Polarization memory in single quantum dots

We measured the polarization memory of excitonic and biexcitonic optical transitions from single quantum dots at either positive, negative or neutral charge states. Positive, negative and no circular or linear polarization memory was observed for various spectral lines, under the same quasi-resonant excitation below the wetting layer bandgap. We developed a model which explains both qualitatively and quantitatively the experimentally measured polarization spectrum for all these optical transitions. We consider quite generally the loss of spin orientation of the photogenerated electron–hole pair during their relaxation towards the many-carrier ground states. Our analysis unambiguously demonstrates that while electrons maintain their initial spin polarization to a large degree, holes completely dephase.     

Use of a temperature‐programmable injector coupled to gas chromatography–combustion–isotope ratio mass spectrometry for compound‐specific carbon isotopic analysis of polycyclic aromatic hydrocarbons

Compound‐specific isotopic analysis (CSIA) can provide information about the origin of analysed compounds; for instance, polycyclic aromatic hydrocarbons (PAHs) in aerosols. This could be a valuable tool in source apportionment of particulate matter (PM) air pollution. Because gas chromatography–combustion–isotope ratio mass spectrometry (GC‐C‐IRMS) analysis requires an amount of at least 10 ng of an individual PAH, a high concentration of PAHs in the injected extract is needed. When the concentration is low a large volume injector creates the possibility of introducing a satisfactory amount of individual PAHs. In this study a temperature‐programmable injector was coupled to GC‐C‐IRMS and injection parameters (solvent level, transfer column flow, transfers time) were optimised using six solid aromatic compounds (anthracene, fluoranthene, pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene) dissolved in n‐pentane and EPA 610 reference mixture. CSIA results for solid PAHs were compared with results obtained for the single components analysed by elemental analysis–isotope ratio mass spectrometry. The injection method was validated for two sample injection volumes, 50 and 100 µL. This method was also compared with commonly used splitless injection. To be included in the study, measurements had to have an uncertainty lower than 0.5‰ for and a minimum peak height of 200 mV. The lower concentration limits at which these criteria were fulfilled for PAHs were 30 mg/L for 1 µL in splitless injection and 0.3 and 0.2 mg/L for 50 and 100 µL, respectively, in large volume injection. Copyright © 2009 John Wiley & Sons, Ltd.     

Fluorinated Boron Nitride Quantum Dots: A New 0D Material for Energy Conversion and Detection of Cellular Metabolism

Quantum dots encompass a broad spectrum of optical, catalytic, and electrochemical properties bringing in novel applications in catalysis, imaging, displays, and optoelectronics. Herein, the unanticipated broad‐spectrum light absorption and high fluorescence quantum yield in fluorinated boron nitride (FBN) quantum dots are discussed. A heterostructure of FBN quantum dots with a wide‐bandgap semiconductor, titania nanotube arrays, exhibits high photocatalytic activity as evidenced by high external quantum efficiency extending from ultraviolet to green region of the solar spectrum (≈24% at 400 nm). The high activity is confirmed using photoelectrochemical hydrogen evolution experiments. Further, it is demonstrated that high fluorescence quantum yield could be tapped for the detection of glycolytic activity in cancer cells compared to normal cells. This finding could shift the paradigm of molecular detection using quantum dots. The 0D structure and the gap states introduced through fluorination are believed to be responsible for these unprecedented characteristics of boron nitride.     

Ultrafast nonadiabatic photodissociation dynamics of F2 in solid Ar

We explore the ultrafast spin-flip dynamics in a diatomic molecule imbedded in a rare gas matrix using the combination of a quantum mechanical and a semiclassical surface hopping method. Specifically, we investigate (1) the extent to which the phenomenon of electronically-localized eigenstates in strongly-coupled manifolds survives in the presence of rapid decay and a multitude of electronically coupled states; (2) the ability of the surface hopping method to predict the short time dynamics; and (3) the time range over which frozen lattice models are valid. Our results point to the active role played by a large number of coupled electronic states in the F₂/Ar dynamics while substantiating our confidence in the validity of the popular surface hopping approach for the system considered.     

