Segmental dynamics in poly(methyl acrylate) on silica: molecular-mass effects

The effect of molecular mass on the segmental dynamics of poly(methyl acrylate) (PMA) adsorbed on silica was studied using deuterium quadrupole-echo nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry. Samples adsorbed on silica (all about 1.5 mg PMA/m2 silica) were shown to have more restricted segmental mobility, and higher Tg's, than the corresponding bulk PMA samples. Around the glass-transition region, adsorbed samples exhibited segmental mobility, which could be classified as heterogeneous due to a superposition of more-mobile and less-mobile components present in the deuterium NMR spectra. This heterogeneity was consistent with a motional gradient with more-mobile segments near the polymer-air interface and the less-mobile species near the polymer-silica interface. The mobility of the adsorbed 77 kDa PMA sample was the lowest among the four different molecular-mass samples studied. Samples studied with masses both larger and smaller than 77 kDa had larger mobile-component fractions in the adsorbed polymer. The additional mobility was attributed to the presence of either longer tail and loop conformations in the higher molecular-mass samples or the inherent mobility of the tails in the lower molecular-mass samples on the surface.     

Optimum folding pathways of proteins: their determination and properties

We develop a dynamic optimization technique for determining optimum folding pathways of proteins starting from different initial configurations. A coarse-grained Go model is used. Forces acting on each bead are (i) the friction force, (ii) forces from bond length constraints, (iii) excluded volume constraints, and (iv) attractive forces between residue pairs that are in contact in the native state. An objective function is defined as the total attractive energy between nonbonded residues, which are neighbors in the native state. The objective function is minimized over all feasible paths, satisfying bond length and excluded volume constraints. The optimization problem is nonconvex and contains a large number of constraints. An augmented Lagrangian method with a penalty barrier function was used to solve the problem. The method is applied to a 36-residue protein, chicken villin headpiece. Sequences of events during folding of the protein are determined for various pathways and analyzed. The relative time scales are compared and scaled according to experimentally measured events. Formation times of the helices, turn, and the loop agree with experimental data. We obtain the overall folding time of the protein in the range of 600 ns-1.2 micros that is smaller than the experimental result of 4-5 micros, showing that the optimal folding times that we obtain may be possible lower bounds. Time dependent variables during folding and energies associated with short- and long-range interactions between secondary structures are analyzed in modal space using Karhunen-Loeve expansion.     

Experimental and numerical investigation of transition to turbulent flow and heat transfer inside a horizontal smooth rectangular duct under uniform bottom surface temperature

In this study, steady-state turbulent forced flow and heat transfer in a horizontal smooth rectangular duct both experimentally and numerically investigated. The study was carried out in the transition to turbulence region where Reynolds numbers range from 2,323 to 9,899. Flow is hydrodynamically and thermally developing (simultaneously developing flow) under uniform bottom surface temperature condition. A commercial CFD program Ansys Fluent 12.1 with different turbulent models was used to carry out the numerical study. Based on the present experimental data and three-dimensional numerical solutions, new engineering correlations were presented for the heat transfer and friction coefficients in the form of $ {\text{Nu}} = {\text{C}}_{2} {\text{Re}}^{{{\text{n}}_{ 1} }} $ and $ {\text{f}} = {\text{C}}_{3} {\text{Re}}^{{{\text{n}}_{3} }} $ , respectively. The results have shown that as the Reynolds number increases heat transfer coefficient increases but Darcy friction factor decreases. It is seen that there is a good agreement between the present experimental and numerical results. Examination of heat and mass transfer in rectangular cross-sectioned duct for different duct aspect ratio (α) was also carried out in this study. Average Nusselt number and average Darcy friction factor were expressed with graphics and correlations for different duct aspect ratios.     

Performance studies of energy consumption for single and multiple nozzle systems under impinging air jets

Impinging air jets of various shapes, sizes and configurations are commonly used in heating, cooling and drying industrial processes. An analytical study has been carried out to optimise the thermal performance of single and multiple nozzle systems using impinging air jets. The optimisation of the nozzle array was given for practical purposes. The results show that within practical limits, a narrower nozzle size results in a greater heat and mass transfer coefficient. An economical analysis of the drying processes is also given for slot nozzles.     

Anti-proliferative effects of gold nanoparticles functionalized with Semaphorin 3F

The new vessel formations play a vital role in growth and spread of cancer. Current anti-angiogenic therapies, predominantly based on vascular endothelial growth factor (VEGF) inhibition, can inhibit vascular development; however, they are usually ineffective against the primary tumor occurrence. The aim of this study was to assess anti-angiogenic effects of gold nanoparticles (AuNPs) functionalized with Semaphorin (Sema) 3F protein. The polyethylene glycol (PEG)-coated AuNPs were covalently functionalized with Sema 3F and labeled with the TAMRA fluorescent dye. The effect of the NPs on human umbilical vein endothelial cells (HUVECs) is probed in the way of internalization and viability assays. AuNP-Sema 3F bioconjugates showed great endothelial cell uptake. AuNP-Sema 3F bioconjugates reduced VEGF₁₆₅-induced endothelial cell proliferation more effectively than Sema 3F alone, suggesting that the therapeutic effects of Sema 3F can be improved by conjugation to AuNPs. Also, no significant toxicity effect was induced by bioconjugates. This is the first study that reports a covalent binding of full length Sema 3F to NPs. The exogenously administration of Sema 3F, which has both anti-angiogenic and anti-tumoral activity, to tumor vasculature via a carrying platform may not only lead to more effective anti-angiogenic treatment but also may make current approach more applicable in clinical use like drug delivery system.

