Spin-diffusion couples proton relaxation rates for proteins in exchange with a membrane interface

Changes in nuclear spin-lattice relaxation rates that are induced by a freely diffusing paramagnetic relaxation agent are examined for a protein in solution and compared to the case where the protein binds to a membrane. In the solution case, the intramolecular cross-relaxation rates are modest and large differences are observed in the oxygen induced protein–proton relaxation rates. In the case where a dynamic equilibrium between solution and membrane-bound environments is established, the intramolecular ¹H cross-relaxation rates for the protein protons increase dramatically because of the slow reorientational motion in the membrane-bound environment. As a consequence, all protein protons relax with nearly the same spin-lattice relaxation rate constants when bound to the membrane, and site specific relaxation effects of the diffusing paramagnet are suppressed. Slowly reorienting sites or rotationally immobilized sites sampled by observable molecules in vivo will demonstrate similar relaxation leveling effects.     

Auditory masking in three pinnipeds: aerial critical ratios and direct critical bandwidth measurements

This study expands the limited understanding of pinniped aerial auditory masking and includes measurements at some of the relatively low frequencies predominant in many pinniped vocalizations. Behavioral techniques were used to obtain aerial critical ratios (CRs) within a hemianechoic chamber for a northern elephant seal (Mirounga angustirostris), a harbor seal (Phoca vitulina), and a California sea lion (Zalophus californianus). Simultaneous, octave-band noise maskers centered at seven test frequencies (0.2-8.0 kHz) were used to determine aerial CRs. Narrower and variable bandwidth masking noise was also used in order to obtain direct critical bandwidths (CBWs). The aerial CRs are very similar in magnitude and in frequency-specific differences (increasing gradually with test frequency) to underwater CRs for these subjects, demonstrating that pinniped cochlear processes are similar both in air and water. While, like most mammals, these pinniped subjects apparently lack specialization for enhanced detection of specific frequencies over masking noise, they consistently detect signals across a wide range of frequencies at relatively low signal-to-noise ratios. Direct CBWs are 3.2 to 14.2 times wider than estimated based on aerial CRs. The combined masking data are significant in terms of assessing aerial anthropogenic noise impacts, effective aerial communicative ranges, and amphibious aspects of pinniped cochlear mechanics.     

Spin exchange in nitroxide-charged membrane models: an ESR method for detecting photodynamic effects

Summary An electron spin resonance (ESR) method for detecting the photodynamic effects induced in membrane models is described. The method is based on the study of the spin exchange line broadening occurring in nitroxide-charged liposomes before and after visible irradiation in the prsence of various photosensitizing molecules.

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Riassunto Si descrive un metodo per la rivelazione degli effetti fotodinamici indotti in modelli di membrane, utilizzante la spettroscopia di risonanza elettronica di spin (ESR). Il metodo è basato sullo studio dell'allargamento di riga dovuto all'interazione di scambio di spin che si ha in liposomi caricati con molecole di nitrosside, prima e dopo l'irraggiamento con luce visibile in presenza di vari fotosensibilizzanti.

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Резюме Описывается метод электронного спинового резонанса для обнау-жения фотодинамическх эффекктов, индуцированных в мембранных моделях. Метод основан на изучении уширения линии, обусловленного спиовым обменом, в липо-сомах с молекулами закиси азота перед и после облучения в видимой части спектра в присутствии различных фоточувствительных молекул.

     

Domain formation in the plasma membrane: roles of nonequilibrium lipid transport and membrane proteins

Compositional lipid domains ("lipid rafts") in plasma membranes are believed to be important components of many cellular processes. The mechanisms by which cells regulate the sizes and lifetimes of these spatially extended domains are poorly understood at the moment. Here we show that the competition between phase separation in an immiscible lipid system and active cellular lipid transport processes naturally leads to the formation of such domains. Furthermore, we demonstrate that local interactions with immobile membrane proteins can spatially localize the rafts and lead to further clustering.     

Preparation and evaluation of ionomeric membranes based on sulfonated-poly (styrene_isobutylene_styrene) membranes for proton exchange membrane fuel cells (PEMFC)

Sulfonated polystyrene-block-poly-(ethylene-ran-butylene)-block-polystyrene membranes with different sulfonated levels have been prepared and evaluated as proton exchange membrane for polymer electrolyte membrane fuel cell. The polymer was sulfonated by chlorosulfonic acid. Homogeneous membranes were prepared by solvent casting method. Ion exchange capacity, degree of sulfonation, absorption, and solubility of the membranes were studied. The membranes were characterized by Fourier transform infrared, thermogravimetric analyzer, differential scanning calorimetry, and impedance spectroscopy.     

