Measurement System for Very Small Photoelastic Constant of Polymer Films

We produced a new system for measuring the small photoelastic constant of a polymer thin film with a small birefringence. Using our mesurement system, we evaluated the photoelastic constant of a polymer film in real time by quantitative analysis. Photoelastic constants of 11.30 × 10⁻¹² Pa⁻¹ for a cellulose triacetate film and 78.38 × 10⁻¹² Pa⁻¹ for a polycarbonate film were obtained. Furthermore, we obtained a small photoelastic constant of 0.12 × 10⁻¹² Pa⁻¹ for a cycloolefin film for liquid crystal displays, using our new measurement system. This value is very small. We emphasize that, if a small change in retardation and stress cannot be detected simultaneously using our system, then we cannot obtain such a small photoelastic constant.     

Thermodynamic properties of the mixture [x1,3-dioxane+(1-x) 1,4-dioxane] at the temperature 298.15 K

Excess enthalpies, excess heat capacities, excess volumes and sound velocities of the mixture of dioxane isomers, 1,3-dioxane and 1,4-dioxane, were measured. One of the isomers, 1,4-dioxane is considered as non-polar liquid and the other as polar liquid. Excess enthalpies are positive and small, less than 55 J mol^-1. Excess heat capacities are also very small and the curve is W-shaped, and the values are from 0.03 to -0.08 J mol^-1 K^-1. Excess volumes and excess isentropic compressibilities are small and positive, and less than 0.03 cm³ mol^-1 and 0.8 TPa^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Signal-amplification detection of small molecules by use of Mg2+- dependent DNAzyme

Because small molecules can be beneficial or toxic in biology and the environment, specific and sensitive detection of small molecules is one of the most important objectives of the scientific community. In this study, new signal amplification assays for detection of small molecules based on Mg²⁺-dependent DNAzyme were developed. A cleavable DNA substrate containing a ribonucleotide, the ends of which were labeled with black hole quencher (BHQ) and 6-carboxyfluorescein (FAM), was used for fluorescence detection. When the small molecule of interest is added to the assay solution, the Mg²⁺-dependent DNAzyme is activated, facilitating hybridization between the Mg²⁺-dependent DNAzyme and the DNA substrate. Binding of the substrate to the DNAzyme structure results in hydrolytic cleavage of the substrate in the presence of Mg²⁺ ions. The fluorescence signal was amplified by continuous cleavage of the enzyme substrate. Ochratoxin A (OTA) and adenosine triphosphate (ATP) were used as model analytes in these experiments. This method can detect OTA specifically with a detection limit as low as 140 pmol?L^?1 and detect ATP specifically with a detection limit as low as 13 nmol?L^?1. Moreover, this method is potentially extendable to detection of other small molecules which are able to dissociate the aptamer from the DNAzyme, leading to activation of the DNAzyme.     

Silicon-29 NMR Study of Alkali-Exchanged NaY Zeolites

High-resolution solid-state ²⁹Si NMR has been applied to the study of partially exchanged Li, K, and Cs NaY zeolites. The order of the ²⁹Si chemical shifts of dehydrated samples is Li, Na-Y < Na-Y < K, Na-Y. The correlation between the ²⁹Si chemical shift and the Li or K loading on Li, Na-Y or K, Na-Y was rationalized in terms of the interaction between the framework and the cations inside the small cages. Because of the restrictive migration of large Cs⁺ ions from the supercages to the small cages, the ²⁹Si chemical shift of Cs, Na-Y was found to be similar to that of Na-Y.     

Separation of Ba and Pb from aqueous solutions of Sr with commercially available “precipitated active manganese dioxide”

Ba and Pb radionuclides can be removed from Sr in aqueous solution in both sodium acetate and acetic acid, containing 20 mg Sr carrier, by stirring with small (0.1–0.5 g) amounts of solid manganese dioxide. In tracer experiments⁸⁵Sr was separated with only small losses from¹³³Ba and²¹⁰Pb by separation factors of 87 and 135, respectively. The separation factor is defined here as the % of the initial⁸⁵Sr activity/ % of the initial¹³³Ba or²¹⁰Pb activity remaining in the aqueous phase after MnO₂ contact. The applicability of this technique for removing Ba and Pb radionuclides in the analysis of⁹⁰Sr in environmental samples (especially milk) is discussed.     

