EPR investigation of the influence of side chain protecting groups on peptide-resin solvation of the Asx and Glx model containing peptides

In spite of all progressive efforts aiming to optimize SPPS, serious problems mainly affecting the assembly of aggregating sequences have persisted. Following the study intended to unravel the complex solvation phenomenon of peptide-resin beads, the XING and XAAAA model aggregating segments were labeled with a paramagnetic probe and studied via EPR spectroscopy. Low and high substituted resins were also comparatively used, with the X residue being Asx or Glx containing the main protecting groups used in the SPPS. Notably, the cyclo-hexyl group used for Asp and Glu residues in Boc-chemistry induced greater chain immobilization than its tert-butyl partner-protecting group of the Fmoc strategy. Otherwise, the most impressive peptide chain immobilization occurred when the large trytil group was used for Asn and Gln protection in Fmoc-chemistry. These surprising results thus seem to stress the possibility of the relevant influence of the amino-acid side chain protecting groups in the overall peptide synthesis yield. (C) 2007 Elsevier Ltd. All rights reserved.

Optically pumped submillimeter laser lines from CD2Cl2 using a large tunability CW CO2 laser

Twenty-five new laser lines have been obtained is the wavelength region from 155 to 830 mu m by optically pumping the CD2Cl2 (deuterated dichloromethane) molecule with a CW CO3 laser having a tunability range of 300 MHz. The wavelength, polarization relative to that of CO2 pumping radiation, and offset relative to the CO2 center frequency were determined for all of the new lines and some other already known laser emissions. For all of them we give also the relative intensity and the optimum pressure of operation.

Chromophore relaxation in a side-chain methacrylate copolymer functionalized with 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2 '-chloro-4 '-nitroazobenzene

A side-chain methacrylate copolymer functionalized with the nonlinear optical chromophore 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2'-chloro-4'-nitroazobenzene, disperse red-13, was prepared and characterized. The chromophore relaxation was investigated measuring the decay of the electrooptic coefficient r(13) and the complex dielectric constant at different temperatures. Results obtained below and above T-g were analyzed using the Kohlrausch-Williams-Watts(KWW) equation, through the study of the temperature dependence of the KWW parameters. Above T-g the relaxation time experimental data were fitted to the Williams-Landel-Ferry (WLF) equation and its parameters determined. Chromophore relaxation leading to the decrease of electrooptic properties was found associated with a primary alpha relaxation. The obtained WLF equation parameters were introduced into the Adam-Gibbs-Tool-Narayanaswamy-Moynihan equation, and the overall relaxation time temperature dependence was successfully obtained in terms of the fictive temperature, accounting for the sample thermal treatment and allowing optimized thermal treatment to be found. The copolymer KWW stretching parameter at the glass transition temperature lies close to the limit value for short-range interactions, i.e., 0.6, suggesting that the chromophore group is participating in primary a relaxation.

Assignments of FIR laser lines from optically pumped (CH3OH)-C-13

We have revisited the assignments of the far-infrared laser lines emitted by (CH3OH)-C-13 by comparing the laser systems to a high resolution Fourier transform absorption spectrum of (CH3OH)-C-13. The absorption spectrum was analyzed by means of the ''Ritz'' program, which calculates the energy level values directly from the Rydberg-Ritz combination principle. We report new assignments for 11 FIR laser transitions, 17 frequency predictions for new possible laser lines, and we confirm 11 previous assignments. (C) 1996 Academic Press, Inc.

NEW FIR LASER LINES AND FREQUENCY MEASUREMENTS FROM OPTICALLY PUMPED CD-13(3)OH-3

We report the discovery of 57 new fir laser lines from (CD3OH)-C-13 molecule optically pumped by a waveguide CO2 laser of 300 MHz tunability. For all lines, precise frequency offset measurements between the CO2 line center and the center of the absorbing (CD3OH)-C-13 line were performed using the transferred Lamb-Dip technique. We have also measured directly the frequency of seven FIR laser lines by heterodyning with already known laser lines.We present a complete list of all known laser lines (134) and frequency measurements (24) for this molecule.

Self-Structuring of Lamellar Bridged Silsesquioxanes with Long Side Spacers

Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers.

