Preparation of platinum nanoparticles by sonochemical reduction of the Pt(IV) ions: role of surfactants

Sonochemical reduction processes of Pt(IV) ions in water have been investigated in the presence of various kinds of surfactants such as sodium dodecylsulfate (SDS) and sodium dodecylbenzenesulfonate (DBS) as anionic surfactants, and polyethylene glycol monostearate (PEG-MS) as non-ionic, dodecyltrimethylammonium chloride (DTAC) and bromide (DTAB) as cationic surfactants. An improved colorimetric determination reveals that Pt(IV) ion is reduced to zero valent metal in two steps: step (1)--Pt(IV) ion to Pt(II) ion, and step (2)--Pt(II) ion to Pt(0), and after the completion of step (1), step (2) sets in. It appears that rapid scrambling reactions among platinum ions and/or atoms, that is, Pt(I) + Pt(IV)-->Pt(II) + Pt(III), etc. take place. In the sonolysis of aqueous solutions of SDS, DBS or PEG-MS, two kinds of organic reducing radicals, R(ab) and R(py), are proposed to contribute to the reduction. Radical R(ab) is formed from the reaction of the surfactants with primary radicals such as hydroxyl radicals and hydrogen atoms originated from the sonolysis of water, and radical R(py) is formed from the direct thermal decomposition of surfactants in the interfacial region between the collapsing cavities and the bulk water. R(ab) is effective for both the reduction steps, whereas R(py) is involved only in the reduction step (1). This fact coincides with the previous reported sonochemical reduction of Pt(II) ions. Hydrogen atoms themselves scarcely participate in the reduction. The average diameter (1.0 nm) of platinum particles prepared from the system of PEG-MS is smaller than those from the aqueous solution of anionic surfactant SDS (3.0 nm) and DBS (3.0 nm).     

Storage-ring measurement of the hyperfine induced 47Ti18+(2s2p 3P0 --> 2s2 1S0) transition rate

The hyperfine induced 2s2p (3)P(0) --> 2s(2) (1)S(0) transition rate A(HFI) in berylliumlike (47)Ti(18+) is measured. Resonant electron-ion recombination in a heavy-ion storage ring is employed to monitor the time dependent population of the (3)P(0) state. The experimental value A(HFI)=0.56(3) s(-1) is almost 60% larger than theoretically predicted.     

Magnetism and superconductivity in Eu0.2Sr0.8(Fe0.86Co0.14)2As2 probed by 75As NMR

We report bulk superconductivity (SC) in Eu(0.2)Sr(0.8)(Fe(0.86)Co(0.14))(2)As(2) single crystals by means of electrical resistivity, magnetic susceptibility and specific heat measurements with T(c) is approximately equal to 20 K and an antiferromagnetic (AFM) ordering of Eu(2+) moments at T(N) is approximately equal to 2.0 K in zero field. (75)As NMR experiments have been performed in the two external field directions (H is parallel to ab) and (H is parallel to c). (75)As-NMR spectra are analysed in terms of first-order quadrupolar interaction. Spin-lattice relaxation rates (1/T(1)) follow a T(3) law in the temperature range 4.2-15 K. There is no signature of a Hebel-Slichter coherence peak just below the SC transition, indicating a non-s-wave or s(±) type of superconductivity. In the temperature range 160-18 K 1/T(1)T follows the C/(T+θ) law reflecting 2D AFM spin fluctuations.     

