The reduction of rotational ambiguity in soft-modeling by introducing hard models

Rotational ambiguity is a major problem in the application of soft-modeling analysis to a variety of multivariate mixture resolution problems and particularly important in the analysis of kinetic data. Soft-modeling analyses rely on constraints that restrict the concentration profiles and/or the spectral responses of all components. The main goal of this work is to demonstrate how a hard-modeling constraint on concentration profiles drastically decreases the extent of the rotational ambiguity. Therefore, in the present paper the discussion is focused on systems in which hard-modeling information is available. The results of simulated examples reveal that the utilized hard constraint decreases the rotational ambiguity in estimated concentration profile even components that do not take part in the explicit model. In addition, the rate constant of known reaction is determined in this method.     

A phosphoryl to spiro-bicyclophosphorane transformation via β-amidic proton elimination in phosphorylated hydrazides

The reaction between phosphoryl-containing reagents and hydrazides has been studied. The tetrahedral phosphoryl structure is transformed into a spiro-bicyclophosphorane system with trigonal bipyramidal geometry by the elimination of a β-amidic proton in the reaction between a hydrazide and phosphoryl reagents with at least two leaving groups (Cl) bound to the phosphorus atom, such as POCl₃ or PhPOCl₂. In the spiro-bicyclophosphorane structure, the CN imine bond is formed upon β-amidic proton elimination, leading to the conversion of the CO into a C-O bond and the formation of a P-O bond. All of these structural rearrangements are supported by X-ray crystallography data, and NMR and IR experiments.     

An efficient regioselective synthesis of highly functionalized 3-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyrimidines via an isocyanide-based three-component reaction

We present a novel, convenient, and efficient method for synthesizing polysubstituted 3-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidines via a three-component reaction. The zwitterions generated from the reaction of isocyanides and dialkyl acetylenedicarboxylates react with 2-imino-1,3-thiazolidin-4-one to produce the title compounds in good yields.     

Nonlinear Analysis and Optimum Design of Guyed Masts

In this paper the nonlinear analysis and design optimization of guyed masts is addressed. The mast is modeled as a 3D truss and is supported by catenary cable elements that have nonlinear elastic behavior. For nonlinear static analysis, an innovative procedure is proposed that divides the structure into linear and nonlinear parts and analyzes them separately. The proposed method satisfies the equilibrium and compatibility by establishing and solution of a set of nonlinear equations. The optimization problem employs the sizes of members, initial cable tensions and the positions of anchor on the ground and tie level of cables on the mast as design variables. To facilitate the optimization solution, a compatible sensitivity analysis procedure is proposed. Sensitivities of objective function, displacement and strength constraints in the mast and cables, subjected to a variety of load combinations including dead, wind and ice loads are calculated. Numerical examples are provided to show the nonlinear analysis procedure and the applicability of the algorithm to optimum design of practical guyed masts.     

The effective conductivity equation for a highly heterogeneous periodic medium

We consider the homogenization of a conductivity equation for a medium made up of a set ${F_\varepsilon}$ ( ${\varepsilon}$ being the size of the period of the medium) of highly conductive vertical fibers surrounded by another material (the matrix) assumed to be a poor conductor. The conductivity coefficients in the fibers behave as ${\frac{1}{\varepsilon^2}}$ while whose of the matrix behave as ${\varepsilon^2}$ . We show that the homogenized problem consists of an equality of the kind u(x) = m(x) f (x) where u denotes the macroscopic temperature, f the source term and m(x) a coefficient given by solving some cell equation.     

Synthesis and characterization of two new fluorescent macrocycles: A novel fluorescent chemosensor for zinc ion

Two new macrocyclic systems (L¹, L²) containing two emissive naphthalene were synthesized and characterized. The macrocycles were studied by ¹H NMR, ¹³C NMR, COSY, HMQC, DEPT, microanalysis and mass spectroscopy. The influence of metal cations Na⁺, Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Hg²⁺ on the spectroscopic properties of the macrocyclic systems in acetonitrile/DMF 9:1 (v/v) mixtures were investigated by means of absorption and emission spectrophotometry. The macrocycle L¹ was found to be as an effective fluorescence sensor for Zn²⁺ ions. Zn²⁺ and Cd²⁺ ions show the most effects on the fluorescence intensity of L².     

