光谱法研究水团簇结构对AlCl3溶液与血清白蛋白作用的影响

研究了冷冻-解冻处理对A1CI₃溶液团簇结构和AICl₃与血清白蛋白相互作用的影响。测定了AICl₃溶液冷冻-解冻处理前后电导率的变化,发现AICI₃溶液经冷冻处理后,电导率有明显增加。采用紫外分光光度法和荧光光谱法对冷冻前后AICI₃溶液与血清白蛋白相互作用的研究表明,A1C1₃溶液经冷冻-解冻处理后,与血清白蛋白的相互作用变弱,配位诱导作用降低,静态猝灭作用变小,这种相互作用变弱的效应是由于水的分子团簇结构变化引起的。     

Holovideo: Real-time 3D range video encoding and decoding on GPU

We present a 3D video-encoding technique called Holovideo that is capable of encoding high-resolution 3D videos into standard 2D videos, and then decoding the 2D videos back into 3D rapidly without significant loss of quality. Due to the nature of the algorithm, 2D video compression such as JPEG encoding with QuickTime Run Length Encoding (QTRLE) can be applied with little quality loss, resulting in an effective way to store 3D video at very small file sizes. We found that under a compression ratio of 134:1, Holovideo to OBJ file format, the 3D geometry quality drops at a negligible level. Several sets of 3D videos were captured using a structured light scanner, compressed using the Holovideo codec, and then uncompressed and displayed to demonstrate the effectiveness of the codec. With the use of OpenGL Shaders (GLSL), the 3D video codec can encode and decode in realtime. We demonstrated that for a video size of 512×512, the decoding speed is 28 frames per second (FPS) with a laptop computer using an embedded NVIDIA GeForce 9400 m graphics processing unit (GPU). Encoding can be done with this same setup at 18 FPS, making this technology suitable for applications such as interactive 3D video games and 3D video conferencing.     

The study of below and above band-edge imperfection states in In2S3 solar energy materials

β-In₂S₃ is a nontoxic buffer layer material usually used in a thin-film solar cell due to a lot of vacancies and surface states naturally existing in the crystal to assist in photoelectric conversion. Transition metal (TM)-incorporated β-In₂S₃ has also been proposed to increase conversion efficiency in In₂S₃ since multi-photons absorption by intermediate band (IB) would happen in the sulfide. In this paper, single crystals of undoped and Nb-doped β-In₂S₃ have been grown by the chemical vapor transport (CVT) method using ICl₃ as a transport agent. Optical properties of the imperfection states of the crystals are probed by thermoreflectance (TR), photoconductivity (PC), photoluminescence (PL), surface photoconductive response (SPR), optical absorption and photo–voltage–current (photo V–I) measurements. The TR and optical-absorption measurements confirmed that the undoped and Nb-doped β-In₂S₃ are direct semiconductors with energy gap of 1.935 eV for undoped β-In₂S₃, 1.923 eV for β-In₂S₃:Nb_0.005, and 1.901 eV for β-In₂S₃:Nb_0.01. For undoped β-In₂S₃, PC and PL measurements are used to characterize defect transitions below band gap. The above band-edge transitions of undoped β-In₂S₃ have also been evaluated using PL, PC, and SPR measurements. For the evaluation of Nb-doped β-In₂S₃, an intermediate band with energy of ∼0.4 eV below the conduction band edge has been detected in the TR measurements in both β-In₂S₃:Nb_0.005 and β-In₂S₃:Nb_0.01. The photo V–I measurements also verified that the photoelectric-conversion efficiency would be enhanced in the β-In₂S₃ with higher niobium content. Based on the experimental analyses, the optical behavior of the defects, surface states, and IB (formed by Nb) in the In₂S₃ crystals is thus explored.     

Studies of the g factors and the local structure of the orthorhombic Ni center in KTaO3 crystal

The local structure and the g factor (g_x, g_y, and g_z) of the Ni⁺ center in KTaO₃ are theoretically studied using the perturbation formulas of the g factors for a 3d⁹ ion in orthorhombically elongated octahedra. The orthorhombic field parameters are determined from the superposition model and the local geometry of the system. In view of the covalency, the contributions from the ligand orbital and spin–orbit coupling interactions are taken into account from the cluster approach. In the calculations, the orthorhombic center is attributed to Ni⁺ occupying the host Ta⁵⁺ site, associated with the nearest-neighboring oxygen vacancy V_O along the c-axis. Furthermore, the planar Ni⁺–O²⁻ bonds are found to experience the relative variation ΔR (≈0.076 Å) along the a- and b-axis, respectively, due to the Jahn–Teller effect and the size mismatching substitution of Ta⁵⁺ by Ni⁺. Meanwhile, the effectively positive V_O can make the central Ni⁺ displace away from V_O along the c-axis by about 0.20 Å. The calculated g factors based on the above local distortions show good agreement with the experimental data.     

