Carbon-13 relaxation study of chain segmental motion and side-chain internal rotations of poly(isobutyl methacrylate) in solution

The dynamics of poly(isobutyl methacrylate) in toluene solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed using the Dejean-Laupretre-Monnerie (DLM) model, which describes the dynamical processes in the backbone in terms of conformational transitions and bond librations. The relaxation data of the side chain nuclei have been analyzed by assuming different motional models, namely, unrestricted rotational diffusion, three site jumps, and restricted rotational diffusion. The different models have been compared for their ability to reproduce the experimental spin-lattice relaxation times and also to predict the behavior of NOE as a function of temperature. Conformational energy calculations have been carried out on a model compound by using the semiempirical quantum chemical method, AM1, and the results confirm the validity of the motional models used to describe the side-chain motion.

Conditional linearization in nonlinear random vibration

In this paper, an improved probabilistic linearization approach is developed to study the response of nonlinear single degree of freedom (SDOF) systems under narrow-band inputs. An integral equation for the probability density function (PDF) of the envelope is derived. This equation is solved using an iterative scheme. The technique is applied to study the hardening type Duffing's oscillator under narrow-band excitation. The results compare favorably with those obtained using numerical simulation. In particular, the bimodal nature of the PDF for the response envelope for certain parameter ranges is brought out.

Needleless Vaccine Delivery Using Micro-Shock Waves

Shock waves are one of the most efficient mechanisms of energy dissipation observed in nature. In this study, utilizing the instantaneous mechanical impulse generated behind a micro-shock wave during a controlled explosion, a novel nonintrusive needleless vaccine delivery system has been developed. It is well-known that antigens in the epidermis are efficiently presented by resident Langerhans cells, eliciting the requisite immune response, making them a good target for vaccine delivery. Unfortunately, needle-free devices for epidermal delivery have inherent problems from the perspective of the safety and comfort of the patient. The penetration depth of less than 100 mu m in the skin can elicit higher immune response without any pain. Here we show the efficient utilization of our needleless device (that uses micro-shock waves) for vaccination. The production of liquid jet was confirmed by high-speed microscopy, and the penetration in acrylamide gel and mouse skin was observed by confocal microscopy. Salmonella enterica serovar Typhimurium vaccine strain pmrG-HM-D (DV-STM-07) was delivered using our device in the murine salmonellosis model, and the effectiveness of the delivery system for vaccination was compared with other routes of vaccination. Vaccination using our device elicits better protection and an IgG response even at a lower vaccine dose (10-fold less) compared to other routes of vaccination. We anticipate that our novel method can be utilized for effective, cheap, and safe vaccination in the near future.

Experimental studies of a distorted turbulent spot in a three-dimensional flow

We report here on the results of a series of experiments carried out on a turbulent spot in a distorted duct to study the effects of a divergence with straight streamlines preceded by a short stretch of transverse streamline curvature, both in the absence of any pressure gradient. It is found that the distortion produces substantial asymmetry in the spot: the angles at which the spot cuts across the local streamlines are altered dramatically (in contradiction of a hypothesis commonly made in transition zone modelling), and the Tollmien-Schlichting waves that accompany the wing tips of the spot are much stronger on the outside of the bend than on the inside. However there is no strong effect on the internal structure of the spot and the eddies therein, or on such propagation characteristics as overall spread rate and the celerities of the leading and trailing edges. Both lateral streamline curvature and non-homogeneity of the laminar boundary layer into which the spot propagates are shown to be strong factors responsible for the observed asymmetry. It is concluded that these factors produce chiefly a geometric distortion of the coherent structure in the spot, but do not otherwise affect its dynamics in any significant way.

Linear and nonlinear optical properties of cumulenes and polyenynes: a model exact study

Model exact static and frequency-dependent polarizabilities, static second hyperpolarizabilities and THG coefficents of cumulenes and polyenynes, calculated within the correlated Pariser-Parr-Pople (PPP) model defined over the pi-framework are reported and compared with the results for the polyenes. It is found that for the same chain length, the polarizabilities and THG coefficients of the cumulenes are largest and those of the polyenynes smallest with the polyenes having an intermediate value. The optical gap of the infinite cumulene is lowest (0.75 eV) and is associated with a low transition dipole moment for an excitation involving transfer of an electron between the two orthogonal conjugated pi-systems. The polyenynes have the largest optical gap (4.37 eV), with the magnitude being nearly independent of the chain length. This excitation involves charge transfer between the conjugated bonds in the terminal triple bond. Chain length and frequency dependence of alpha(ij) and gamma(ijkl) of these systems are also reported. The effect of a heteroatom on the polarizability and THG coefficients of acetylenic systems is also reported. It has been found that the presence of the heteroatom reduces the polarizability and THG coefficients of these systems, an effect opposite to that found in the polyenes and cyanine dyes. This result has been associated with the different nature of the charge transfer in the acetylenic systems.

