Solid phase synthesis of novel α/β‐tetrapeptides,electrospray ionization mass spectrometric evaluation of their metal cation complexation behavior,and conformational analysis using density functional theory (DFT)

Thirty‐four novel α/β‐tetrapeptides ( 1–34 ) have been prepared employing solid‐phase and in‐parallel synthetic protocols. α/β ‐Tetrapeptides 1 – 34 were prepared by a combination of three α‐amino acid residues (alanine (Ala), phenylalanine (Phe), and isoleucine (Ile)) with one β‐amino acid residue (β³‐homophenylglycine). The corresponding complexes of several selected α/β‐tetrapeptides with alkali, alkaline earth, and transition metals, [tP + M⁺], were evaluated using ion electrospray‐ionization mass spectrometry (ESI‐MS). According to the results from analysis of mixtures, we can conclude that the position of the β‐amino acid is determinant in the affinity toward different metal cations. Computational modeling (DFT, B3LYP 6‐311++G) provided useful information regarding the most likely coordination sites of the metal ions on the receptor α/β‐tetrapeptide 12 , HO₂C‐α‐Phe‐α‐Phe‐α‐Ile‐β³‐hPhg‐NH₂, as well as the conformational changes induced by the metal upon [tP + M⁺] complex formation. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and infrared,microwave spectra,conformational stability,adjusted r0 structural parameters,and vibrational assignments of cyclopentylamine

Fourier transform microwave spectrum of cyclopentylamine, c–C₅H₉NH₂ has been recorded, and seven transitions have been assigned for the most abundant conformer, and the rotational constants have been determined: A = 4909.46(5), B = 3599.01(4), and C = 2932.94(4). From the determined microwave rotational constants and ab initio MP2(full)/6‐311 + G(d,p) predicted structural values, adjusted r₀ parameters are reported with distances (Å): rC_α–C_β = 1.529(3), rC_β–C_γ = 1.544(3), rC_γ–C_γ = 1.550(3), rC_α–N = 1.470(3), and angles (°) ∠CCN = 108.7(5), ∠C_βC_αC_β = 101.4(5), and τC_βC_αC_β′C_γ′ = 42.0(5). The infrared spectra (4000–220 cm⁻¹) of the gas have been recorded. Additionally, the variable temperature (−60 to −100 °C) Raman spectra of the sample dissolved in liquefied xenon was recorded from (3800–50 cm⁻¹). The four possible conformers have been identified, and their relative stabilities obtained with enthalpy difference relative to t‐Ax of 211 ± 21 cm⁻¹ for t‐Eq ≥ 227 ± 22 cm⁻¹ for g‐Eq ≥ 255 ± 25 cm⁻¹ for g‐Ax. The percentage of the four conformers is estimated to be 53% for the t‐Ax, 11 ± 1% for t‐Eq, 20 ± 2% for g‐Ax and 16 ± 2% for g‐Eq at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug‐cc‐pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for the observed bands for all four conformers, which are predicted by MP2(full)/6‐31G(d) ab initio calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities, and depolarization ratios for all of the conformers. The results are discussed and compared to the corresponding properties of some related molecules. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of fundamental power coupler for C-ADS superconducting elliptical cavities

5-cell elliptical cavities have been selected for the main linac of the China Accelerator Driven subcritical System(C-ADS) in the medium energy section. According to the design, each cavity should be driven with radio frequency(RF) energy up to 150 kW by a fundamental power coupler(FPC). As the cavities work with high quality factor and high accelerating gradient, the coupler should keep the cavity from contamination in the assembly procedure. To fulfil the requirements, a single-window coaxial type coupler was designed with the capabilities of handling high RF power, class 10 clean room assembly, and heat load control. This paper presents the coupler design and gives details of RF design, heat load optimization and thermal analysis as well as multipacting simulations. In addition, a primary high power test has been performed and is described in this paper.     

Study of medium beta elliptical cavities for CADS

The China Accelerator-Driven Sub-critical System(CADS) is a high intensity proton facility to dispose of nuclear waste and generate electric power.CADS is based on a 1.5 GeV,10 mA CW superconducting(SC) linac as a driver.The high energy section of the linac is composed of two families of SC elliptical cavities which are designed with geometrical beta 0.63 and 0.82.In this paper,the 650 MHz β=0.63 SC elliptical cavity is studied,including cavity optimization,multipacting,high order modes(HOMs) and generator RF power calculation.     