Cesium adsorption in hydrated iron oxide particles suspensions: an NMR study

137Cs is an important component of nuclear waste which may pollute water. Its migration in natural environments is slowed down by adsorption on minerals. Cesium adsorption on akaganeite (beta-FeOOH) particles, dextran-coated ferrihydrite (5 Fe(2)O(3)-9H(2)O) particles, and ferritin in aqueous solutions is studied with (133)Cs nuclear magnetic resonance measurements. The longitudinal relaxation time (T(1)) of (133)Cs in the presence of such magnetic particles depends on whether the ions bind to the particle or not. T(1) of (133)Cs ions in aqueous solutions containing the same amount of magnetized particles will not depend on cesium concentration if relaxation is governed by diffusion (when cesium is not able to bind), but it will depend on cesium concentration if exchange governs relaxation (when cesium is able to bind). The method is successfully tested using TEMPO, a nitroxide stable free radical whose relaxation is due to diffusion. (133)Cs relaxation in solutions of ferritin, akaganeite, and dextran-coated ferrihydrite particles is found to result from a cationic exchange of cesium ions between particles surface and bulk ions, owing to adsorption. The effect of pH on (133)Cs relaxation in solutions of the particles is consistent with the adsorption properties of cations on hydrated iron oxides.     

Methods for the measurement of (1)J(NCalpha) and (2)J(NCalpha) from a simplified 2D (13)C(alpha)-coupled (15)N SE-HSQC spectrum

Two methods for the measurement of (2)J(NCalpha) and (1)J(NCalpha) in (15)N/(13)C-labeled small and medium-size proteins are described. The current approach is based on simplified (13)C(alpha)-coupled (15)N HSQC spectra, where the two (2)J(NCalpha) doublets are separated into two subspectra corresponding to the alpha and beta spin states of the residue's own alpha carbon. The displacement of the two (2)J(NCalpha) doublets between the two subspectra provides an accurate value for (1)J(NCalpha). The alpha/beta filtration is achieved by taking the sum and difference of the recorded complementary in-phase and antiphase J-coupled spectra. J-multiplication is utilized in one of the proposed methods. In this method, an additional coupling evolution period, which is incremented in concert with t(1), is included in the pulse sequence making it possible to scale the peak-to-peak separation.     

Low-temperature thermal fixing of holograms in photorefractive La(3)Ga(5)SiO(14):Pr(3+) crystal

Thermal fixing in a La(3)Ga (5)SiO (14):Pr (3+) photorefractive crystal is demonstrated all the way down to room temperature. This, to our knowledge, is the first report of such an effect in any photorefractive material. From the temperature dependence of the process the activation energy of the carriers involved in the fixing process is measured to be E(A)=0.89 eV . Further, an effective photorefractive charge density of (1.4+/-0.2)x10(16) cm (-3) and Debye screening length of (6.8+/-0.7)x10(-6) cm is measured.     

First-principles study on the electronic structure and magnetism of layered oxyselenide La2Mn2Se2O3

The electronic structure and magnetism of layered oxyselenide La(2)Mn(2)Se(2)O(3) have been studied by using first-principles calculations within the generalized gradient approximation (GGA) and GGA + U methods. The G-type antiferromagnetic (AF) state is calculated to be the most stable phase among the various magnetic configurations of interest, irrespective of the choice of the functional used, which is in good agreement with the experiments. In contrast to La(2)Fe(2)Se(2)O(3) and La(2)Co(2)Se(2)O(3), in which the AF states show metallic behavior under the GGA method, we predict the ground state of La(2)Mn(2)Se(2)O(3) is a semiconductor with an indirect band gap of ～0.52 eV via the GGA calculations. This is closely related to a closed shell configuration and large exchange splitting (～3.5 eV) in the Mn 3d states. Moreover, the magnetic properties are also discussed in terms of the calculated Heisenberg spin exchange constants, suggesting that La(2)Mn(2)Se(2)O(3) is a strong two-dimensional magnetically frustrated system.     

