbS-dithiocarbamate chalcogenide semiconductor thin films: elucidation of optoelectronic and electrochemical features

Abstract

This work reports the first investigation on the physical vapor deposition of thin films of tin sulfide doped lead sulfide (SnS:PbS). In-situ synthesis route using diethyldithiocarbamate (DTC) ligand was adopted for SnS-DTC, PbS-DTC and SnS:PbS-DTC complex formation. PbS-DTC and SnS:PbS-DTC expressed an average crystallite size of 30.98 and 29.74?nm, respectively shown by X-ray diffraction (XRD) analysis. A face centered cubic geometry was revealed from XRD. Ultraviolet visible spectrophotometry expressed a direct and indirect band gap of 3.4 and 3.2?eV, respectively for SnS:PbS-DTC. A smooth morphology with presence of larger agglomerated particles was disclosed by scanning electron microscopy for SnS:PbS-DTC thin films with 615?nm thickness. SnS:PbS-DTC thin films expressed remarkable electrochemical behavior explored via cyclic voltammetry, linear sweep voltammetry and chronoamperometry showing an improvement in the photo-current response upon potential bias increment. The results of the current research indicated the potential of SnS:PbS-DTC thin films for utilization in different types of photovoltaic devices.     

Non-Stationary Ordering Policies for Multi-Item Inventory Systems Subject to a Single Resource Constraint

This paper studies the multi-item inventory problem with a single constraint. Two well-known approaches to this problem are the Lagrangian method and the fixed-cycle approach. Both of these methods generate stationary ordering policies. A competing approach is presented here that generates non-stationary ordering policies, with order quantities that vary over time. These non-stationary policies are, in all cases, preferred to those generated by the Lagrangian approach, and in some cases preferred to those generated by the fixed-cycle approach. Computational results comparing the three methods are also given.