Numerical study of random lasing in three dimensional amplifying disordered media

In this paper, the lasing action in three-dimensional active random systems has been numerically investigated. Here, random systems of spherical dielectric particles imbedded in an active medium are considered. The quasi steady state approximation for the population inversion of the active medium is applied to solve three dimensional governing equations. Results show that when the density of particles increases to an upper limit, the intensity of lasing modes is enhanced. Also, the effects of pumping rate and particle size on the number of lasing modes and their intensity are studied. Lasing threshold of laser modes in different disordered systems is calculated and it is shown that by an appropriate selection of the central frequency of gain line-shape, the output power intensity of random lasers increases. These results are in agreement with the experimental results observed by others.     

The numerical and experimental study of photon diffusion inside biological tissue using boundary integral method

In this study, the diffusion of photons in turbid media, like biological tissue has been studied. Due to scattering and absorption of photons in such media, the study of photon propagation in biological tissue is complicated. The several numerical methods have been presented to simulate the behavior of diffused photons. Recently, Boundary Integral Method (BIM) has been offered to simulate photon migration inside biological tissues. This method has advantage, e.g. lower computational time in compared with other numerical methods. In this study, the accuracy and precision of BIM compares with another numerical method like Monte Carlo technique and finite difference method, and also the calculated results obtained by BIM and Monte Carlo method evaluate with measured results. Furthermore, the effects of scattering and absorption coefficient of tissue on the measured signal are studied.     

Synthesis of 1H,7H,12bH‐Pyrano[3′,4′: 5,6]pyrano[3,4‐c][1]benzopyran‐1‐one via Domino Knoevenagel/Hetero‐Diels?Alder Reaction with Theoretical Investigations

The CuI‐catalyzed intramolecular oxa‐Diels? Alder reaction of 2‐(prop‐2‐yn‐1‐yloxy)benzaldehydes as unactivated terminal alkynes with 4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one is described. The reaction proceeds with remarkable chemoselectivity to yield pyranones 3 (Scheme 1). A theoretical investigation of the reaction in terms of HOMO? LUMO interactions in the gas phase is also reported. The reaction could be regarded as an inverse‐electron‐demand Diels? Alder cycloaddition. The theoretical results are in high agreement with the experimental evidences.     

Oxidative addition of MeI to some cyclometalated organoplatinum(II) complexes: Kinetics and mechanism

New cyclometalated platinum(II) complexes [PtMe(C^N)L], 1, in which C^N = deprotonated 2-phenylpyridine (ppy), benzo[h]quinoline (bhq) or 2-(p-tolyl)pyridine (tpy) and L = PPh₃ or PMePh₂, were synthesized by the reaction of [PtMe(C^N)(SMe₂)] with 1 equiv of L. The reaction of complexes 1 with MeI gave the cyclometalated Pt(IV) complexes [PtMe₂I(C^N)L], 3. On the basis of kinetic studies, using Uv–visible spectroscopy, it was suggested that the latter oxidative addition reactions were proceeded by an S_N2 mechanism. The rates of the reactions at different temperatures were measured and consistent with the proposed mechanism, large negative ΔS³ values were found for each reaction. Besides, rate of reactions (in CHCl₃) involving the PPh₃ complexes [PtMe(C^N)(PPh₃)], were almost 3–5 times slower than those involving the PMePh₂ complexes [PtMe(C^N)(PMePh₂)]. This was attributed to the electronic and steric effects of PPh₃ ligand as compared with that of PMePh₂ ligand which was further confirmed using density functional theory (DFT) calculations through finding approximate structures for the described complexes.