Generation of novel materials for nonlinear optics: Analysis of hydrogen-bonded networks in haloaromatic and aliphatic amine-tartrate complexes

Five tartrate-amine complexes have been studied in terms of crystal packing and hydrogen bonding frameworks. The salts are 3-bromoanilinium-L-monohydrogen tartrate 1, 3-fluoroanilinium-D-dibenzoylmonohydrogen tartrate 2, 1-nonylium-D-dibenzoylmonohydrogen tartrate 3, 1 -decylium-D-dibenzoylmonohydrogen tartrate 4, and 1,4-diaminobutanium-D-dibenzoyl tartrate trihydrate 5. The results indicate that there are no halogen-halogen interactions in the haloaromatic-tartrate complexes. The anionic framework allows accomodation of ammonium ions that bear alkyl chain residues of variable lengths. The long chain amines in these structures remain disordered while the short chain amines form multidirectional hydrogen bonds on either side.

Nonlinear static and dynamic damped response of a composite rectangular plate resting on a two-parameter elastic foundation

Nonlinear static and dynamic response analyses of a clamped. rectangular composite plate resting on a two-parameter elastic foundation have been studied using von Karman's relations. Incorporating the material damping, the governing coupled, nonlinear partial differential equations are obtained for the plate under step pressure pulse load excitation. These equations have been solved by a one-term solution and by applying Galerkin's technique to the deflection equation. This yields an ordinary nonlinear differential equation in time. The nonlinear static solution is obtained by neglecting the time-dependent variables. Thc nonlinear dynamic damped response is obtained by applying the ultraspherical polynomial approximation (UPA) technique. The influences of foundation modulus, shear modulus, orthotropy, etc. upon the nonlinear static and dynamic responses have been presented.

Obliquely incident water waves against a vertical cliff

Utilizing the commutativity property of the Cartesian coordinate differential operators arising in the boundary conditions associated with the propagation of surface water waves against a vertical cliff, under the assumptions of linearized theory, the problem of obliquely incident surface waves is considered for solution. The case of normal incidence, handled by previous workers follow as a particular limiting case of the present problem, which exhibits a source/sink type behavior of the velocity potential at the shore-line. An independent method of attack is also presented to handle the case of normal incidence.

Model Hamiltonians for nonlinear optical properties of conjugated polymers

Quantum cell models for delocalized electrons provide a unified approach to the large NLO responses of conjugated polymers and pi-pi* spectra of conjugated molecules. We discuss exact NLO coefficients of infinite chains with noninteracting pi-electrons and finite chains with molecular Coulomb interactions V(R) in order to compare exact and self-consistent-field results, to follow the evolution from molecular to polymeric responses, and to model vibronic contributions in third-harmonic-generation spectra. We relate polymer fluorescence to the alternation delta of transfer integrals t(1+/-delta) along the chain and discuss correlated excited states and energy thresholds of conjugated polymers.

Nonlinear dynamics of a rigid block on a rigid base

The planar rocking of a prismatic rectangular rigid block about either of its corners is considered. The problem of homoclinic intersections of the stable and unstable manifolds of the perturbed separatrix is addressed to and the corresponding Melnikov functions are derived. Inclusion of the vertical forcing in the Hamiltonian permits the construction of a three-dimensional separatrix. The corresponding modified Melnikov function of Wiggins for homoclinic intersections is derived. Further, the 1-period symmetric orbits are predicted analytically using the method of averaging and compared with the simulation results. The stability boundary for such orbits is also established.

Crystal growth and defects characterization of zinc tris (thiourea) sulfate: a novel metalorganic nonlinear optical crystal

Single crystals of the metalorganic nonlinear optical material zinc tris (thiourea) sulfate (ZTS) were grown from aqueous solution. The morphology of the crystals was indexed. The grown crystals were characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. Spectrophotometric studies on ZTS reveal that it has good transparency for the Nd: YAG laser fundamental wavelength. Differential thermal analysis of ZTS indicates that the material does not sublime before melting but decomposes immediately after melting. The defect content of the crystals was estimated using etching and X-ray topography. The mechanical hardness anisotropy was evaluated in the (100) plane, which indicates the presence of soft directions.