Structural,optical and electrical properties of 60 MeV C5+ ion-irradiated poly(3-methylthiophene) films

The structural, optical and electrical properties of 60 MeV C⁵⁺ ion-irradiated poly(3-methylthiophene) (P3MT) synthesized by the chemical oxidation polymerization method have been studied. The P3MT powder was dissolved in chloroform (CHCl₃), and thin films of thickness 2 μm were prepared on glass and Si substrates. The polymerization was confirmed by the FTIR spectrum. Then films were irradiated by 60 MeV C⁵⁺ ions at different fluences. FTIR spectra show methyl group evolution after irradiation. The optical band gap decreases slightly after irradiation and the DC conductivity increases by about one order of magnitude after irradiation at the highest fluence. The role of S _e has also been discussed when compared with 60 MeV Si⁵⁺ ion irradiation of P3MT. The morphological changes are observed using SEM.     

Effect of the geometric shape of Lu 2 O 3 : Eu spherical nanocrystals on their spontaneous luminescence

Monodisperse red phosphor particles 100 nm in diameter with the Lu_1.90Eu_0.10O₃ composition have been prepared using the developed technique for synthesizing spherical colloidal lutetium oxide particles with a size dispersion in the range 10–15%. The structure of spherical nanoparticles has been investigated, their excitation and photoluminescence spectra have been analyzed, and the lifetime of the ⁵ D ₀ excited state of Eu³⁺ ions has been considered. It has been found that the luminescence decay time for spherical particles increases by a factor of 1.39 compared to that for a powdered phosphor Lu₂O₃: Eu (5 at %) prepared and treated under the same temperature conditions as the Lu₂O₃: Eu (5 at %) spherical particles. This effect has been associated with the change in the photonic local density of states in spherical optical cavities consisting of particles of the phosphor.     

Photon,quantum and collective,effects from rydberg atoms in cavities

I review some theories of the interaction ofN Rydberg atoms interacting collectively with radiation in microwave cavities. The radiation may be incoherent (black body) radiation or it may be coherent. In the former case theories of the steady state inversion and of the superradiance from initially inverted atoms in low-Q cavities agree well with experimental observations. In the latter case in low-Q cavities ‘phase transitions’ of both first and second order types are predicted and should be observable by monitoring the output of an atomic beam by an atomic ionisation detector. The first order transition which occurs at opposite detunings of the cavity and atoms from the frequency of the coherent driving field is of “optically” bistable type but hysteresis is suppressed by quantum fluctuations which can be large in the cavity field close to the transition. I also review a theory of the spectra from single atoms in cavities ofarbitrary Q containing a few microwave photons. A transition from a single peaked Lorentzian spectrum at low-Q to a double-peaked spectrum forQ≃10⁶ is predicted and peaks representing one or more photon transitions of the Jaynes-Cummings model are also expected to be observable at these or largerQ values. The collective theories are all based onN atom Dicke type models driven by the coherent or incoherent field. Substantial squeezing of the fluorescent radiation field from these Dicke models is also predicted and may be observable with Rydberg atoms.     

Effect of simultaneous helium implantation on the microstructure evolution of Inconel X-750 superalloy during dual-beam irradiation

This study focuses on investigation into the effect of helium implantation on microstructure evolution in Inconel X-750 superalloy during dual-beam (Ni⁺/He⁺) irradiation. The 1 MeV Ni⁺ ions with the damage rate of 10^?3 dpa/s as well as 15 keV He⁺ ions using rate of 200 appm/dpa were simultaneously employed to irradiate specimens at 400 °C to different doses. Microstructure characterization has been conducted using high-resolution analytical transmission electron microscopy (TEM). The TEM results show that simultaneous helium injection has significant influence on irradiation-induced microstructural changes. The disordering of γ′ (Ni₃ (Al, Ti)) precipitates shows noticeable delay in dose level compared to mono heavy ion irradiation, which is attributed to the effect of helium on promoting the dynamic reordering process. In contrast to previous studies on single-beam ion irradiation, in which no cavities were reported even at high doses, very small (2–5 nm) cavities were detected after irradiation to 5 dpa, which proved that helium plays crucial role in cavity formation. TEM characterization also indicates that the helium implantation affects the development of dislocation loops during irradiation. Large 1/3 〈1?1?1〉 Frank loops in the size of 10–20 nm developed during irradiation at 400 °C, whereas similar big loops detected at higher irradiation temperature (500 °C) during sole ion irradiation. This implies that the effect of helium on trapping the vacancies can help to develop the interstitial Frank loops at lower irradiation temperatures.     