HACACO revisited: residual dipolar coupling measurements and resonance assignments in proteins

The revisited version of the HACACO experiment here presented, is more robust and straightforward to implement and continues to be, to a greater extent, a convenient tool for protein backbone resonance assignment. Additionally, it turns out to be a sensitive and accurate method to measure C(alpha)-H(alpha) residual dipolar couplings (RDCs). The performance of our new pulse scheme for measurement of RDCs was tested on two proteins with different secondary structures: one characterized by a high beta-sheet content, the second dominated by the presence of alpha-helices. In both examples the new method provided significantly more accurate data, compared to all previously published 3D techniques.     

Statistical potentials for 3D structure evaluation:From proteins to RNAs

Structure evaluation is critical to in silico 3-dimensional structure predictions for biomacromolecules such as proteins and RNAs.For proteins,structure evaluation has been paid attention over three decades along with protein folding problem,and statistical potentials have been shown to be effective and efficient in protein structure prediction and evaluation.In recent two decades,RNA folding problem has attracted much attention and several statistical potentials have been developed for RNA structure evaluation,partially with the aid of the progress in protein structure prediction.In this review,we will firstly give a brief overview on the existing statistical potentials for protein structure evaluation.Afterwards,we will introduce the recently developed statistical potentials for RNA structure evaluation.Finally,we will emphasize the perspective on developing new statistical potentials for RNAs in the near future.     

Target ion source and charge exchange cell development for the EXCYT facility

The EXCYT facility at the INFN-LNS is based on a K-800 superconducting cyclotron delivering stable ion beams on a Target Ion Source (TIS) assembly to produce the required nuclear species, and on a 15 MV Tandem for post-accelerating the radioactive beams. For some ion beams such as for Li, the extraction efficiency from the TIS is higher when obtained by positive ionisation, while the injection into the Tandem is possible only after a charge exchange to obtain negative ions. In this work we present the procedures together with the results of the production of ^6,7,8,9Li beams extracted at EXCYT during the last year. The production of the radioactive elements was performed by sending a ¹³C⁴⁺ primary beam of 45 MeV/u on a graphite target. The ionisation of the production species was achieved by a tungsten positive surface ioniser. The Li⁺ has been extracted from TIS at different energies to cross-check the transmission and the charge exchange efficiency. To perform the conversion from positive to negative ions we employed a Charge Exchange Cell (CEC) containing Cs vapours. The Li beam interacts with the latter in a two-step reaction, thus converting its charge from +1 to –1. The CEC was already characterised during off-line tests; the results obtained at EXCYT confirmed both the isotopic shift effect and the efficiency values at several given extraction energies. Future improvements of the TIS and the CEC are discussed.     

Order and membrane stability from magnetic resonance measurements: an application of statistical thermodynamics

Summary This paper compares different approaches, reported in the literature, for obtaining thermodynamic statistical information from ESR and NMR measurements on the conformations of lipid bilayers. A statistical approach recently proposed by the authors has been employed to reexamine several literature values of order parameters and to calculate Helmholtz free energy and entropy. This approach was applied to eggphosphatidylcholine, cerebroside and gangliosoyds, spin labelled at different acyl chain positions, and to bilayered membranes containing phosphatidylcholine and different gangliosides (GM1, GD1a and GT1b) at increasing glycolipid mole percent. The variation of the stability of the membrane with the peroxidation is also reexamined at different intramembrane locations by various probes. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Total cross section measurements for charge exchange of He++ ions with He and Ar atoms

Total charge exchange cross sections were measured for He⁺⁺ in He and Ar gas in the energy range from 50 to 540 eV using a single beam apparatus. For He⁺⁺ in He the measured cross section is in agreement with calculations for symmetric resonant charge exchange. For He⁺⁺ in Ar the cross section for charge exchange decreases with decreasing energy below 300 eV. The measured cross section suggests the formation of Ar⁺ ions to be more important at lower energies and the production of Ar⁺⁺ to be dominant at higher energies.     

Design and development of original WSN sensor for suspended particulate matter measurements

This paper comprehensively presents key issues in design of an original optoelectronic measurement device built to assess amount of suspended particulate matter. The paper is introduced with a short explanation of concerns with a suspended particulate matter, what role it has in the air quality and how it affects health of human population. Then, problems of construction of the measurement device supported by a theoretical explanation on the basis of Mie theory are discussed. Subsequently, it is followed by an analysis of the device operation both in laboratory and in real conditions. Results obtained with the presented device are compared with the professional measurement equipment and an expensive, outdoor measurement station. Paper is concluded with observations of differences in spatio-temporal PM change at very close but significantly different city locations.     

