Construction and Analysis of Lifson?Roig Models for the Helical Conformations of α‐Peptides

New forms of Lifson? Roig algorithms are introduced for modeling stabilities of helices formed by polypeptides derived from α‐amino acids. The principles of constructing and generalizing these algorithms are developed, and their application to modeling of circular dichroism ellipticities and protection factors derived from H/D exchange of α‐peptide backbone amide residues are critically reviewed. With the aim of comparing the properties of structured conformations formed by α‐ and β‐peptides, the intrinsic limitations of Lifson? Roig algorithms and their underlying assumptions are analyzed. Lifson? Roig state sums that provide easy structural analysis are generated by new algorithms based on products of 8×8 and 16×16 matrices, and a simple protocol is introduced for generating new state sums that are tailored for specific purposes. The N‐ and C‐capping of highly helical α‐peptides by means of tailored helix‐stabilizing templates is shown to result in helical conformational manifolds that approach those of helical β‐peptides in conformational homogeneity.     

Evaluation of protein-A chromatography media

In process-scale antibody purification, protein-A affinity chromatography is commonly used as the initial purification step. In this paper, two different protein-A media were evaluated. These adsorbents have a porous glass backbone with different pore sizes: 700 A and 1000 A. Adsorption equilibrium data of human immunoglobulins on these media were measured via a batch technique and correlated using the Langmuir isotherm model. A larger static capacity was found for the smaller pore size material, which is probably a result of the larger specific surface area and associated higher ligand concentration. The protein uptake kinetics were also obtained via a stirred tank experiment using different initial protein concentrations. A surface layer model was used to represent the protein uptake by the media and to estimate values of a concentration-independent effective diffusivity within the particle. Experimental breakthrough curves were also obtained from packed beds operated under different conditions. Calculated breakthrough profiles were found to be in good agreement with the experimental results. Experimental breakthrough data were used to determine the dependence of the dynamic capacity of the media as a function of the fluid residence time. A larger dynamic capacity was also found for the smaller pore size media. The permeability of large scale packed beds was also reported and used in conjunction with the dynamic capacity to calculate the process production rate.     

Aqueous RAFT Synthesis of Low Molecular Weight Anionic Polymers for Determination of Structure/Binding Interactions with Gliadin

Gliadin, a component of gluten and a known epitope, is implicated in celiac disease (CeD) and results in an inflammatory response in CeD patients when consumed. Acrylamide‐based polyelectrolytes are employed as models to determine the effect of molecular weight and pendent group on non‐covalent interaction modes with gliadin in vitro. Poly(sodium 2‐acrylamido‐2‐methylpropane sulfonate) and poly(sodium 3‐methylpropyl‐3‐butanoate) are synthesized via aqueous reversible addition fragmentation chain transfer (aRAFT) polymerization and characterized by gel permeation chromatography‐multiangle laser light scattering. The polymer/gliadin blends are examined via circular dichroism, zeta potential measurements, 8‐anilinonaphthalene‐1‐sulfonic acid fluorescence spectroscopy, and dynamic light scattering. Acrylamide polymers containing strong anionic pendent groups have a profound effect on gliadin secondary structure and solution behavior below the isoelectric point, while polymers containing hydrophobic character only have a minor impact. The polymers have little effect on gliadin secondary structure and solution behavior at the isoelectric point.     

Crystalline Aluminium Borates with the Mullite Structure: A <Superscript>11</Superscript>B and <Superscript>27</Superscript>Al Solid-State NMR Study

²⁷Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were acquired at 8.45, 14.1 and 16.45 T for a series of aluminium borates with the mullite structure (Al_6−x B _x O₉, where x has nominal values of 1 to 4) augmented with ²⁷Al multiple-quantum MAS NMR spectra at 8.45 T. Even though the ²⁷Al NMR spectra are complex, simulation of the combined set of data produced a relatively well-defined set of parameters (e.g., quadrupolar interaction, isotropic chemical shift, etc.) for each site. The ¹¹B MAS NMR spectra of the same compounds were also acquired at 14.1 T. Linear changes in the X-ray a-, b- and c-cell parameters with composition suggest that these compounds constitute a continuous series. Based on a Rietveld structural refinement of the compound synthesized as Al₄B₂O₉, the resulting site occupancies and relative site distortions allow the identification of particular sites with specific NM resonances. Changes in the ²⁷Al and ¹¹B MAS NMR spectra of the related compounds with x = 1–4 show at the lowest Al contents a greater degree of asymmetry in the Al sites of the octahedral chains. A fairly distorted cross-linking tetrahedral site, which persists throughout the composition range, is accompanied in the lower Al compositions by two 5-fold coordinated Al–O units which are replaced by two more-regular tetrahedral Al–O sites as the Al content increases. In the compounds of lowest Al composition (i.e., highest B content) both the tetrahedral and trigonal cross-linking sites are distinguishable, but as the Al content increases, the BO₄ units progressively disappear. Authors' address: Kenneth J. D. MacKenzie, School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington, New Zealand     