Pressure-induced phase transition in silicon nitride material

The equilibrium crystal structures,lattice parameters,elastic constants,and elastic moduli of the polymorphs α-,β-,and γ-Si3N4,have been calculated by first-principles method.β-Si3N4 is ductile in nature and has an ionic bonding.γSi3N4 is found to be a brittle material and has covalent chemical bonds,especially at high pressures.The phase boundary of the β→γ transition is obtained and a positive slope is found.This indicates that at higher temperatures it requires higher pressures to synthesize γ-Si3N4.On the other hand,the α→γ phase boundary can be described as P = 14.37198+ 3.27 × 10?3T-7.83911 × 10?7T2-3.13552 × 10?10T3.The phase transition from α-to γ-Si3N4 occurs at 16.1 GPa and 1700 K.Then,the dependencies of bulk modulus,heat capacity,and thermal expansion on the pressure P are obtained in the ranges of 0 GPa-30 GPa and 0 K-2000 K.Significant features in these properties are observed at high temperatures.It turns out that the thermal expansion of γ-Si3N4 is larger than that of α-Si3N4 over wide pressure and temperature ranges.The evolutions of the heat capacity with temperature for the Si3N4 polymorphs are close to each other,which are important for possible applications of Si3N4.     

EPR Study of Nd3☎ Ions in β-BaB2O4 Single Crystals

An Electron Paramagnetic Resonance (EPR) study of Nd^3? ions in single crystals of the low-temperature phase of barium borate (β-BaB₂O₄ or BBO) is presented. The EPR spectra show the existence of a minimum of three different Nd^3? centres. The g-matrices for three of the centres have been determined from the analysis of the angular dependencies of the spectrum in two planes of the crystal. This study allows us to conclude that neodymium is incorporated in the low-symmetry Ba^2? site. Possible reasons for the appearance of various Nd^3? centres are discussed.     

Diamond anvil cell syntheses and compressibility studies of the spinel-structured gallium oxonitride

The formation conditions of cubic spinel-structured gallium oxonitride have been investigated in situ under high-pressure/high-temperature conditions using a laser-heated diamond anvil cell. As starting materials, a mixture of the end members w-GaN/β-Ga₂O₃ in a molar ratio of 3:2 and a gallium oxonitride ceramic derived during pyrolysis from the metallo-organic precursor (Ga(O^tBu)₂NMe₂)₂ were used. In the mixture of the end members, spinel-structured gallium oxonitride starts crystallizing at a pressure of 3 GPa and at a temperature of about 1300 °C. The precursor-derived ceramic with predefined bondings reacted completely to the spinel phase, without by-products, at a pressure of 0.7 GPa. For the spinel-structured gallium oxonitride we determined a bulk modulus K of 216(7) GPa using a fixed value of 4 for K′. The spinel-structured gallium oxonitride exhibits a cell volume of 552.9(5) ų at ambient pressure.     

Food additives characterization by infrared,Raman, and surface‐enhanced Raman spectroscopies