STM observation of Au fine-particles on graphite

Gold particles deposited on graphite in vacuum have been studied by STM observation in air. Liquid-like coalescence between small gold-particles has been observed near room temperature. Preparation of small particles in vacuum is discussed. Small particles are formed in nucleation process if the degree of coalescence of particles is reduced. Over 400 Au particles of 5 nm in diameters with a narrow size-distribution with FWHM 2 nm and a high density of 3×10¹²/cm² is prepared by evaporating gold in a vacuum of about 2×10^?5 Torr and at the substrate (HOPG) temperature of 20°C.     

Enthalpies of transfer from water to methanol of cations complexed with 18-crown-6

Enthalpies of transfer from water to methanol have been obtained via a thermochemical cycle for the [M⁺18C6] complexes where M⁺  Na⁺, K⁺, Rb⁺, Cs⁺, and Ag⁺. Variation of the transfer enthalpy with M⁺ is small.     

Oxycarbonylation of methanol over modified CuY: Enhanced activity by improving accessibility of active sites

To improve the accessibility of Cu⁺ species located in the small cages, Y zeolite was post-treated with NH₄F solution etching. The small cages were opened effectively, which allowed the reactants to interact with more Cu⁺ sites. As a result, an enhanced activity was obtained over modified CuY catalyst in oxidative carbonylation of methanol.     

Application of the two-body density matrix of the ground state for calculations of some excited states

It is pointed out that the density matrices of the ground state contain valuable information concerning the calculation of particle-hole excited states. As an illustration, results on the nuclei ¹⁶O, ²⁰Ne, and ²⁸Si are presented, using small model spaces.     

掺杂Zr4+对纳米Au/TiO2催化剂结构和性能的影响

采用氨水反滴加沉淀法合成了Zr4+掺杂的系列TiO2载体,以尿素溶液为沉淀剂,用沉积-沉淀法制备负载金催化剂。运用N2吸附-脱附(BET)、X射线衍射(XRD)、X射线荧光(XRF)、高分辨电镜(HR-TEM)和氨吸附红外光谱(NH3-IR)等技术对催化剂的结构与形貌进行了表征,并在色谱-微反应装置上考察了催化剂对CO氧化反应的活性。结果表明:(1)少量的Zr4+掺杂可形成锐钛矿型固溶体,且载体的比表面积增大;随着Zr4+掺杂量增加至10%以上,载体逐渐向无定形转变,同时比表面积急剧增大。(2)保持规整锐钛矿晶相的Zr4+掺杂载体,其表面Lewis酸位占有率较高,且具备结构缺陷,而无定形载体表面的Lewis酸位占有率大幅度降低。(3)载体表面的Lewis酸位以及结构缺陷有利于增强载体对Au颗粒的锚定作用,从而减弱焙烧过程中的颗粒聚集。(4)少量Zr4+掺杂入TiO2载体中,可以提高Au颗粒的抗烧结能力,焙烧所得的Au颗粒尺寸较小(3.63 nm),且表现出优异的催化活性,在常温下就可以将CO完全氧化。     

Temperature dependence of the chemical shifts of commonly employed proton n.m.r. reference compounds

The temperature dependence of the chemical shifts of ten commonly employed ¹H n.m.r. reference compounds of interest to both organic and biological workers was determined using the temperature independent standard ethane at low density. The water soluble standards sodium 2,2-dimethyl-2-silapentane-5-sulfonate and sodium 3-trimethylsilylpropionate-d₆ exhibited very small chemical shift changes over the range of 20–65 °C. Outside of this temperature interval the chemical shift is distinctly nonlinear, but still is sufficiently small to be neglected for many n.m.r. studies. In contrast, the temperature dependence of seven neat organic liquid reference standards was observed to be linear over a significant temperature range with slopes varying between 0.0009 and 0.0023 ppm °C^?1. Only tetramethylammonium chloride (in ²H₂O) exhibited a small but pronounced nonlinear temperature dependence over the full range investigated.     

