In situ electrochemical contact angle study of hemoglobin and hemoglobin–Fe3O4 nanocomposites

The electrochemical redox-induced contact angle changes of hemoglobin droplets in the absence and presence of tetraheptylammonium-capped Fe₃O₄ nanoparticles have been explored by using in situ electrochemical contact angle measurements. The results indicate that the electrochemical redox process may lead to some structure changes of hemoglobin (Hb), which could further induce the hydrophobic-to-hydrophilic changes of the relative droplets. Our observations demonstrate that hemoglobin could self-assemble on the surface of the functionalized Fe₃O₄ nanoparticles as Hb–Fe₃O₄ nanocomposites, which may contribute to much more significant change of the electrochemical redox-induced contact angle values than that with free nano-Fe₃O₄. These results suggest that in situ electrochemical contact angle measurements could be readily applied as a new and convenient method to detect some specific biological process. Figure Schematic drawing of the possible process and contact angle changes for the self-assembly of hemoglobin on the tetraheptylammonium-capped Fe₃O₄ nanoparticles Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Preparation of superhydrophobic PET fabric from Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> hybrid: geometrical approach to create high contact angle surface from low contact angle materials

In this work we prepare high contact Poly Ethylene Terephthalate (PET) fabric surface from low contact angle materials. Superhydrophobic PET fabric is prepared by coating the fabric with hybrid Al₂O₃–SiO₂ sol. In this case, the high contact angle Al₂O₃–SiO₂ hybrid is created from low contact angle Al₂O₃ and SiO₂ precursors. PET treated with hybrid Al₂O₃–SiO₂ exhibit Water Contact Angle (WCA) as 150°, while PET treated with individual Al₂O₃ sol or SiO₂ sol exhibits lower WCA, (Al₂O₃ WCA = 137°; SiO₂ WCA = 141°). FESEM and AFM investigations show that the hybrid Al₂O₃–SiO₂ sol and individual Al₂O₃ or SiO₂ sol imparted different roughness geometry on the PET fabric surface. We observe surface structure of fish fin-like, particle-like and hybrid fin-particle for treated PET fabric with; Al₂O₃, SiO₂ and hybrid Al₂O₃–SiO₂ sol, under FESEM and AFM observations.AFM observations show the evolution of roughness (Ra) dimension of different surface structures with the order of: SiO₂ < Al₂O₃ < Al₂O₃–SiO₂ (Ra = 31, 63 and 273 nm). We believe that the disparity of the surface geometries lead into different surface WCA. FTIR spectra of Hybrid Al₂O₃–SiO₂ shows additional peak at 902, 850, 557, and 408 cm⁻¹ which can be ascribed to the hybridization structure.     

How does tack depend on time of contact and contact pressure?

The tack of polymer melts on rigid substrates under conditions of short contact times and low pressures is examined. The substrate is modeled as a random rough surface with a distribution of asperities heights. The true contact area between the adhesive and the substrate is calculated for a given total load and elastic modulus of the substrate. The dependence of tack on contact time is accounted for by introducing the relaxation of the adhesive through a time-dependent elastic modulus. For relatively high pressures the tack is predicted to scale with 1/E so that for short contact times, t_c, the tack is predicted to scale with (t_c/τ_e)^1/2, where τ_e is the entanglement time. For lower pressures this simple scaling law is no longer valid and we predict a complex variation of tack with contact time and molecular parameters. © 1996 John Wiley & Sons, Inc.     