萘茜光度法直接测定茶叶中的微量铜

茶叶中含有许多对人体有益的微量元素 (如Cu ,Zn ,Mn等 )而倍受人们的青睐。在中国、日本和许多其他国家都有茶文化。因此 ,有必要对茶叶中微量元素的含量进行准确测定。目前微量铜的测定方法有火焰原子吸收光谱法[1 ,2 ] 、荧光法[3,4] 、分光光度法[5～8] 和流动注射分析法[9～ 1 2 ] 。测定铜方法很多 ,由于分光光度是一种经典的方法 ,具有快速、灵敏度高 ,选择性好 ,特别是不要求贵重仪器等特点 ,它仍是检测铜重要手段之一。本文研究发现 ,在 0 1mol·L- 1 NH4Ac介质中 ,在表面活性剂SDS的存在下 ,痕量Cu(Ⅱ )与 5 ,8 二羟基 1 ,4 萘醌 (Naph)络合具有灵敏的显色反应 ,有色络合物的最大吸收波长为 330nm ,而Naph的最大吸收波长为5 1 5nm ,建立了测定痕量Cu(Ⅱ )的分光光度法。本法快速准确、灵敏度高 ,选择性好 ,可满意地测定茶叶中的微量铜。     

No confinement without Coulomb confinement

We compare the physical potential V(D)(R) of an external quark-antiquark pair in the representation D of SU(N), to the color-Coulomb potential V(coul)(R) which is the instantaneous part of the 44-component: of the gluon propagator in Coulomb-gauge D44(x-->,t)=V(coul)(|x-->|)delta(t)+(noninstantaneous). We show that if V(D)(R) is confining, lim(V(D)(R)=+ infinity, as is believed to hold in the absence of dynamical quarks, then the inequality V(D)(R)0 is the Casimir in the representation D. This implies that -V(coul)(R) is also confining.     

Yield of singlet excitons in organic light-emitting devices: a double modulation photoluminescence-detected magnetic resonance study

Double-modulation (DM) photoluminescence (PL) detected magnetic resonance (PLDMR) measurements on poly(2-methoxy-5-(2(')-ethyl)-hexoxy-1,4-phenylene vinylene) are described. In these measurements, the laser excitation power is modulated at 1相似文献   

苯基酞嗪类三环铱配合物的合成及其电致发光性能

通过含苯氧基团的苯基酞嗪衍生物配体与IrCl₃一步反应生成了三环铱配合物Ir(mppppz)₃。在480 nm光激发下其二氯甲烷溶液的发光波长为608 nm,量子产率约为0.31,磷光寿命为268 ns,其纯固态发光波长为640 nm。配合物的HOMO能级为5.14 eV,LUMO能级为2.91 eV。当Ir(mppppz)₃以2%的质量分数掺杂于PVK-PBD中做成电致发光器件后,电致发光波长为616 nm。器件的启亮电压为3.9 V,最大外量子效率为1.48%,最大亮度为1 030 cd/m²,对应的流明效率为0.81 cd/A,所发出的光的色坐标是(0.64, 0.35),接近标准红色。     

Signatures of spin-glass behaviour in PrIr2B2 and heavy fermion behaviour in PrIr2B2C

The magnetic and transport properties of PrIr(2)B(2) and PrIr(2)B(2)C have been investigated by dc and ac magnetic susceptibility, specific heat, electrical resistivity and magnetoresistance measurements. PrIr(2)B(2) forms in CaRh(2)B(2)-type orthorhombic crystal structure (space group Fddd). At low fields the dc magnetic susceptibility of PrIr(2)B(2) exhibits a sharp anomaly near 46 K which is followed by an abrupt increase below 10 K with a peak at 6 K, and split-up in ZFC and FC data below 46 K. In contrast, the specific heat exhibits only a broad Schottky type hump near 9 K which indicates that there is no long range magnetic order in this compound. The thermo-remanent magnetization is found to decay very slowly with a mean relaxation time τ = 3917 s. An ac magnetic susceptibility measurement also observes two sharp anomalies; the peak positions strongly depend on the frequency and shift towards high temperature with an increase in frequency, obeying the Vogel-Fulcher law as expected for a canonical spin-glass system. The two spin-glass transitions occur at freezing temperatures T(f1) = 36 K and T(f2) = 3.5 K with shifts in the freezing temperatures per decade of frequency δT(f1) = 0.044 and δT(f2) = 0.09. An analysis of the frequency dependence of the transition temperature with critical slowing down, τ(max)/τ(0) = [(T(f)-T(SG))/T(SG)](-zν), gives τ(0) = 10(-7) s and exponent zν = 8, and the Vogel-Fulcher law gives an activation energy of 84 K for T(f1) and 27.5 K for T(f2). While zν = 8 is typical for spin-glass system, the characteristic relaxation time τ(0) = 10(-7) s is very large and comparable to that of superspin-glass systems. An addition of C in PrIr(2)B(2) leads to PrIr(2)B(2)C which forms in LuNi(2)B(2)C-type tetragonal structure (space group I4/mmm) and remains paramagnetic down to 2 K. The specific heat data show a broad Schottky type anomaly, which could be fairly reproduced with CEF analysis which suggests that the ground state is a CEF-split singlet and the first excited state singlet is situated 15 K above the ground state. The Sommerfeld coefficient γ～300 mJ mol(-1) K(-2) of PrIr(2)B(2)C is very high and reflects a heavy fermion behaviour in this compound. We believe that the heavy fermion state in PrIr(2)B(2)C has its origin in low lying crystal field excitations as has been observed in PrRh(2)B(2)C.     

