Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Diketopyrrolopyrrole-Based Donor-Acceptor Copolymers as Organic Sensitizers for Dye Sensitized Solar Cells

In this work diketopyrrolopyrrole based copolymers (PDPP-BBT and TDPP-BBT) containing a donor-acceptor structural unit have been explored as organic Sensitizers for quasi-solid state dye Sensitized solar cells. Polymer-sensitized solar cells (PSSC) fabricated utilizing PDPP-BBT and TDPP-BBT as the active layer resulted in a typical power conversion efficiency of 1.43% and 2.41%, respectively. The power conversion efficiency of PSSCs based on TDPP-BBT With use of TiCl4-modified TiO2 photoanode was about 3.06%, attributed to the reduced back recombination reaction and more charge carriers in the external Circuit.

Electronic structures of electron donor-acceptor complexes: results from ultraviolet photoelectron spectroscopy and molecular orbital calculations

HeI photoelectron spectra of 1:1 electron donor-acceptor complexes are discussed in the light of molecular orbital calculations. The complexes discussed include those formed by BH3, BF3 and SO2. Some systematics have been found in the ionization energy shifts of the complexes compared to the free components and these are related to the strength of the donor-acceptor bond. Hel spectra of hydrogen bonded complexes are discussed in comparison with results from MO calculations. Limitations of such studies as well as scope for further investigations are indicated.

Narrowband Detection of Acoustic Source in Shallow Ocean using Vector Sensor Array

The problem of narrowband CFAR (constant false alarm rate) detection of an acoustic source at an unknown location in a range-independent shallow ocean is considered. If a target is present, the received signal vector at an array of N sensors belongs to an M-dimensional subspace if N exceeds the number of propagating modes M in the ocean. A subspace detection method which utilises the knowledge of the signal subspace to enhance the detector performance is presented in thisMpaper. It is shown that, for a given number of sensors N, the performance of a detector using a vector sensor array is significantly better than that using a scalar sensor array. If a target is detected, the detector using a vector sensor array also provides a concurrent coarse estimate of the bearing of the target.

A rectangular laminated anisotropic shallow thin shell finite element

This report contains the details of the development of the stiffness matrix for a rectangular laminated anisotropic shallow thin shell finite element. The derivation is done under linear thin shell assumptions. Expressing the assumed displacement state over the middle surface of the shell as products of one-dimensional first-order Hermite interpolation polynomials, it is possible to insure that the displacement state for the assembled set of such elements, to be geometrically admissible. Monotonic convergence of the total potential energy is therefore possible as the modelling is successively refined. The element is systematically evaluated for its performance considering various examples for which analytical or other solutions are available

A study of the spectrum of an acoustic field in shallow water due to noise sources at the surface

An expression for the spectrum and cross spectrum of an acoustic field measured at two vertically separated sensors in shallow water has been obtained for any correlated noise sources distributed over the surface. Numerical results are presented for the case where the noise sources, white noise and wind-induced colored noise, are contained within a circular disk centered over the sensors. The acoustic field is generally inhomogeneous except when the channel is deep. The coherence function becomes real for a large disk, for a radius greater than 25 times the depth of the channel, decreases with further increase of the size of the disk, and finally tapers off after certain limiting size, approximately given by 1/alpha, where alpha is the attenuation coefficient.

Signal subspace approach in localization of sound source in shallow water

A new algorithm based on signal subspace approach is proposed for localizing a sound source in shallow water. In the first instance we assumed an ideal channel with plane parallel boundaries and known reflection properties. The sound source is assumed to emit a broadband stationary stochastic signal. The algorithm takes into account the spatial distribution of all images and reflection characteristics of the sea bottom. It is shown that both range and depth of a source can be measured accurately with the help of a vertical array of sensors. For good results the number of sensors should be greater than the number of significant images; however, localization is possible even with a smaller array but at the cost of higher side lobes. Next, we allowed the channel to be stochastically perturbed; this resulted in random phase errors in the reflection coefficients. The most singular effect of the phase errors is to introduce into the spectral matrix an extra term which may be looked upon as a signal generated coloured noise. It is shown through computer simulations that the signal peak height is reduced considerably as a consequence of random phase errors.

Second harmonic generation in some donor-acceptor ethylenes—I

We report the absorption spectra, oscillator strengths, ground state and excited state dipole moments, and molecular second order polarizability coefficients (βCT) due to donor—acceptor charge transfer in four trisubstituted ethylenes, namely 1,1-bisdimethylamino-2-nitroethylene, 1,1-bispyrolidino-2-nitroethylene, 1,1-bispiperidino-2-nitroethylene and 1,1-bismorpholino-2-nitroethylene. The results are compared with that of trans-N,N-dimethylamino-nitroethylene, which has a large βCT. The powder second harmonic generation (SHG) intensity of all these molecules is also measured and only 1,1-bispiperidino-2-nitroethylene is found to possess an efficiency of 20% of that of urea under the same conditions. The SHG efficiency of this compound and deficiency in the other molecules in the powdered state is discussed in terms of their arrangements in the unit cell. The crystal structure of the active molecule is also presented and the structure—property relationship is critically examined in all these molecules.

Electron Donor-Acceptor Complexes of the Fullerenes C60 and C70 with Amines

Based on electronic absorption spectroscopy, C60 is found to form complexes with aromatic amines with an enthalpy of association in the range 9-16 kJ mol-1. Interaction of C70 with the amines is negligible. Cyclic voltammetric measurements confirm these observations.