Comparison of hydrophobicity studies of silica aerogels using contact angle measurements with water drop method and adsorbed water content measurements made by Karl Fischer’s titration method

Hydrophobic silica aerogels possesses potential applications as insulating materials for refrigerators, furnaces and thermos flasks. In such applications, aerogel materials may get exposed for longer time to atmosphere and the adsorbed water content from surroundings may deteriorate its properties. Therefore, hydrophobicity of the arogels becomes crucial parameter and needs to be evaluated critically. In the present works, silica alcogels were prepared using the mixture of tetramethoxysilane and methyltrimethoxysilane (MTMS) as precursor chemicals for silica. The concentration of MTMS, which is used as hydrophobic reagent, in the said mixture of silicon alkoxide was varied between 0 and 100% in steps of 25%. After gelation, the alcogels were dried supercritically by solvent extraction method. Resulted aerogels were exposed to relative humidity of 90% for a period of one month which were then characterized to assess hydrophobicity by the contact angle using water drop method and adsorbed water content measurements by Karl Fischer’s Titration method. Observed contact angle and water content measurements were compared and the results are reported in the present research paper.     

Magic angle Raman optical activity: β-pinene and nopinone

Applying the Stokes—Mueller formalism to the case of right angle scattering of chiral molecules randomly oriented in an optically isotropic phase, orientations of the polarization analyzer in the scattered beam at the ‘magic angle’ of ∼ ±35.26° to the vertical have been identified to isolate the pure magnetic dipole contribution to the ROA intensity. Magic angle ROA spectra of(−) β-pinene and (+) nopinone from 350 to 1350 cm⁻¹ are presented as first examples. Comparing the magic angle ROA spectra of both terpenes with their corresponding depolarized spectra, the origin of the couplet at 716 and 765 cm⁻¹ in the magic angle ROA spectrum of β-pinene is ascribed to interactions between deformations and torsions of the olefinic group with a skeletal mode of the pinane structure.     

Probability Properties of Multi－contact in Protein Molecules

The compact conformations of polymers are important because the native conformations of all bio-polymers with certain function are highly compact. The properties of mutil-contact bio-polymer chains were studied by Gaussian statistics of the random-flight chain. The theoretical expressions(were given, also), the calculations of probability distributions and correlation functions for different topologic cases were derived and made respectively. Comparison between single, double and triple contacts was also made. By means of setting the parameters, the results of the current calculations of the multiple contacts are just the same as those calculated by single, double or tripe contacts separately. It is a useful method to investigate native conformations of biopolymers. The probabilities of multi contacts and correlation functions between chain‘s contacts were calculated for the Gaussian chains. Because the bond probability distributions are Gaussian‘s distributions, the probability distributions of the separations of various points along the chains are always consecutive. All the contacts may break up into several groups, and each group consists of many contacts. Here we investigated the probability distribution from one group to three groups of contacts.     

Rubbing angle effect on in‐plane switching liquid crystal displays

The rubbing angle effect on transmissive in‐plane switching liquid crystal displays is analysed by the Jones matrix method. Simulation results show that the optimum rubbing angle is around 30°–40°; the cell gap/birefringence product (dΔn) is about 0.33 µm. Increasing the rubbing angle can shorten the rise time and enlarge the grey scale voltage intervals. The optical characteristics are similar in two cells with different rubbing angles. These effects are particularly attractive for liquid crystal TV applications.     

What really drives chemical reactions on contact charged surfaces?

Although it is known that contact-electrified polymers can drive chemical reactions, the origin of this phenomenon remains poorly understood. To date, it has been accepted that this effect is due to excess electrons developed on negatively charged surfaces and to the subsequent transfer of these electrons to the reactants in solution. The present study demonstrates that this view is incorrect and, in reality, the reactions are driven by mechanoradicals created during polymer-polymer contact.     

I-V Characteristics of ZnO?ZnO contact during oxygen adsorption

The adsorption of oxygen on ZnO has been studied by observing the nonohmic characteristics of contacted ZnO crystals. When the sample assembly was evacuated at 773 K, there was a negative peak at the bias of 10 mV in the(I-kV) vs. V plot. When the assembly was exposed to oxygen at 298–573 K, the mean conductivity decreased and a negative peak at the bias of 50–230 mV was found in the(I-kV) vs. V plot. To analyze the experimental results, a simple model was developed assuming the contact to be of two semiconductor surfaces separated by a finite distance. From the experimental results and theoretical suggestions, we estimated the height of surface barrier during oxygen adsorption.     