Non-LTE population probabilities of the excited ionic levels in a steady state plasma

A Complete-Steady-State (CSS) model for the charge state distribution and the ionic levels population probabilities of ions in hot non-LTE plasmas is described. The following properties of this model are described in the paper: (i) it is shown that CSS covers LTE and Corona Equilibrium (CE) in the high and low electron density regimes respectively, (ii) an explicit expression is founf for the low electron density asymptotic behavior of the population probabilities, (iii) it is shown that at intermediate density regions the CSS model predicts results similar to that of the Quasi-Steady-State model, (iv) new validity limits are derived for LTE and CE, (v) the population distribution of the excited levels is revised, (vi) an analytical expression is found for the high electron density asymptotic behavior of the population distribution, (vii) the influence of the radiation reabsorption in a spherically symmetric CSS plasma is briefly described, and (viii) the effect of the inaccuracies in the rate-coefficients on the results of CSS calculations is evaluated.     

C80n (D2,Ih)的Jahn-Teller畸变和电子光谱

用INDO系列方法研究C80n(D2,Ih)的Jahn-Teller畸变,表明C80(D2)比C80(Ih)稳定,与实验一致;C80n(D2)未发生Jahn-Teller畸变,C80n(Ih)的部分离子发生明显的Jahn-Teller畸变,电荷对C80(Ih)稳定性有显著影响.首次计算其电子光谱,不仅得到C80(D2)与实验一致的吸收峰,还预测了C80n(D2,Ih)的电子光谱,对电子跃迁进行理论指认.C80n(D2)光谱与C80(D2)相比发生吸收峰红移,而C80n(Ih)光谱与C80(Ih)相比发生吸收峰兰移,其原因是C80n(D2)的LUMO-HOMO能隙比C80(D2)小,而C80n(Ih)的能隙则比C80(Ih)的能隙大.     

Measurement of one-bond 13Calpha-1Halpha residual dipolar coupling constants in proteins by selective manipulation of CalphaHalpha spins

We have developed new 2D and 3D experiments for the measurement of C(alpha)-H(alpha) residual dipolar coupling constants in (13)C and (15)N labelled proteins. Two experiments, 2D (HNCO)-(J-CA)NH and 3D (HN)CO-(J-CA)NH, sample the C(alpha)-H(alpha) splitting by means of C(alpha) magnetization, while 2D (J-HACACO)NH and 3D J-HA(CACO)NH use H(alpha) magnetization to achieve a similar result. In the 2D experiments the coupling evolution is superimposed on the evolution of the (15)N chemical shifts and the IPAP principle is used to obtain (1)H-(15)N HSQC-like spectra from which the splitting is determined. The use of a third dimension in 3D experiments reduces spectral overlap to the point where use of an IPAP scheme may not be necessary. The length of the sampling interval in the J-dimension of these experiments is dictated solely by the relaxation properties of C(alpha) or H(alpha) nuclei. This was made possible by the use of C(alpha) selective pulses in combination with either a DPFGSE or modified BIRD pulses. Inclusion of these pulse sequence elements in the J-evolution periods removes unwanted spin-spin interactions. This allows prolonged sampling periods ( approximately 25 ms) yielding higher precision C(alpha)-H(alpha) splitting determination than is achievable with existing frequency based methods.     