Preparation of Nd-doped BiFeO3 films and their electrical properties

The Nd-doped BiFeO₃ thin films were prepared on SnO₂(FTO) substrates spin-coated by the sol–gel method using Nd(NO₃)₃·6H₂O, Fe(NO₃)₃·9H₂O and Bi(NO₃)₃·5H₂O as raw materials. The microstructure and electric properties of the BiFeO₃ thin films were characterized and tested. The results indicate that the diffraction peak of the Nd-doped BiFeO₃ films is shifted towards right as the doping amounts are increased. The structure is transformed from the rhombohedral to pseudotetragonal phase. The crystal grain is changed from an elliptical to irregular polyhedron. Structure transition occurring in the Bi_0.85Nd_0.15FeO₃ films gives rise to the largest Pr of 64 μC/cm². The leakage conductance of the Nd doped thin films is reduced. The dielectric constant and dielectric loss of Bi_0.85Nd_0.15FeO₃ thin film at 10 kHz are 190 and 0.017 respectively.     

Stereochemical analysis of ferrocene and the uncertainty of fluorescence XAFS data

Methods for the quantification of statistically valid measures of the uncertainties associated with X‐ray absorption fine structure (XAFS) data obtained from dilute solutions using fluorescence measurements are developed. Experimental data obtained from 10 mM solutions of the organometallic compound ferrocene, Fe(C₅H₅)₂, are analysed within this framework and, following correction for various electronic and geometrical factors, give robust estimates of the standard errors of the individual measurements. The reliability of the refinement statistics of standard current XAFS structure approaches that do not include propagation of experimental uncertainties to assess subtle structural distortions is assessed in terms of refinements obtained for the staggered and eclipsed conformations of the C₅H₅ rings of ferrocene. Standard approaches (XFIT, IFEFFIT) give refinement statistics that appear to show strong, but opposite, preferences for the different conformations. Incorporation of experimental uncertainties into an IFEFFIT‐like analysis yield refinement statistics for the staggered and eclipsed forms of ferrocene which show a far more realistic preference for the eclipsed form which accurately reflects the reliability of the analysis. Moreover, the more strongly founded estimates of the refined parameter uncertainties allow more direct comparison with those obtained by other techniques. These XAFS‐based estimates of the bond distances have accuracies comparable with those obtained using single‐crystal diffraction techniques and are superior in terms of their use in comparisons of experimental and computed structures.     

Simple dose rate measurements for a very high synchrotron X‐ray flux

Dose measurements based on methylene blue (MB) bleaching, widely used for ultraviolet light, can also be applied to X‐rays including very high flux levels. This method has been tested by using both MB bleaching and Fricke dosimetry for a conventional monochromatic X‐ray source and then for `white‐beam' synchrotron radiation. The results show that MB bleaching dosimetry can easily measure X‐ray doses up to at least 10⁵ Gy s^?1, as long as the MB concentration is sufficiently high. This condition can be verified from the deviations from linearity of the bleaching versus exposure time.     

Origin of the X‐ray magnetic circular dichroism at the L‐edges of the rare‐earths in RxR1−x′Al2 systems

An X‐ray magnetic circular dichroism (XMCD) study performed at the rare‐earth L_2,3‐edges in the R_xR_1?x′Al₂ compounds is presented. It is shown that both R and R′ atoms contribute to the XMCD recorded at the L‐edges of the selected rare‐earth, either R or R′. The amplitude of the XMCD signal is not directly correlated to the magnetization or to the value of the individual (R, R′) magnetic moments, but it is related to the molecular field acting on the rare‐earth tuned in the photoabsorption process. This result closes a longstanding study of the origin of the XMCD at the L‐edge of the rare‐earths in multi‐component systems, allowing a full understanding of the exact nature of these signals.     

Up-conversion emissions of Er<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> codoped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by the arc discharge synthesis method

The Er³⁺-Yb³⁺ codoped Al₂O₃ nanoparticles with an average particle size of about 50 nm have been synthesized by an arc discharge synthesis method. The green and red up-conversion emissions centered at about 526, 547 and 677 nm, corresponding respectively to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The Annealing has evident effect on the up-conversion emissions of the samples: The red up-conversion emission is noticeable before annealing; however, the green up-conversion emission becomes predominant after annealing. The mixture of (Er,Yb)₃Al₅O₁₂ and α-(Al,Er,Yb)₂O₃ phases is more favorable for green up-conversion emissions due to an enhancement of the ESA (I) of ⁴I_11/2+a photon→⁴F_7/2 and ET (III) of ²F_5/2(Yb³⁺)+⁴I_11/2(Er³⁺)→²F_7/2(Yb³⁺)+⁴F_7/2(Er³⁺) processes. The two-photon absorption up-conversion process is involved in the green and red up-conversion emissions. The results have proved that arc discharge synthesis is a new promising preparation technology for optical materials. Supported by National Natural Science Foundation of China (Grant No. 10804015), the Scientific Research Foundation for Doctor of Liaoning Province (Grant No. 20071095), and the Educational Committee Foundation of Liaoning Province (Grant No. 2008123)     

Improved synthesis of polyfluorinated l-lysine for 19F NMR-based screening

Polyfluorinated N-α-Fmoc--Boc-l-lysine represents the best-in-class among a set of polyfluorinated amino acids (PFAs) which are useful tools for ¹⁹F NMR-Based Screening. In this communication, optimized reaction conditions that allowed for the multi-gram preparation of this unnatural amino acid are reported.