How random are intrinsically disordered proteins? A small angle scattering perspective

While the crucial role of intrinsically disordered proteins (IDPs) in the cell cycle is now recognized, deciphering their molecular mode of action at the structural level still remains highly challenging and requires a combination of many biophysical approaches. Among them, small angle X-ray scattering (SAXS) has been extremely successful in the last decade and has become an indispensable technique for addressing many of the fundamental questions regarding the activities of IDPs. After introducing some experimental issues specific to IDPs and in relation to the latest technical developments, this article presents the interest of the theory of polymer physics to evaluate the flexibility of fully disordered proteins. The different strategies to obtain 3-dimensional models of IDPs, free in solution and associated in a complex, are then reviewed. Indeed, recent computational advances have made it possible to readily extract maximum information from the scattering curve with a special emphasis on highly flexible systems, such as multidomain proteins and IDPs. Furthermore, integrated computational approaches now enable the generation of ensembles of conformers to translate the unique flexible characteristics of IDPs by taking into consideration the constraints of more and more various complementary experiment. In particular, a combination of SAXS with high-resolution techniques, such as x-ray crystallography and NMR, allows us to provide reliable models and to gain unique structural insights about the protein over multiple structural scales. The latest neutron scattering experiments also promise new advances in the study of the conformational changes of macromolecules involving more complex systems.     

Does compressibility affect the results obtained by small angle neutron scattering?

Recently a few papers have been devoted to the scattering by polymer solutions and blends^(1,2) assuming that the systems under investigation are compressible, contrarily to what is usually done. This is motivated by the fact that if one uses the theory of incompressible mixtures in scattering experiments, one obtains values of the Flory⁽³⁾ χ parameter which are inconsistent with the values obtained by other techniques. In this paper we would like to show that, contrarily to what has been said, the effect of compressibility can be easily evaluated; it is very small and already corrected in the classical treatment of the data used in light or neutron scattering experiments.     

Exact tilt angle profiles for splay–bend deformations in nematic liquid crystals

The exact tilt angle profiles for splay–bend deformations, in nematic liquid crystal samples limited by inhomogeneous surfaces, are determined in the one‐constant approximation. The boundary value problem concerning the situation of strong anchoring at the surfaces of a sample of slab shape of thickness d (Dirichlet's problem) is analytically solved in the presence of an external uniform field. The boundary value problem concerning the weak anchoring situation (mixed problem) is also exactly solved in the absence of an external field. The results are used to obtain the thickness dependence of the optical path difference between the ordinary and extraordinary rays, from which the physical properties of the sample can be deduced.     

Is ammonia a better solvent than water for contact ion pairs?

The existence of a charge-transfer-to-solvent process when a KI contact ion pair (CIP) dissolved in supercritical water (SCW) is excited by UV light was confirmed by use of electronic structure calculations applied to molecular dynamics trajectories. We observed similar behavior with fluid density as that found for the KI-CIP in supercritical ammonia (SCA); nevertheless, there are some distinct features in the two supercritical solvents. First, the effect of the solvent field due to the molecules lying beyond the first solvation shell is very different in SCW compared with that observed in SCA; in SCW it actually has a destabilizing effect over the ground and excited states. Second, our results for the thermodynamic behavior of the CIP indicate that SCA is better solvent than SCW for this species. The differences found can be attributed to the solvent molecules surrounding the CIP and bridging the two ions; they shield more efficiently the ion pair from long-range solvent effects in SCA. The different behavior is partially attributed to a stronger solvent-solvent interaction in SCW than in SCA.     

Résonance surharmonique d'ordre deux dans un contact sphère-plan

For an impact oscillator with an Hertzian contact (sphere-plane contact), we study the superharmonic resonance of order two. Without loss of contact, one can describe this resonance by approximating the elastic contact force (third order Taylor expansion) and by using the method of multiple scales. With impacts, we use a shooting method. Results show that this resonance constitutes a precursor of vibro-impact conditions.     