2—溴甲基萘荧光和室温磷光性质研究

研究了２－溴甲基萘（２－ＢｒＭＮ）的荧光及磷光性质。２－溴甲基萘是一种优良的荧光试剂,λｅｘ／λｅｍ＝２７４／３３４ｎｍ,其浓度在１．０×１０＾－６～１．２×１０＾－４ｍｏｌ·Ｌ＾－１范围内与荧光强度呈良好的线性关系,相关系数ｒ＝０．９９９,最低检测限为４．７×１０＾－８ｍｏｌ·Ｌ＾－１。以β－环糊精（β－ＣＤ）作保护剂和１,２－二溴丙烷（ＤＢＰ）为重原子微扰剂的２－ＢｒＭＮ／β－ＣＤ／ＤＢＰ体系     

Electronic and magnetic properties of Ti(2)O(3), Cr(2)O(3), and Fe(2)O(3) calculated by the screened exchange hybrid density functional

The electronic and magnetic properties of the transition metal sesqui-oxides Cr(2)O(3), Ti(2)O(3), and Fe(2)O(3) have been calculated using the screened exchange (sX) hybrid density functional. This functional is found to give a band structure, bandgap, and magnetic moment in better agreement with experiment than the local density approximation (LDA) or the LDA+U methods. Ti(2)O(3) is found to be a spin-paired insulator with a bandgap of 0.22?eV in the Ti d orbitals. Cr(2)O(3) in its anti-ferromagnetic phase is an intermediate charge transfer Mott-Hubbard insulator with an indirect bandgap of 3.31?eV. Fe(2)O(3), with anti-ferromagnetic order, is found to be a wide bandgap charge transfer semiconductor with a 2.41?eV gap. Interestingly sX outperforms the HSE functional for the bandgaps of these oxides.     

最小摩阻场

前文简略地提到塑压陡线规律。本文视最小摩阻条件所定义之塑压接触面为一曲面“流”场,旨在于提出此“最小摩阻场”之场线规律与场函数(摩擦应力τ,压应力p)规律。主要结果为:推广前文之陡线规律于广泛情况,指出“摩擦场”与“滑质场”之基本区别在于前者为发散场,向外减阻;后者为收敛场,向内减阻。二者之复合场有“分水岭”,内场收敛,外场发散。金属表面之粘性粘着区须为一收敛场。陡线规律之库仑标量方程引出两重要推论:(1)摩擦力正比于压力之陡率(并给出比例函数之实例);(2)一切塑性压力分布皆为摩擦线弧长之函数,常含一指数项。这概括进现存不少特解。由严格不滑动条件定出具体之粘着区域。试图研究(τ,p)在应力圆中定义之“摩擦点”变化规律。以重叠应力圆法定出平面应变时此点之变域,说明在平压中摩擦系数不大时,压力约近于第一主应力。本文仅涉及原则问题。场函数解法之一见作者另文。     

Measurements of F2 and xF(nu)(3) - xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe Data in a Physics Model-Independent Way

We report on the extraction of the structure functions F2 and DeltaxF(3) = xF(nu)(3)-xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe differential cross sections. The extraction is performed in a physics model-independent (PMI) way. This first measurement of DeltaxF(3), which is useful in testing models of heavy charm production, is higher than current theoretical predictions. The ratio of the F2 (PMI) values measured in nu(mu) and mu scattering is in agreement (within 5%) with the predictions of next-to-leading-order parton distribution functions using massive charm production schemes, thus resolving the long-standing discrepancy between the two sets of data.