Frequency upconversion in Er3+-doped fluoroindate glasses pumped at 1.48 μm

We report on efficient frequency upconversion in Er3+-doped fluoroindate glass. The process is observed under 1.48 μm laser diode excitation and results in fluorescence generation in the range from ultraviolet to near-infrared radiation. The study was performed for samples containing 1, 2, and 3 ErF3 mol % in the range of temperatures from 24 to 448 K. The upconverted signals were studied as a function of the laser intensity, and their dynamical behavior is described using a rate equation model which allows us to obtain the energy transfer rates between Er3+ ions in pairs and triads.

Numerical and experimental analysis of natural convection in a cavity with flush mounted heat sources on a side wall

This work considers a problem of interest in several technological applications such as the thermal control of electronic equipment. It is also important to study the heat transfer performance of these components under off-normal conditions, such as during failure of cooling fans. The effect of natural convection on the flow and heat transfer in a cavity with two flush mounted heat sources on the left vertical wall, simulating electronic components, is studied numerically and experimentally. The influence of the power distribution, spacing between the heat sources and cavity aspect ratio have been investigated. An analysis of the average Nusselt number of the two heat sources was performed to investigate the behavior of the heat transfer coefficients. The results obtained numerically and experimentally, after an error analysis, showed a good agreement.

Consistency of side choice in the milking parlour by holstein-friesian cows and its relationship with their reactivity and milk yield

Dairy cows often have to choose which of two sides to enter in the milking parlour. Some cows are very consistent in this choicė, and it is common to assume that when these cows are more disturbed are being milked in their non-preferred side. Such disturbance might involve significantly poor welfare. In order to assess this assumption, we decided to study the behaviour and milk yield of dairy cows and their relationships with side preference in the milking parlour. The study was carried out at Cambridge University Farm, in a two-sided tandem milking parlour. The data collection followed the daily management routine. We recorded the side chosen by each cow (left or right) during 40 milking sessions. Data from 70 cows, which were present in at least 25 milking sessions (mode = 36), were included in the statistical analysis. Cows' reactivity (CR) during premilking udder preparation, time spent fitting the milking cluster (FT), milk yield (MY) and duration of milking (DM) were measured. There was evident individual variation in the consistency of side choice. Individual differences (ANOVA, P < 0.001) were also found in CR, FT, MY and DM; although these variables were not significantly affected by the side or the interaction animal × side (ANOVA, P < 0.05). The comparison between left and right side means (paired t-test) of these variables did not show significant differences (P < 0.05). We concluded that there is no evidence that the cows were discomforted or stressed when milked in the non-preferred side of the milking parlour. © 2001 Elsevier Science B.V.

Innovaciones en la gestión y calidad de los revestimientos refractarios en la Compañía Sideŕurgica Nacional (Brasil)

The work describes actions carried out in colaboration among the National Steel Company - (CSN)-Brazil and the Interdisciplinary Laboratory of Electrochemistry and Ceramic - LIEC of the Federal University of Sao Carlos Brazil (UFSCar-Brazil), in the area of I&D, for integral management and improvement of the quality and performance of the refractory linings in the sintering areas, blast furnace, hot air pipe lines transferency to the blast furnace, pig-iron ladles, running channels, blast furnaces hearths, torpedo car, etc., as well as, the economic impact generated by the installation of the adopted measures.

DCOOD optically pumped by a13CO2 laser: New terahertz laser lines

In this work, we report new optically pumped terahertz laser lines from DCOOD. An isotopic 13CO2 laser was used for first time as pump source, and a Fabry-Perot open cavity was used as a terahertz laser resonator. Optoacoustic absorption spectra were used as a guide to search for new terahertz laser lines. We could observe six new laser lines in the range from 303.8μm (0.987 THz) to 725.1μm (0.413 THz). The lines were characterized according to wavelength, relative polarization, relative intensity, and optimum working pressure. The transferred Lamb-dip technique was used to measure the frequency absorption transition both for this laser lines. © 2008 American Institute of Physics.

Utilizing cross-domain SOAP Web services using client-side languages in an enterprise mashup platform

Service oriented architectures (SOA) based on Simple Object Access Protocol (SOAP) Web services have attracted the attention of enterprises mainly for business-to-business integration and to create composite applications that execute business processes. An existing problem is the lack of preoccupation with non technical users due to the fact that to create a composite application to fulfill users needs, it is necessary to be in contact with IT staff. To overcome this issue, enterprises can take advantage of web 2.0, 'introducing in the development stage some technologies like mashups and some concepts like user empowerment, collaborative work and collective intelligence. Some results [3] [13] have shown how web 2.0 concepts can help non technical users to produce relative complex business processes. However, traditional enterprise requirements goes beyond typical web 2.0 solutions in several aspects: (1) traditional enterprise systems are based on heterogeneous stack of technologies that are not directly exploitable from a web-based client (where SOAP web services play an important role); (2) web browsers set some cross-domain security constraints making difficult to integrate services from diverse domains. In this paper, a contribution to two web 2.0 research projects [14] [15] partially solves the problems described: provide a way to invoke cross-domain backend services (based on SOAP technologies) directly only using clientside languages, without a need for any adaptation layer. © 2010 ACM.