Un nouveau modèle de la zone de contact outil copeau

In the study of the cutting, we develop a model for the contact between ship and tool based on the notion of stress couple. We present the main hypotheses for the associated 3D analytic model and the results arising premil.     

Defined solid angle absolute β-counting for use in the radioanalysis of environmental samples

Defined solid angle absolute -counting (DSAABC) of thin samples using an end-window Geiger-Müller counter is shown to be a useful auxiliary method in some fields of environmental radioanalysis. Correction factors are used in the DSAABC method to account for the numerous effects responsible for losses and gains in the -counting rate. A few new proposals are made in connection with the possiblities of the reduction and evaluation of the above factors on the basis of the comprehensive review of the literature. New formulas are proposed in order to evaluate correction factors for backscattering and internal backscattering. The case of the exponential decrease of activity as function of the depth in filter sample is treated separately. The most important experiences related to the use of the DSAABC method in three practical applications are presented.     

Communication: Accurate determination of side-chain torsion angle χ1 in proteins: phenylalanine residues

Quantitative side-chain torsion angle χ(1) determinations of phenylalanine residues in Desulfovibrio vulgaris flavodoxin are carried out using exclusively the correlation between the experimental vicinal coupling constants and theoretically determined Karplus equations. Karplus coefficients for nine vicinal coupling related with the torsion angle χ(1) were calculated using the B3LYP functional and basis sets of different size. Optimized χ(1) angles are in outstanding agreement with those previously reported by employing x ray and NMR measurements.     

Contact angle and adsorption behavior of carboxylic acids on α-Al2O3 surfaces

There is good correlation of contact angle measurements and contact angles calculated from surfactant adsorption density data for an electrically neutral surface, as reported in a previous paper for the system hematite-aqueous solution-ketone, with surfactant hexadecyl sulfonic acid. The same method is not sufficient when the hematite surface is electrically charged. Data was collected to develop the appropriate form of an electrostatic term for the analysis. Acid-base titration was used to evaluate surface electrical properties versus pH for the hematite used in the study. Surfactant adsorption isotherms were measured at pH of 4.5, 5.5, 6, and 7 to use in developing an equation for effect of surface potential on contact angle. After adding a term for the contribution of the electric field, the contact angles calculated from adsorption data follow the measured contact angles well.     

On the orientation of a designed transmembrane peptide: toward the right tilt angle?

The orientation of the transmembrane peptide WALP23 under small hydrophobic mismatch has been assessed through long-time-scale molecular dynamics simulations of hundreds of nanoseconds. Each simulation gives systematically large tilt angles (>30 degrees). In addition, the peptide visits various azimuthal rotations that mostly depend on the initial conditions and converge very slowly. In contrast, small tilt angles as well as a well-defined azimuthal rotation were suggested by recent solid-state 2H NMR studies on the same system. To optimally compare our simulations with NMR data, we concatenated the different trajectories in order to increase the sampling. The agreement with 2H NMR quadrupolar splittings is spectacularly better when these latter are back-calculated from the concatenated trajectory than from any individual simulation. From these ensembled-average quadrupolar splittings, we then applied the GALA method as described by Strandberg et al. (Biophys J. 2004, 86, 3709-3721), which basically derives the peptide orientation (tilt and azimuth) from the splittings. We find small tilt angles (6.5 degrees), whereas the real observed tilt in the concatenated trajectory presents a higher value (33.5 degrees). We thus propose that the small tilt angles estimated by the GALA method are the result of averaging effects, provided that the peptide visits many states of different azimuthal rotations. We discuss how to improve the method and suggest some other experiments to confirm this hypothesis. This work also highlights the need to run several and rather long trajectories in order to predict the peptide orientation from computer simulations.