Determination of Iron in Calf Serum Using Bathophenanthroline and Thermal Lens Spectrometry

ABSTRACT

Thermal lens spectrometry has been used for the determination of iron in calf serum. The method is based on dissociation of Fe³⁺ from proteins, reduction of Fe³⁺ to Fe²⁺ and formation of a coloured complex between Fe²⁺ and bathophenanthroline. Contrary to the spectrophotometric method, it is shown that thermal lens spectrometry is less sensitive to scattering caused by the presence of small particles remaining in the test solution after the deproteinization step. The background signal is very small and the response is only slightly dependent on the amount of scattering particles. The method is reliable, sensitive and reproducible. The limit of detection for iron is 4 ppb and the relative standard deviation is around 2%. It is expected that the volume of serum sample necessary for an analysis can be reduced to less than 100 μl.     

Enhancing the ratio of molecular ions to non-covalent compounds in the electrospray interface of LC-MS in quantitative analysis

A common problem encountered during the development of MS methods for the quantitation of small organic molecules by LC-MS is the formation of non-covalently bound species or adducts in the electrospray interface. Often the population of the molecular ion is insignificant compared to those of all other forms of the analyte produced in the electrospray, making it difficult to obtain the sensitivity required for accurate quantitation. We have investigated the effects of the following variables: orifice potential, nebulizer gas flow, temperature, solvent composition and the sample pH on the relative distributions of ions of the types MH⁺, MNa⁺, MNH₄⁺, and 2MNa⁺, where M represents a small organic molecule: BAY 11-7082 ((E)-3-[4-methylphenylsulfonyl]-2-propenenitrile). Orifice potential, solvent composition and the sample pH had the greatest influence on the relative distributions of these ions, making these parameters the most useful for optimizing methods for the quantitation of small molecules.     

Structural Characterization of YMexMn1−xO3 (Me=Cu, Ni, Co) Perovskites

The structural properties of the YMe_xMn_1−xO₃ (Me=Cu, Ni, Co) pseudobinary oxides have been studied by X-ray diffraction and electrical measurements. The powders were prepared by solid state reaction between the corresponding oxides. The incorporation in solid solution of small divalent cations, Cu²⁺, Ni²⁺, and Co²⁺, substituting for Mn in the hexagonal YMnO₃ compound, leads to a phase transition in which a perovskite-type structure is formed. The amount of substituting cation necessary for such a transition depends on the cation nature and, to a small extent, on the ionic radius. The phase transition depends strongly on the progressive substitution of the Jahn-Teller Mn³⁺ cation and therefore of the cooperative Jahn-Teller interaction weakness. The steric influence plays a secondary role, as is shown by the very small variation of the tolerance factor, t, as a function of the cation content. The solid solutions with perovskite-type structure show semiconducting behavior. The conductivity mechanism is of a thermally activated small polaron hopping.     

Analytical aspects of some organic acids

Summary o-Phenylenedioxydiacetic acid has been found to be a selective reagent for the estimation of zirconium. As little as 2.1 mg of zirconium can be easily estimated. The composition of the precipitate varies somewhat and therefore, direct weighing is not possible. This difficulty is overcome by igniting as oxide. Be²⁺, Ca²⁺, Ba²⁺, Zn²⁺, Hg²⁺, Al³⁺, Ce³⁺, Ti⁴⁺, Th⁴⁺, UO²⁺, Mn²⁺, Fe³⁺, Co²⁺, and Ni²⁺, ions do not interfere. Although V₂O₂ ⁴⁺ and Cr³⁺ ions are not precipitated in neutral or slightly acidic solutions they contaminate the zirconium precipitate, at about 0.30 N HCl concentration. The amount of contamination is so small that it is removed by double precipitation. This method gives satisfactory results even in the presence of small amounts of SO₄ ^2–ions.     

Bond‐Forming Reactions of Small Triply Charged Cations with Neutral Molecules

Time‐of‐flight mass spectrometry reveals that atomic and small molecular triply charged cations exhibit extensive bond‐forming chemistry, following gas‐phase collisions with neutral molecules. These experiments show that at collision energies of a few eV, I³⁺ reacts with a variety of small molecules to generate molecular monocations and molecular dications containing iodine. Xe³⁺ and CS₂³⁺ react in a similar manner to I³⁺, undergoing bond‐forming reactions with neutrals. A simple model, involving relative product energetics and electrostatic interaction potentials, is used to account for the observed reactivity.     