Fourier‐transform infrared (FT‐IR), Raman (RS), and surface‐enhanced Raman scattering (SERS) spectra of β‐hydroxy‐β‐methylobutanoic acid (HMB), L ‐carnitine, and N‐methylglycocyamine (creatine) have been measured. The SERS spectra have been taken from species adsorbed on a colloidal silver surface. The respective FT‐IR and RS band assignments (solid‐state samples) based on the literature data have been proposed. The strongest absorptions in the FT‐IR spectrum of creatine are observed at 1398, 1615, and 1699 cm⁻¹, which are due to ν_s(COOH) + ν(CN) + δ(CN), ρ_s(NH₂), and ν(C O) modes, respectively, whereas those of L ‐carnitine (at 1396/1586 cm⁻¹ and 1480 cm⁻¹) and HMB (at 1405/1555/1585 cm⁻¹ and 1437–1473 cm⁻¹) are associated with carboxyl and methyl/methylene group vibrations, respectively. On the other hand, the strongest bands in the RS spectrum of HMB observed at 748/1442/1462 cm⁻¹ and 1408 cm⁻¹ are due to methyl/methylene deformations and carboxyl group vibrations, respectively. The strongest Raman band of creatine at 831 cm⁻¹ (ρ_w(R NH₂)) is accompanied by two weaker bands at 1054 and 1397 cm⁻¹ due to ν(CN) + ν(R NH₂) and ν_s(COOH) + ν(CN) + δ(CN) modes, respectively. In the case of L ‐carnitine, its RS spectrum is dominated by bands at 772 and 1461 cm⁻¹ assigned to ρ_r(CH₂) and δ(CH₃), respectively. The analysis of the SERS spectra shows that HMB interacts with the silver surface mainly through the  COO⁻, hydroxyl, and  CH₂ groups, whereas L ‐carnitine binds to the surface via  COO⁻ and  N⁺(CH₃)₃ which is rarely enhanced at pH = 8.3. On the other hand, it seems that creatine binds weakly to the silver surface mainly by  NH₂, and C O from the  COO⁻ group. Copyright © 2006 John Wiley & Sons, Ltd.     

Reactivity of the insecticide chlorpyrifos‐methyl toward hydroxyl and perhydroxyl ion. Effect of cyclodextrins

The reactivity of Chlorpyrifos‐Methyl ( 1 ) toward hydroxyl ion and the α‐nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25 °C in water containing 10% ACN or 7% 1,4‐dioxane at NaOH concentrations between 0.01 and 0.6 M ; the second‐order rate constant is 1.88 × 10^?2 M ^?1 s^?1 in 10% ACN and 1.70 × 10^?2 M ^?1 s^?1 in 7% 1,4‐dioxane. The reaction with H₂O₂ was studied in a pH range from 9.14 to 12.40 in 7% 1,4‐dioxane/H₂O; the second‐order rate constant for the reaction of HOO^? ion is 7.9 M ^?1 s^?1 whereas neutral H₂O₂ does not compete as nucleophile. In all cases quantitative formation of 3,5,6‐trichloro‐2‐pyridinol ( 3 ) was observed indicating an S_N2(P) pathway. The hydrolysis reaction is inhibited by α‐, β‐, and γ‐cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ‐cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α‐ and β‐cyclodextrin (β‐CD), whereas γ‐cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β‐ or γ‐cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin‐mediated reaction is the reaction of HO^? or HOO^? ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

Solvatochromism of catechol derivatives – solute/solvent interactions

The solvatochromism of nine push–pull substituted catechol derivatives has been studied in a set of 39 various solvents. The influence of successive methyl substitution at the catechol OH groups on the extent of the solvatochromic shift has been investigated. The positive solvatochromism of 2‐(3,4‐dihydroxybenzylidene)‐2H‐indene‐1,3‐dione amounts 4360 cm^–1, which ranges from toluene to hexamethyl‐phosphoric triamide. To the best of our knowledge, it is one of the largest positive solvatochromic extent measured for a positive solvatochromic dye, comparable with Brooker's thiobarbituric acid with an extent of 4400 cm^–1. The detailed analyses of the solvatochromism were carried out by alternatively using the Kamlet–Taft and Catalán solvent parameters to achieve information of dipolarity versus polarizability effects of solvent upon solvatochromic properties. In solvents with high β values such as alcohols (0.66 < β < 0.90), amides (0.48 < β < 0.80), dimethyl sulfoxide (β = 0.76), tetramethyl urea (β = 0.80) and hexamethyl‐phosphoric triamide (β = 1.05) UV–Vis absorption spectra show two separate λ_max, which are caused by a deprotonation reaction. The solvatochromic behaviour of the anionic species is compared with those of the catechol derivatives. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of iron doping at Mn-site on complex impedance spectroscopy properties of Nd0.67Ba0.33MnO3 perovskite

The effect of Fe-doping at Mn-site on the structural and electrical properties of Nd_0.67Ba_0.33Mn_1?xFe_xO₃ (0 ≤ x ≤ 0.05) perovskites has been investigated. X-ray diffraction patterns show that the structural parameters change slightly due to the fact that the Fe³⁺ ions replacing the Mn³⁺ have similar ionic radius. The electrical properties of these samples have been investigated using complex impedance spectroscopy technique. a function of the frequency at different temperatures. When increasing the Fe-content, a decrease of dc conductivity was observed throughout the whole explored temperature range and the deduced activation energy values are found to increase from 128 meV for x = 0 to 166 meV for x = 0.05. The curves of the imaginary part of impedance (Z″) show the presence of relaxation phenomenon in our samples. The complex impedance spectra show semicircle arcs at different temperatures and an equivalent circuit of the type of R_g + (R_gb//C_gb) has been proposed to explain the impedance results.     