Hemoglobin polymorphism and hematological profile of Geoffroy's side-necked turtle (Phrynops geoffroanus, Testudines) in the northwestern region of São Paulo State, Brazil

Complete blood counts and hemoglobin isoform data were gathered from 36 specimens of the turtle species Phrynops geoffroanus from the northwestern region of São Paulo State, Brazil. They were collected in an urban area. The hemoglobin profiles were obtained after red blood cell lysis and by electrophoretic migration in alkaline pH, acid pH, and neutral pH buffer. The hemoglobin components were confirmed using high-performance liquid chromatography (HPLC). Erythrogram analysis included hematocrit, total hemoglobin concentration, total red blood cell count, and red blood cell indices. The leukogram included a total white blood cell count and a calculation of the percent values of neutrophils, lymphocytes, monocytes, basophils, eosinophils, heterophils, and azurophils. HPLC analysis revealed three hemoglobin components; the first with a concentration of 5.5%, the second was a major component with an average concentration of 67.1%, and the third with a concentration of 28.5%. The hematological profile obtained for these specimens allowed us to establish a pattern for P. geoffroanus in São Paulo State Northwestern region. The average hematocrit values were 22.5% for females and 24.0% for males. For total hemoglobin, we found average values of 6.66 g/dL in females and 7.22 g/dL in males. The number of white blood cells was 2725 x 103/μL for females and 2775 x 103/μL for males. There was a predominance of heterophils, eosinophils, and monocytes in both sexes. No significant differences were found between males and females for hematological profile. The hematological results were compared to literature data for other Chelonia. They were similar to what is known for fresh water turtles. © FUNPEC-RP.

Prevalence of chewing side preference in the deciduous, mixed and permanent dentitions

Aim: This study evaluated the prevalence of the chewing side preference (CSP) in the deciduous, mixed and permanent dentitions. Materials and methods: Three-hundred subjects were divided in three groups (n = 100): Group 1 - children with deciduous dentition; group 2-children with mixed dentition; group 3 - subjects with permanent dentition. The CSP was determined using a direct method (visual observation) developed by McDonnell et al. (2004). Descriptive statistic was used to observe the prevalence of CSP. The Pearson's Chi-square was used to investigate signicant associations between gender, presence of CSP and preferred side (right/left). Results and conclusion: Eighty-seven percent of group 1 had a CSP. Eighty-two percent of group 2 had a CSP. Seventy-six percent of group 3 had a CSP. There was no statistically significant association between presence of CSP and gender in all groups. There was no statistically significant association between preferred side (right/left) and gender in all groups. Clinical significance: There is a higher prevalence of subjects in deciduous, mixed and permanent dentition that presented chewing side preference. The early diagnosis of the presence of chewing side preference can prevent the unilateral chewing pattern with prophylactic therapy applied to the first teeth (deciduous).

Observation of long-range, near-side angular correlations in pPb collisions at the LHC

Results on two-particle angular correlations for charged particles emitted in pPb collisions at a nucleon-nucleon center-of-mass energy of 5.02 TeV are presented. The analysis uses two million collisions collected with the CMS detector at the LHC. The correlations are studied over a broad range of pseudorapidity, η, and full azimuth, φ, as a function of charged particle multiplicity and particle transverse momentum, pT. In high-multiplicity events, a long-range (2<|δη|<4), near-side (δφ≈0) structure emerges in the two-particle δη-δφ correlation functions. This is the first observation of such correlations in proton-nucleus collisions, resembling the ridge-like correlations seen in high-multiplicity pp collisions at s=7 TeV and in AA collisions over a broad range of center-of-mass energies. The correlation strength exhibits a pronounced maximum in the range of pT=1-1.5 GeV/c and an approximately linear increase with charged particle multiplicity for high-multiplicity events. These observations are qualitatively similar to those in pp collisions when selecting the same observed particle multiplicity, while the overall strength of the correlations is significantly larger in pPb collisions. © 2012 CERN.