Unique carrier properties of neutral lanthanide complex for inorganic anions

Lipophilic lanthanide tris(fluorinated β-diketonates) exhibited interesting carrier properties for inorganic anions. Negative FABMS and ¹³C NMR studies revealed that they bound small Cl⁻ anion with a large hydration energy more strongly than large Br⁻ and I⁻ anions with small hydration energies. The direct anion coordination features of lanthanide complexes offered unique carrier properties for inorganic anions in liquid membrane transport.     

Characterization of the primary thermal degradation processes of peptides using the mass spectrometric technique K+IDS,K+ ionization of desorbed species

The mass spectrometric technique of K⁺ ionization of desorbed species, K⁺IDS, is used here to characterize the primary thermal degradation chemistry of small peptides. In this technique, a small amount of a compound is rapidly heated in the condensed phase. Desorption of the intact molecule can occur. Also, thermal degradation products are formed which quickly desorb as well, rather than remain on the surface and undergo subsequent chemistry. The desorbed molecules form adducts with gas phase K⁺ ions, and a mass spectrum is obtained. Deuterium labeling experiments, and the use of derivatizing reagents, allows for the thermal degradation chemistry of small peptides to be elucidated. Apparently, skeletal bond cleavages are accompanied by H-shifts, although the hydrogen atoms shift from “remote” sites, brought into close proximity with the fragmenting skeletal bond via secondary interactions. Experimental results are presented that allow for correlations between thermal degradation chemistry and the resulting K⁺IDS mass spectra to be made.     

Role of metal co-cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

First principle calculations based on density functional theory are conducted to investigate the influence of metal cations including Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, La (OH)²⁺ and Ce (OH)²⁺ in the small cage of zeolite on the electronic environment of adjacent active center, Cu⁺ in CuY zeolite as well as the process of CO insertion into CH₃O to form CH₃OCO for oxidative carbonylation of methanol. The study explains the theoretical reasons for the effects of metal cations on the catalytic activity of zeolites. It was found that, the presence of co-cations in the small cage can affect the electronic properties and also the catalytic activity in two ways. Firstly, the presence of co-cations, viz., Ca²⁺, Sr²⁺, Mg²⁺, Ba²⁺ and La species in small cage hinders the migration of active Cu⁺ cations from the super cage to small cage. Secondly, the co-cations greatly affect the charge transfer from zeolite framework to Cu⁺ present in the adjacent super cage, leading to the increase of the net charge and binding energy of Cu⁺. The findings can improve the CO adsorption and insertion efficiencies, and the stability of transition states, which results in the enhanced catalytic activity of corresponding zeolites.     

Synthesis and Characterization of Acetylene‐Linked Bisphenalenyl and Metallic‐Like Behavior in Its Charge‐Transfer Complex

We prepared and isolated a phenalenyl‐based neutral hydrocarbon ( 1 b ) with a biradical index of 14 %, as well as its charge‐transfer (CT) complex 1 b –F₄‐TCNQ. The crystal structure and the small HOMO–LUMO gap assessed by electrochemical and optical methods support the singlet‐biradical contribution to the ground state of the neutral 1 b . This biradical character suggests that 1 b has the electronic structure of phenalenyl radicals coupled weakly through an acetylene linker, that is, some independence of the two phenalenyl moieties. The monocationic species 1 b^{. +} was obtained by reaction with the organic electron acceptor F₄‐TCNQ. The cationic species has a small disproportionation energy ΔE for the reaction 2× 1 b^{. +}? 1 b + 1 b ²⁺, which presumably originates from the independence of the phenalenyl moieties. The small ΔE led to a small on‐site Coulombic repulsion U_eff=0.61 eV in the CT complex. Moreover, a very effective orbital overlap of the phenalenyl rings between molecules afforded a relatively large transfer integral t=0.09 eV. The small U_eff/4t ratio (=1.7) resulted in a metallic‐like conductive behavior at around room temperature. Below 280 K, the CT complex showed a transition into a semiconductive state as a result of bond formation between phenalenyl and F₄‐TCNQ carbon atoms.