Open image in new window

Graphical abstract Anti-proliferative effects of gold nanoparticles conjugated with Semaphorin 3F against VEGF₁₆₅-stimulated cell proliferation

     

Electron paramagnetic resonance and thermoluminescence study of Ag ions in Li2B4O7 crystals

Electron paramagnetic resonance (EPR) is used to investigate the effects of ionizing radiation on Ag-doped lithium tetraborate (Li₂B₄O₇) crystals. Two similar, yet distinct, trapped-hole centers (Ag²⁺ ions substituting for Li⁺ ions) are produced by 60 kV x rays. One Ag²⁺ ion, labeled Center A, has no nearby defects and the other Ag²⁺ ion, labeled Center B, has a neighboring impurity which is most likely a Ag⁺ ion substituting for a Li⁺ ion. The production and thermal decay properties of the two Ag²⁺ ions are described and their g matrices and ¹⁰⁷Ag and ¹⁰⁹Ag hyperfine matrices are obtained from the EPR angular dependences. The principal values of the g matrices are similar for the two centers, but the hyperfine principal values differ significantly (Center B has smaller values than Center A). There are also differences in the directions of the principal axes for the two centers. Together, these results imply (1) that the unpaired spin is less localized for Center B and (2) that the ground-state positions of the neighboring oxygen ions are different for Centers A and B. This explains why the peaks of the Ag²⁺ charge-transfer photoluminescence bands associated with Centers A and B occur at different wavelengths (502 and 725 nm, respectively). An isochronal pulsed thermal anneal shows that these radiation-induced Ag²⁺ ions serve as the recombination site for the intense thermoluminescence peak observed near 152 °C.     

The design of Helmholtz resonator based acoustic lenses by using the symmetric Multi-Level Wave Based Method and genetic algorithms

Sonic crystals can be used as acoustic lenses in certain frequencies and the design of such systems by creating vacancies and using genetic algorithms has been proven to be an effective method. So far, rigid cylinders have been used to create such acoustic lens designs. On the other hand, it has been proven that Helmholtz resonators can be used to construct acoustic lenses with higher refraction index as compared to rigid cylinders, especially in low frequencies by utilizing their local resonances. In this paper, these two concepts are combined to design acoustic lenses that are based on Helmholtz resonators. The Multi-Level Wave Based Method is used as the prediction method. The benefits of the method in the context of design procedure are demonstrated. In addition, symmetric boundary conditions are derived for more efficient calculations. The acoustic lens designs that use Helmholtz resonators are compared with the acoustic lens designs that use rigid cylinders. It is shown that using Helmholtz resonator based sonic crystals leads to better acoustic lens designs, especially at the low frequencies where the local resonances are pronounced.     

Experimental investigation of flow and heat transfer in rectangular cross-sectioned duct with baffles mounted on the bottom surface with different inclination angles

In this study, steady-state forced convection heat transfer and pressure drop characteristics in a horizontal rectangular cross-sectioned duct, baffles mounted on the bottom surface with different inclination angles were investigated experimentally in the Reynolds number range from 1 × 10³ to 1 × 10⁴. The study was performed under turbulent flow conditions. Effects of different baffle inclination angles on flow and heat transfer were studied. Results are also presented in terms of thermal enhancement factor. It is observed that increasing in baffle inclination angle enhances the heat transfer and causes an increase in pressure drop in the duct.     

A mononuclear, mixed (salicylato) (nicotinamide) complex of Zn(II) with penta- and hexa-coordination sites: a novel framework structure

The title compound, diaqua(bissalicylato-??O)(bisnicotinamide-??N)zinc(II)][bis(triaqua (monosalicylato-??O)(mononicotinamide-??N)zinc(II)salicylate, includes three Zn(II) ions, four nicotinamide ligands, six salicylate ligands and eight coordinated aqua ligands in the asymmetric unit in complex structure. The geometry around one of the Zn(II) ions is a slightly distorted octahedron, of which the equatorial plane is formed by two carboxylate oxygens and two aqua oxygens, while the axial positions are occupied by two pyridyl nitrogen atoms. The other Zn(II) ions adopt fivefold coordinations with one carboxylate oxygen atom from salicylate ligand, one N atom from nicotinamide ligand and three oxygen atoms from aqua ligands. In addition, there are two salicylate anions in the unit cell that are not coordinated. They provide charge balance as counter-ions in the complex framework.