Dy3+掺杂Ge-Ga-S-CsI玻璃中红外发光特性研究

用熔融淬冷法制备了系列掺杂浓度的Dy³⁺:Ge-Ga-S-CsI硫卤玻璃样品,测试了样品拉曼光谱、折射率、吸收光谱、近红外及中红外荧光谱.应用Judd-Ofelt理论计算了Dy³⁺离子的强度参数 (Ω_i, i=2,4,6)、自发辐射跃迁概率(A)、荧光分支比(β)、以及辐射寿命(τ_rad)等光谱参数.研究了810 nm激光抽运下样品中红 关键词： 硫系玻璃 中红外发光 3+掺杂')" href="#">Dy³⁺掺杂 多声子弛豫     

Positioning photonic crystal cavities to single InAs quantum dots

We have investigated the optical properties of planar photonic crystal cavities formed by removing a single hole from a two-dimensional square lattice of air holes etched through a thin GaAs slab. We have demonstrated cavity resonances with quality factors (Q’s) as high as 8500, using an internal light source provided by an ensemble of InAs quantum dots (QDs) grown by molecular beam epitaxy (MBE). The high-Q modes are confined to a very small mode volume, V = 0.7(λ/n)³, making them attractive to study in the context of cavity quantum electrodynamics with single QDs, where a high is needed to observe the strong coupling between an electronic state of the dot and the optical cavity mode. To this end, we have developed an accurate and robust alignment technique that positions a photonic crystal cavity to a single QD with 25 nm resolution. We present the details of this new technology and demonstrate its effectiveness by strategically positioning a number of QDs within photonic crystal cavities at points where the electric field intensity is high.     

Study of multipacting effect in superconducting cavity

A number of superconducting cavities of axis-symmetric geometry have been considered to study the effect in order to achieve the desired performance.It is shown that the multipacting effect is strongly dependent on the condition of the RF surface and can be suppressed with reconsideration of the geometry.The simulation result is compared with the result of the semi-analytical model in the end.     

Simulation of near-infrared photodiode detectors based on β-FeSi2/4H-SiC heterojunction

In this paper, we propose the near-infrared p-type β-FeSi₂/n-type 4H-SiC heterojunction photodetector with semiconducting silicide (β-FeSi₂) as the active region for the first time. Optoelectronic characteristics of the photodetector are simulated using a commercial simulator at room temperature. The results show that the photodetector has a good rectifying character and a good response to the near-infrared light. Interface states should be minimized to obtain a lower reverse leakage current. The response spectrum of the β-FeSi₂/4H-SiC detector, which consists of a p-type β-FeSi₂ absorption layer with a doping concentration of 1×10¹⁵ cm^-3 and a thickness of 2.5 μm, has a peak of 755 mA/W at 1.42 μm. The illumination of the SiC side obtains a higher responsivity than that of the β-FeSi₂ side. The results illustrate that the β-FeSi₂/4H-SiC heterojunction can be used as a near-infrared photodetector compatible with near-infrared optically-activated SiC-based power switching devices.     

Die Übergangstemperatur verschiedener Supraleiter zweiter Art unter hydrostatischem Druck

An apparatus for production of hydrostatic pressure is described using a mixture of n-pentane and iso-pentane, which transmits pressure uniformly still at low temperatures. The superconductive transitions of the A 15(β- W type)-compounds Nb₃Sn, Nb₃Al, V₃Si and the B 1(NaCl type)-compound NbN have been measured under pressure up to 18 · 10³ kp/cm². The transition temperatures of the compounds V₃Si and NbN are increasing with pressure. Further measurements have been done on some selected ternary compounds, e.g. Nb₃(Al_1?x Ge _x ), to prove some predictions for the effect of pressure on superconductive transition.