Spectral collocation methods for polymer brushes

We provide an in-depth study of pseudo-spectral numerical methods associated with modeling the self-assembly of molten mixed polymer brushes in the framework of self-consistent field theory (SCFT). SCFT of molten polymer brushes has proved numerically challenging in the past because of sharp features that arise in the self-consistent pressure field at the grafting surface due to the chain end tethering constraint. We show that this pressure anomaly can be reduced by smearing the grafting points over a narrow zone normal to the surface in an incompressible model, and/or by switching to a compressible model for the molten brush. In both cases, we use results obtained from a source (delta function) distribution of grafting points as a reference. At the grafting surface, we consider both Neumann and Dirichlet conditions, where the latter is paired with a masking method to mimic a confining surface. When only the density profiles and relative free energies of two comparison phases are of interest, either source or smeared distributions of grafting points can be used, but a smeared distribution of grafting points exhibits faster convergence with respect to the number of chain contour steps. Absolute free energies converge only within the smeared model. In addition, when a sine basis is used with the masking method and a smeared distribution, fewer iterations are necessary to converge the SCFT fields for the compressible model. The numerical methods described here and investigated in one-dimension will provide an enabling platform for computationally more demanding three-dimensional SCFT studies of a broad range of mixed polymer brush systems.     

Optical mouse acting as biospeckle sensor

In this work we propose some experiments with the use of optical computer mouse, associated to low cost lasers that can be used to perform several measurements with applications in industry and in human health monitoring. The mouse was used to grab the movements produced by speckle pattern changes and to get information through the adaptation of its structure. We measured displacements in wood samples under strain, variations of the diameter of an artery due to heart beat and, through a hardware simulation, the movement of an eye, an experiment that could be of low cost help for communication to severely handicapped motor patients. Those measurements were done in spite of the fact that the CCD sensor of the mice is monolithically included into an integrated circuit so that the raw image cannot be accessed. If, as was the case with primitive optical mouse, that signal could be accessed, the quality and usefulness of the measurements could be significantly increased. As it was not possible, a webcam sensor was used for measuring the drying of paint, a standard phenomenon for testing biospeckle techniques, in order to prove the usefulness of the mouse design. The results showed that the use of the mouse associated to a laser pointer could be the way to get metrological information from many phenomena involving the whole field spatial displacement, as well as the use of the mouse as in its prime version allowed to get images of the speckle patterns and to analyze them.     

Moderator for neutron activation with the photoneutrons produced by a LINAC

Using Monte Carlo methods a polyethylene moderator has been designed to induce activation using the photoneutrons field of a 15 MV linear accelerator for radiotherapy. In the calculations the photoneutron spectrum at 1 m from the isocenter was used as a source term and the neutron spectra were calculated in the center of different size cylindrical moderators. The best size was selected defining the thermal-to-fast-neutron ratios as a figure of merit. The moderator was built and its performance was evaluated by inducing the activation of Mn dissolved in water, silver coins and souvenir coin. The thermal neutron fluence rate was determined with the Mn samples being 9.96 × 10⁵ cm^?2 Gy _x ^?1 .     

Fluorescent Probes Based on Nucleophilic Substitution–Cyclization for Hydrogen Sulfide Detection and Bioimaging

The design, synthesis, properties, and cell imaging applications of a series of 2‐pyridyl disulfide based fluorescent probes (WSP1, WSP2, WSP3, WSP4 and WSP5) for hydrogen sulfide detection are reported. The strategy is based on the dual‐nucleophilicity of hydrogen sulfide. A hydrogen sulfide mediated tandem nucleophilic substitution‐cyclization reaction is used to release the fluorophores and turn on the fluorescence. The probes showed high sensitivity and selectivity for hydrogen sulfide over other reactive sulfur species, including cysteine and glutathione.     

Imidate-Based Cross-Linkers for Structural Proteomics: Increased Charge of Protein and Peptide Ions and CID and ECD Fragmentation Studies

Chemical cross-linking is an attractive low-resolution technique for structural studies of protein complexes. Distance constraints obtained from cross-linked peptides identified by mass spectrometry (MS) are used to construct and validate protein models. Amidinating cross-linkers such as diethyl suberthioimidate (DEST) have been used successfully in chemical cross-linking experiments. In this work, the application of a commercial diimidate cross-linking reagent, dimethyl suberimidate (DMS), was evaluated with model peptides and proteins. The peptides were designed with acetylated N-termini followed by random sequences containing two Lys residues separated by an Arg residue. After cross-linking reactions, intra- and intermolecular cross-linked species were submitted to CID and ECD dissociations to study their fragmentation features in the gas phase. Fragmentation of intramolecular peptides by collision induced dissociation (CID) demonstrates a unique two-step fragmentation pathway involving formation of a ketimine as intermediate. Electron capture and electron transfer dissociation (ECD and ETD) experiments demonstrated that the cyclic moiety is not dissociated. Intermolecular species demonstrated previously described fragmentation behavior in both CID and ECD experiments. The charge state distributions (CSD) obtained after reaction with DMS were compared with those obtained with disuccinimidyl suberate (DSS). CSDs for peptides and proteins were increased after their reaction with DMS, owing to the higher basicity of DMS modified species. These features were also observed in LC-MS experiments with bovine carbonic anhydrase II (BCA) after cross-linking with DMS and tryptic proteolysis. Cross-linked peptides derived from this protein were identified at high confidence and those species were in agreement with the crystal structure of BCA.

Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of indium(III) halides

The ligands o-C6H4(PMe2)2 and o-C6H4(AsMe2)2 (L-L) react with anhydrous InX3 (X = Cl, Br, or I) in a 2:1 InX3/ligand ratio to form [InX2(L-L)][InX4] containing distorted tetrahedral cations, established by X-ray crystal structures for L-L = o-C6H4(PMe2)2 (X = Br or I) and o-C6H4(AsMe2)2 (X = I). IR, Raman, and multinuclear NMR ((1)H, (31)P, (115)In) spectroscopy show that these are the only species present in solution in chlorocarbons and in the bulk solids. The products from reactions in a 1:1 or 1:2 molar ratio are more diverse and include the halide-bridged dimers [In2Cl6{o-C6H4(PMe2)2}2] and [In2X6{o-C6H4(AsMe2)2}2] (X = Cl or Br) and the distorted octahedral cation trans-[InBr2{o-C6H4(PMe2)2}2][InBr4]. The neutral complexes partially rearrange in chlorocarbon solution, with multinuclear NMR spectroscopy revealing [InX4](-) among other species. The iodo complexes trans-[InI2(L-L)2][InI4(L-L)] contain rare examples of six-coordinate anions, as authenticated by an X-ray crystal structure for L-L = o-C6H4(PMe2)2. Two species of formula [In2Cl5(L-L)2]n[InCl4]n (L-L = o-C6H4(PMe2)2 and o-C6H4(AsMe2)2) were identified crystallographically and contain polymeric cations with six-coordinate indium centers bonded to one chelating L-L and a terminal chlorine, linked by alternating single and double chlorine bridges into chains. The complicated chemistry of InX3 with these two rigid chelates is contrasted with that of the flexible diphosphane Et2P(CH2)2PEt2, which forms [In2Cl6{Et2P(CH2)2PEt2}2], and with more sterically demanding o-C6H4(PPh2)2 (Sigl et al. Eur. J. Inorg. Chem. 1998, 203-210). The results also contrasted with those found for GaX3 with the same ligands (Cheng et al. Inorg. Chem. 2007, 46, 7215-7223).     

Microfluidic add-on for standard electrophysiology chambers

We have developed a microfluidic brain slice device (microBSD) that marries an off-the shelf brain slice perfusion chamber with an array of microfluidic channels set into the bottom surface of the chamber substrate. As this device is created through rapid prototyping, once optimized, it is trivial to replicate and share the devices with other investigators. The device integrates seamlessly into standard physiology and imaging chambers and it is immediately available to the whole slice physiology community. With this technology we can address the flow of neurochemicals and any other soluble factors to precise locations in the brain slice with the temporal profile we choose. Dopamine (DA) was chosen as a model neurotransmitter and we have quantified delivery in brain tissue using cyclic voltammetry (CV) and fluorescence imaging.     

Neutron spectrum and doses in a 18 MV LINAC

Bonner sphere spectrometer with TLDs pairs has been utilized to measure the neutron spectrum 100 cm from isocenter of a 18 MV LINAC, simultaneously the ambient dose equivalent due to neutrons and photons was measured in the control room area with neutron and gamma-ray area monitors. Measurements were carried out when the LINAC was delivering a dose of 600 MU at the isocentre that was located at 5 cm depth of a head phantom. Undesired neutron field in the treatment room produce activation reactions with nuclei in different materials of LINAC, couch, air, and phantom. To determine the dose due to decay of activation nuclei the ambient dose due to gamma-rays was measured inside the treatment room immediately after dose was delivered. Measured spectrum has two peaks, one between 0.1–1 MeV and other in the thermal region, the ambient dose equivalent in the control room are 3.1 and 0.93 μSv h⁻¹ for photons and neutrons, respectively. In the treatment room the ambient dose equivalent due to photons produced during decay of activation nuclei varies from 6 to 26.1 μSv h⁻¹.     

Flow separation behind ellipses at Reynolds numbers less than 10

Flow separation behind two-dimensional ellipses with aspect ratios ranging from 0, a flat plate, to 1, a circular cylinder, were investigated for Reynolds numbers less than 10 using both a cellular automata model and a commercial computational fluid dynamics software program. The relationship between the critical aspect ratio for flow separation and Reynolds number was determined to be linear for Reynolds numbers greater than one. At slower velocities, the critical aspect ratio decreases more quickly as the Reynolds number approaches zero. The critical Reynolds numbers estimated for flow separation behind a flat plate and circular cylinder agree with extrapolations from experimental observations. Fluctuations in the values of the stream function for laminar flow behind the ellipses were found at combinations of Reynolds number and aspect ratio near the critical values for separation.     

On the use of wavelength and time diversity in optical wireless communication systems over gamma–gamma turbulence channels

Optical wireless communication or free space optical systems have gained significant research and commercial attention in recent years due to their cost-effective and license-free high bandwidth access characteristics. However, by using the atmosphere as transmission media, the performance of such a system depends on the atmospheric conditions that exist between transmitter and receiver. Indeed, for an outdoor optical channel link, the existence of atmospheric turbulence may significantly degrade the performance of the associated communication system over distances longer than 1 or even 0.5 km. In order to anticipate this, particular attention has been given to diversity methods. In this work, we consider the use of wavelength and time diversity in wireless optical communication systems that operate under weak to strong atmospheric turbulence conditions modeled by the gamma–gamma distribution, and we derive closed form mathematical expressions for estimating the system's achievable outage probability and average bit error rate. Finally, numerical results referred to common practical cases are also obtained in order to show that wavelength and time diversity schemes enhances considerably these systems’ availability and performance.