Quadratic Nonlinearity of One- and Two-Electron Oxidized Metalloporphyrins and Their Switching in Solution

We report the quadratic nonlinearity of one- and two-electron oxidation products of the first series of transition metal complexes of meso-tetraphenylporphyrin (TPP). Among many MTPP complexes, only CuTPP and ZnTPP show reversible oxidation/reduction cycles as seen from cyclic voltammetry experiments. While centrosymmetric neutral metalloporphyrins have zero first hyperpolarizability, β, as expected, the cation radicals and dications of CuTPP and ZnTPP have very high β values. The one- and two-electron oxidation of the MTPPs leads to symmetry-breaking of the metal−porphyrin core, resulting in a large β value that is perhaps aided in part by contributions from the two-photon resonance enhancement. The calculated static first hyperpolarizabilities, β0, which are evaluated in the framework of density functional theory by a coupled perturbed Hartree−Fock method, support the experimental trend. The switching of optical nonlinearity has been achieved between the neutral and the one-electron oxidation products but not between the one- and the two-electron oxidation products since dications that are electrochemically reversible are unstable due to the formation of stable isoporphyrins in the presence of nucleophiles such as halides.

The effect of halogen atom on the molecular quadratic nonlinearity of half sandwich complexes in the presence of an acceptor

Half sandwich complexes of the type [CpM(CO)(n)X] {X=Cl, Br, I; If, M=Fe, Ru; n=2 and if M=Mo; n=3} and [CpNiPPh3X] {X=Cl, Br, I} have been synthesized and their second order molecular nonlinearity (beta) measured at 1064 nm in CHCl3 by the hyper-Rayleigh scattering technique. Iron complexes consistently display larger beta values than ruthenium complexes while nickel complexes have marginally larger beta values than iron complexes. In the presence of an acceptor ligand such as CO or PPh3, the role of the halogen atom is that of a pi donor. The better overlap of Cl orbitals with Fe and Ni metal centres make Cl a better pi donor than Br or I in the respective complexes. Consequently, M-pi interaction is stronger in Fe/Ni-Cl complexes. The value of beta decreases as one goes down the halogen group. For the complexes of 4d metal ions where the metal-ligand distance is larger, the influence of pi orbital overlap appears to be less important, resulting in moderate changes in beta as a function of halogen substitution. (C) 2006 Elsevier B.V. All rights reserved.

Enantioselective syntheses of diquinane and (cis, anti, cis)-linear triquinanes

The enantioselective syntheses of diquinane and cis, anti, cis-linear triquinanes, starting from the readily available (S)-campholenaldehyde, employing an intramolecular rhodium carbenoid CH insertion reaction, are described. (C) 2010 Elsevier Ltd. All rights reserved.

Fluorescent resonant excitation energy transfer in linear polyenes

We have studied the dynamics of excitation transfer between two conjugated polyene molecules whose intermolecular separation is comparable to the molecular dimensions. We have employed a correlated electron model that includes both the charge-charge, charge-bond, and bond-bond intermolecular electron repulsion integrals. We have shown that the excitation transfer rate varies as inverse square of donor-acceptor separation R-2 rather than as R-6, suggested by the Foumlrster type of dipolar approximation. Our time-evolution study alsom shows that the orientational dependence on excitation transfer at a fixed short donor-acceptor separation cannot be explained by Foumlrster type of dipolar approximation beyond a certain orientational angle of rotation of an acceptor polyene with respect to the donor polyene. The actual excitation transfer rate beyond a certain orientational angle is faster than the Foumlrster type of dipolar approximation rate. We have also studied the excitation transfer process in a pair of push-pull polyenes for different push-pull strengths. We have seen that, depending on the push-pull strength, excitation transfer could occur to other dipole coupled states. Our study also allows for the excitation energy transfer to optically dark states which are excluded by Foumlrster theory since the one-photon transition intensity to these states (from the ground state) is zero.

Linear transconductor with flipped voltage follower in 130 nm CMOS

This paper presents a modified design method for linear transconductor circuit in 130 nm CMOS technology to improve linearity, robustness against process induced threshold voltage variability and reduce harmonic distortion. Source follower in the adaptively biased differential pair (ABDP) linear transconductor circuit is replaced with flipped voltage follower to improve the efficiency of the tail current source, which is connected to a conventional differential pair. The simulation results show the performance of the modified circuit also has better speed, noise performance and common mode rejection ratio compared to the ABDP circuit.

Interactions of linear dicationic molecules with lipid A: structural requisites for optimal binding affinity

The structural determinants of the binding affinity of linear dicationic molecules toward lipid A have been examined with respect to the distance between the terminal cationic functions, the basicity, and the type of cationic moieties using a series of spermidine derivatives and pentamidine analogs by fluorescence spectroscopic methods, The presence of two terminal cationic groups corresponds to enhanced affinity, A distinct sigmoidal relationship between the intercationic distance and affinity was observed with a sharp increase at 11 Angstrom, levelling off at about 13 Angstrom. The basicity (pK) and nature of the cationic functions are poor correlates of binding potency, since molecules bearing primary amino, imidazolino, or guanido termini are equipotent, The interaction of pentamidine, a bisamidine drug, with lipid A, characterized in considerable detail employing the putative intermolecular excimerization of the drug, suggests a stoichiometry of 1:1 in the resultant complex, The binding is driven almost exclusively by electrostatic forces, and is dependent on the ionization states of both lipid A and the drug, Under conditions when lipid A is highly disaggregated, pentamidine binds specifically to bis-phosphoryl- but not to monophosphoryl-lipid A indicating that both phosphate groups of lipid A are necessary for electrostatic interactions by the terminal amidininium groups of the drug, Based on these data, a structural model is proposed for the pentamidine-lipid A complex, which may be of value in designing endotoxin antagonists from first principles.