Perspectives of solution NMR spectroscopy for structural and functional studies of integral membrane proteins

This article discusses future perspectives of solution NMR spectroscopy to study structures and functions of integral membrane proteins at atomic resolution, based on a review of recent progress in this area. Several selected examples of structure determinations, as well as functional studies of integral membrane proteins are highlighted. We expect NMR spectroscopy to make future key scientific contributions to understanding membrane protein function, in particular for large membrane protein systems with known three-dimensional structure. Such situations can benefit from the fact that functional NMR studies have substantially less limitations by molecular size than a full de novo structure determination. Therefore, the general potential for NMR spectroscopy to solve biologic key questions associated with integral membrane proteins is very promising.     

Synthesis and properties of side-chain-type ion exchange membrane PEEK-g-StSO3Na for bipolar membranes

Side-chain-type ion exchange membranes (PEEK-g-StSO₃Na) were prepared by grafting poly (ether ether ketone) (PEEK) containing propenyl groups with sodium sulfonic styrene (StSO₃Na) and KH570. PEEK was synthesized by the aromatic nucleophilic polycondensation reaction of 4,4′-difluorobenzophenone, bisphenol A and diallylbisphenol A. The synthesized copolymers with the -SO₃Na group on the side chain of polymers possessed high molecular weights. The cross-linking reaction was carried out through a sol-gel reaction of the trimethoxysilane group. The copolymer membranes exhibited excellent mechanical properties due to their aromatic structure extending through the backbone and flexible StSO₃Na aliphatic chains. The ion exchange capacities (IECs) of the membranes ranged from 2.27 to 2.50 mmol g⁻¹ and the water content ranged from 107.2 to 126.1%, with both parameters increasing with StSO₃Na grafting degree. The H⁺ permeability of copolymer membranes increased with increasing IEC, reaching value above 0.3056 mol/L at 2 h, which is higher than that of Nafion^® 117 at the same measurement condition. They displayed reasonably high H⁺ permeability due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water occupation, and the lower AC impedance of the bipolar membrane.     

Speckle-based modulation transfer function measurements for comparative evaluation of CCD and CMOS detector arrays

Charge-coupled device (CCD) and complementary metal-oxide semiconductor (CMOS) matrices offer excellent features in imaging systems. For assessing the suitability of each technology according to the application, the complete characterization of the detector arrays becomes necessary. A system is optically characterized by the modulation transfer function (MTF). We have comparatively studied the results provided by the speckle method for detectors of two types: CCD and CMOS. To do so, we first analysed the precision in determining the MTF of the CCD using two apertures at the exit port of an integrating sphere: a single and a double-slit. For the single-slit, we propose a new procedure of fitting the experimental data which overcomes the drawbacks of the conventional procedure. Since it offered lower uncertainty and better reproducibility, the single-slit was used for the study with the CMOS detector. Significant differences were found between the MTF of the CCD and the CMOS detectors.     

An efficient method for evaluation of the complex probability function: The Voigt function and its derivatives

An efficient method is developed to evaluate the function w(z)=e^-z2(1+(2i/√π)∫^z₀e^t2dt) for the complex argument z = x + iy. The real part of w(z) is the Voigt function describing spectral line profiles; the imaginary part can be used to compute derivatives of the spectral line shapes, which are useful, e.g. in least-squares fitting procedures. As an example of the method a simple and fast FORTRAN subroutine is listed in the Appendix from which w(z) in the entire y ? 0 half-plane can be calculated, the maximum relative error being less than 2 × 10^-6 and 5 × 10^-6 for the real and imaginary parts, respectively.     

An evaluation of solution algorithms and numerical approximation methods for modeling an ion exchange process

The focus of this work is on the modeling of an ion exchange process that occurs in drinking water treatment applications. The model formulation consists of a two-scale model in which a set of microscale diffusion equations representing ion exchange resin particles that vary in size and age are coupled through a boundary condition with a macroscopic ordinary differential equation (ODE), which represents the concentration of a species in a well-mixed reactor. We introduce a new age-averaged model (AAM) that averages all ion exchange particle ages for a given size particle to avoid the expensive Monte-Carlo simulation associated with previous modeling applications. We discuss two different numerical schemes to approximate both the original Monte-Carlo algorithm and the new AAM for this two-scale problem. The first scheme is based on the finite element formulation in space coupled with an existing backward difference formula-based ODE solver in time. The second scheme uses an integral equation based Krylov deferred correction (KDC) method and a fast elliptic solver (FES) for the resulting elliptic equations. Numerical results are presented to validate the new AAM algorithm, which is also shown to be more computationally efficient than the original Monte-Carlo algorithm. We also demonstrate that the higher order KDC scheme is more efficient than the traditional finite element solution approach and this advantage becomes increasingly important as the desired accuracy of the solution increases. We also discuss issues of smoothness, which affect the efficiency of the KDC–FES approach, and outline additional algorithmic changes that would further improve the efficiency of these developing methods for a wide range of applications.