Molecular structure of electron donor-acceptor complexes of metallotetraphenylporphyrins with trinitrobenzene

The metallotetraphenylporphyrins, MTPPs, where M=Co(II), Cu(II) and Ag(II) form one to one molecular complexes in solution with 1,3,5-trinitrobenzene (TNB). The crystal structure of CoTPP.TNB.2CH3OH revealed that the mean separation between the porphyrin and TNB planes is 3·27 Å and the centre of the aryl ring of TNB is displaced by 0·90 Å from the centre of the porphyrin plane. Extended Huckel molecular orbital calculations suggest that acceptor orbitals are predominantly nitro-group based rather than an aryl π framework. The contribution of the metal orbitals in the donation is also seen as predicted by the structural data. Electrochemical redox measurements in solution provide evidence for charge-transfer stabilisation in these complexes.

Folding of a Donor-Containing Ionene by Intercalation with an Acceptor

Cationic ionenes that bear electron-rich 1,5-dialkoxynaphthalene (DAN) units within the alkylene segment were allowed to interact with different types of electron-deficient, acceptor-containing molecules in an effort to realize intercalation-induced folding of the ionenes; the collapse of the chains was expected to occur in such a way that the donor and acceptor units become arranged in an alternating fashion. Several acceptor-bearing molecules were prepared by the derivatization of pyromellitic dianhydride and naphthalene tetracarboxylic dianhydride with two different oligoethylene glycol monomethyl ether monoamines. This yielded acceptor molecules with different water solubility and allowed the examination of solvophobic effects in the folding process. UV/Vis spectroscopic studies were carried out by using a 1:1 mixture of the DAN-ionenes and different acceptor molecules in water/DMSO solvent mixtures. The intensity of the charge-transfer (CT) band was seen to increase with the water content in the solvent mixture, thereby suggesting that the intercalation is indeed aided by solvophobic effects. The naphthalene diimide (NDI) bearing acceptor molecules consistently formed significantly stronger CT complexes when compared to the pyromellitic diimide (PDI) bearing acceptor molecules, which is a reflection of the stronger pi-stacking tendency of the former. AFM studies of drop-cast films of different ionene-acceptor combinations revealed that compact folded structures are formed most effectively under conditions in which the strongest CT complex is formed.

Pulsed laser deposition film of a donor-acceptor-donor polymer as possible active layer in devices

A molecule having a ketone group between two thiophene groups was synthesized. Presence of alternating electron donating and accepting moieties gives this material a donor-acceptor-donor (DAD) architecture. PolyDAD was synthesized from DAD monomer by oxidative polymerization. Device quality films of polyDAD were fabricated using pulsed laser deposition technique. X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectra (FTIR) data of both as synthesized and film indicate the material does not degrade during ablation. Optical band gap was determined to be about 1.45 eV. Four orders of magnitude increase in conductivity was observed from as synthesized to pulsed laser deposition (PLD) fabricated film of polyDAD. Annealing of polyDAD films increase conductivity, indicating better ordering of the molecules upon heating. Rectifying devices were fabricated from polyDAD, and preliminary results are discussed.

Exact free-surface flows for shallow-water equations .1. - the incompressible case

A comprehensive exact treatment of free surface flows governed by shallow water equations (in sigma variables) is given. Several new families of exact solutions of the governing PDEs are found and are shown to embed the well-known self-similar or traveling wave solutions which themselves are governed by reduced ODEs. The classes of solutions found here are explicit in contrast to those found earlier in an implicit form. The height of the free surface for each family of solutions is found explicitly. For the traveling or simple wave, the free surface is governed by a nonlinear wave equation, but is arbitrary otherwise. For other types of solutions, the height of the free surface is constant either on lines of constant acceleration or on lines of constant speed; in another case, the free surface is a horizontal plane while the flow underneath is a sine wave. The existence of simple waves on shear flows is analytically proved. The interaction of large amplitude progressive waves with shear flow is also studied.

Characterization and Acceptor Preference of a Soluble Meningococcal Group C Polysialyltransferase

Vaccines against Neisseria meningitidis group C are based on its alpha-2,9-linked polysialic acid capsular polysaccharide. This polysialic acid expressed on the surface of N. meningitidis and in the absence of specific antibody serves to evade host defense mechanisms. The polysialyltransferase (PST) that forms the group C polysialic acid (NmC PST) is located in the cytoplasmic membrane. Until recently, detailed characterization of bacterial polysialyltransferases has been hampered by a lack of availability of soluble enzyme preparations. We have constructed chimeras of the group C polysialyltransferase that catalyzes the formation alpha-2,9-polysialic acid as a soluble enzyme. We used site-directed mutagenesis to determine the region of the enzyme necessary for synthesis of the alpha-2,9 linkage. A chimera of NmB and NmC PSTs containing only amino acids 1 to 107 of the NmB polysialyltransferase catalyzed the synthesis of alpha-2,8-polysialic acid. The NmC polysialyltransferase requires an exogenous acceptor for catalytic activity. While it requires a minimum of a disialylated oligosaccharide to catalyze transfer, it can form high-molecular-weight alpha-2,9-polysialic acid in a nonprocessive fashion when initiated with an alpha-2,8-polysialic acid acceptor. De novo synthesis in vivo requires an endogenous acceptor. We attempted to reconstitute de novo activity of the soluble group C polysialyltransferase with membrane components. We found that an acapsular mutant with a defect in the polysialyltransferase produces outer membrane vesicles containing an acceptor for the alpha-2,9-polysialyltransferase. This acceptor is an amphipathic molecule and can be elongated to produce polysialic acid that is reactive with group C-specific antibody.