First CNGS events detected by LVD

The CERN Neutrino to Gran Sasso (CNGS) project aims to produce a high energy, wide band ν_μ beam at CERN and send it toward the INFN Gran Sasso National Laboratory (LNGS), 732 km away. Its main goal is the observation of the ν_τ appearance, through neutrino flavour oscillation. The beam started its operation in August 2006 for about 12 days: a total amount of 7.6×10¹⁷ protons were delivered to the target. The LVD detector, installed in hall A of the LNGS and mainly dedicated to the study of supernova neutrinos, was fully operating during the whole CNGS running time. A total number of 569 events were detected in coincidence with the beam spill time. This is in good agreement with the expected number of events from Monte Carlo simulations. PACS 14.60.Pq; 29.27.Fh; 29.40.Mc; 95.55.Vj     

Ultralow emittance, multi-MeV proton beams from a laser virtual-cathode plasma accelerator

The laminarity of high-current multi-MeV proton beams produced by irradiating thin metallic foils with ultraintense lasers has been measured. For proton energies >10 MeV, the transverse and longitudinal emittance are, respectively, <0.004 mm mrad and <10(-4) eV s, i.e., at least 100-fold and may be as much as 10(4)-fold better than conventional accelerator beams. The fast acceleration being electrostatic from an initially cold surface, only collisions with the accelerating fast electrons appear to limit the beam laminarity. The ion beam source size is measured to be <15 microm (FWHM) for proton energies >10 MeV.     

Solid-state NMR characterisation of the thermal transformation of a Hungarian white illite

(1)H, (27)Al, (29)Si and (39)K solid-state NMR are reported from a Hungarian illite 2:1 clay for samples heated up 1600 degrees C. This single-phase sample has a small amount of aluminium substitution in the silica layer and very low iron-content ( approximately 0.4wt%). Thermal analysis shows several events that can be related to features in the NMR spectra, and hence changes in the atomic scale structure. As dehydroxylation occurs there is increasing AlO(4) and AlO(5)-contents. The silica and gibbsite layers become increasingly separated as the dehydroxylation progresses. Between 900 and 1000 degrees C the silica layer forms a potassium aluminosilicate glass. The gibbsite-layer forms spinel/gamma-Al(2)O(3) and some aluminium-rich mullite. Then on heating to 1600 degrees C changes in the (29)Si and (27)Al MAS NMR spectra are consistent with the aluminosilicate glass increasing its aluminium-content, the amount of mullite increasing probably with its silicon-content also increasing, and some alpha-Al(2)O(3) forming.     

Modeling mode arrivals in the 1995 SWARM experiment acoustic transmissions

As part of the Shallow Water Acoustics in a Random Medium (SWARM) experiment, a 16 element WHOI vertical line array (WVLA) was moored in 70 m of water off the New Jersey coast. A 400-Hz acoustic tomography source was moored some 32-km shoreward of this array, such that an acoustic path was created that was anti-parallel to the primary propagation direction for shelf-generated internal wave solitons. The presence of these soliton internal waves in the acoustic waveguide causes significant coupling of energy between propagating acoustic modes, creating fluctuations in modal intensities and modal peak arrival times, as well as time spreading of the pulses. Two methods by which acoustic propagation and scattering in soliton-filled waveguides can be modeled are presented here in order to understand and explain the scattering observed in the SWARM field data. The first method utilizes the Preisig and Duda [IEEE J. Ocean. Eng. 22, 256-269 (1997)] Sudden Interface Approximation (SIA) to represent the solitons. The second method, which is computationally slower, uses a finely meshed, "propagated" thermistor record to simulate the solitons in the SWARM experiment waveguide. Both numerical methods are found to generate scattering characteristics that are similar to the SWARM field data.     

Nucleophilic SN2 displacements on penicillin-6- and cephalosporin-7- triflates; 6β-iodopenicillanic acid,a new β-lactamase inhibitor

Triflate or nonaflate esters of alkyl 6α (or β) hydroxypenicillanates are substituted (with inversion) by the soft nucleophiles iodide, bromide, chloride, azide, arylselenoxide,¹ thiocyanate, thiols, and thiolacids; carbon nucleophiles fail. Methoxide (hard) attacks the lactam bond, opening both rings to give a known¹¹ 1,4 thiazine. Iodide substitutes 7α-trifloxycephalosporins, giving 7β-iodocephalosporins.