BER-optimized linear parallel interference cancellers for multicarrier DS-CDMA systems

In this paper, we consider the design and bit-error performance analysis of linear parallel interference cancellers (LPIC) for multicarrier (MC) direct-sequence code division multiple access (DS-CDMA) systems. We propose an LPIC scheme where we estimate and cancel the multiple access interference (MAT) based on the soft decision outputs on individual subcarriers, and the interference cancelled outputs on different subcarriers are combined to form the final decision statistic. We scale the MAI estimate on individual subcarriers by a weight before cancellation. In order to choose these weights optimally, we derive exact closed-form expressions for the bit-error rate (BER) at the output of different stages of the LPIC, which we minimize to obtain the optimum weights for the different stages. In addition, using an alternate approach involving the characteristic function of the decision variable, we derive BER expressions for the weighted LPIC scheme, matched filter (MF) detector, decorrelating detector, and minimum mean square error (MMSE) detector for the considered multicarrier DS-CDMA system. We show that the proposed BER-optimized weighted LPIC scheme performs better than the MF detector and the conventional LPIC scheme (where the weights are taken to be unity), and close to the decorrelating and MMSE detectors.

Approximate methods for step function response of undamped non-linear spring mass systems with arbitrary hardening type spring characteristic

The possibility of applying two approximate methods for determining the salient features of response of undamped non-linear spring mass systems subjected to a step input, is examined. The results obtained on the basis of these approximate methods are compared with the exact results that are available for some particular types of spring characteristics. The extension of the approximate methods for non-linear systems with general polynomial restoring force characteristics is indicated.

Effect of static deflection on natural frequency of non-linear spring mass system by direct linearization method

An exact expression for the frequency of a non-linear cubic spring mass system is obtained considering the effect of static deflection. An alternative expression for the approximate frequency is also obtained by the direct linearization procedure; it is shown that this is very accurate as compared with the exact method. This approximate frequency equation is used to explain a “dual behaviour” of the frequency amplitude curves.

Theory of laminar flame propagation with non-normal diffusion.

A study has been made of the problem of steady, one-dimensional, laminar flame propagation in premixed gases, with the Lewis number differing from (and equal to) unity. Analytical solutions, using the method of matched asymptotic expansions, have been obtained for large activation energies. Numerical solutions have been obtained for a wide range of the reduced activation temperature parameter (n {geometrically equal to} E/RTb), and the Lewis number δ. The studies reveal that the flame speed eigenvalue is linear in Lewis number for first order and quadratic in Lewis number for second order reactions. For a quick determination of flame speeds, with reasonable accuracy, a simple rule, expressing the flame speed eigenvalue as a function of the Lewis number and the centroid of the reaction rate function, is proposed. Comparisons have been made with some of the earlier works, for both first and second order reactions.

On the design of quadratic weirs

This paper considers the problem of the design of the quadratic weir notch, which finds application in the proportionate method of flow measurement in a by-pass, such that the discharge through it is proportional to the square root of the head measured above a certain datum. The weir notch consists of a bottom in the form of a rectangular weir of width 2W and depth a over which a designed curve is fitted. A theorem concerning the flow through compound weirs called the “slope discharge continuity theorem” is discussed and proved. Using this, the problem is reduced to the determination of an exact solution to Volterra's integral equation in Abel's form. It is shown that in the case of a quadratic weir notch, the discharge is proportional to the square root of the head measured above a datum Image a above the crest of the weir. Further, it is observed that the function defining the shape of the weir is rapidly convergent and its value almost approximates to zero at distances of 3a and above from the crest of the weir. This interesting and significant behaviour of the function incidentally provides a very good approximate solution to a particular Fredholm integral equation of the first kind, transforming the notch into a device called a “proportional-orifice”. A new concept of a “notch-orifice” capable of passing a discharge proportional to the square root of the head (above a particular datum) while acting both as a notch, and as an orifice, is given. A typical experiment with one such notch-orifice, having A = 4 in., and W = 6 in., shows a remarkable agreement with the theory and is found to have a constant coefficient of discharge of 0.61 in the ranges of both notch and orifice.

Response spectrum of non-linear spring mass system subjected to transient disturbances

The transient response spectrum of a cubic spring mass system subjected to a step function input is obtained. An approximate method is adopted where non-linear restoring force characteristic is replaced by two linear segments, so that the mean square error between them is a minimum. The effect of viscous damping on the peak response is also discussed for various values of the damping constant and the non-linearity restoring force parameter.

Non-Linear vibration of an elastic string

Equations proposed in previous work on the non-linear motion of a string show a basic disagreement, which is here traced to an assumption about the longitudinal displacement u. It is shown that it is neither necessary nor justifiable to assume that u is zero; and also that the velocity of propagation of u disturbances in a string is different from that in an infinite medium, although this difference is usually negligible. After formulating the exact equations of motion for the string, a systematic procedure is described for obtaining approximations to these equations to any order, making only the assumption that the strain in the material of the string is small. The lowest order equations in this scheme are non-linear, and are used to describe the response of a string near resonance. Finally, it is shown that in the absence of damping, planar motion of a string is always unstable at sufficiently high amplitudes, the critical amplitude falling to zero at the natural frequency and its subharmonics. The effect of slight damping on this instability is also discussed.

A new approach to the study of non-linear non-autonomous systems

In this paper, a new approach to the study of non-linear, non-autonomous systems is presented. The method outlined is based on the idea of solving the governing differential equations of order n by a process of successive reduction of their order. This is achieved by the use of “differential transformation functions”. The value of the technique presented in the study of problems arising in the field of non-linear mechanics and the like, is illustrated by means of suitable examples drawn from different fields such as vibrations, rigid body dynamics, etc.