红外光谱法研究低温焚烧稻壳灰对Cr(Ⅵ)的吸附机理

采用Boehm滴定法量化了低温焚烧稻壳灰表面官能团,考察了溶液初始pH值和温度对吸附效能的影响,借助动力学方程和吸附等温线,研究了稻壳灰对Cr(Ⅵ)的吸附性能,利用红外图谱、扫描电镜表征了稻壳灰的表面形貌和吸附机理。结果表明：在pH值为5时,稻壳灰对Cr(Ⅵ)取得最优去除效果,吸附前后溶液pH值变化很小。稻壳灰对Cr(Ⅵ)有较强的去除能力,对于20 mg·L-1的Cr(Ⅵ)溶液,最高去除率能达到95%左右,达到《污水综合排放标准GB8978—1996》1～2级标准。吸附过程能更好地符合准二级反应动力学方程和Langmuir等温线方程,饱和吸附容量可达3.277 6 mg·g-1。红外光谱表明酰胺Ⅱ带、Si—O—Si、O—Si—O等在Cr(Ⅵ)吸附过程中可能有重要贡献。扫描电镜图片表明吸附Cr(Ⅵ)后,稻壳灰表面分布有众多的光亮沉积物,有条带状或不规则点斑出现,推测无机微沉淀和氧化还原机理在吸附过程中起重要作用。稻壳灰是一种价格低廉、有应用潜力的高效吸附剂,可以用于水体重金属污染的治理修复。     

Two-electron repulsion integrals over Gaussian s functions

We present an efficient scheme to evaluate the [ 0 ]^(m) integrals that arise in many ab initio quantum chemical two-electron integral algorithms. The total number of floating-point operations (FLOPS ) required by the scheme has been carefully minimized, both for cases where multipole expansions of the integrals are admissable and for cases where this is not so. The algorithm is based on the use of a modified Chebyshev interpolation formula to compute the function exp(?T) and the integral F_m(T) = ∫₀¹u^2mexp(?Tu²) du very cheaply.     

A gate to organokrypton chemistry: HKrCCH

An organic molecule containing krypton, HKrCCH, is reported. The preparation of HKrCCH includes 193-nm photolysis of H2C2/Kr solid mixtures at 8 K and subsequent thermal mobilization of hydrogen atoms at >/=30 K. The identification is based on infrared absorption spectroscopy and supported by ab initio calculations which show ionic and covalent contributions to the bonding. We believe that a series of similar organokrypton molecules can be prepared as computationally demonstrated for HKrC4H and HKrC3H3. These results feature a generally novel way for activating chemically the H-CC- group, which can find practical applications of the krypton catalysis.     

Split-pool method for synthesis of solid-state material combinatorial libraries

The synthesis and analysis of inorganic material combinatorial libraries by the split-pool bead method were demonstrated at the proof-of-concept level. Millimeter-size spherical beads of porous gamma-alumina, a commonly used support material for heterogeneous catalysts, were modified with Al(13)O(4)(OH)(24)(H(2)O)(12)(7+) cations in order to promote irreversible adsorption of the anionic fluorescent dyes Cascade Blue, Lucifer Yellow, and Sulforhodamine 101. The compositions of individual beads were easily determined through three split-pool cycles using a conventional fluorescence plate reader. Small split-pool material libraries were made by adsorbing noble metal salts (H(2)PtCl(6), H(2)IrCl(6), and RhCl(3)) into the beads. Analysis of these beads by micro-X-ray fluorescence showed that quantitative adsorption of metal salts without cross-contamination of beads could be achieved at levels (0.3 wt % metal loading) relevant to heterogeneous catalysis. The method offers the potential for synthesis of rather large libraries of inorganic materials through relatively simple benchtop split-pool chemistry.     

Synthesis and characterization of novel rhenium(V) tetradentate N2O2 Schiff base monomer and dimer complexes

Several rhenium(V) oxo complexes with tetradentate N(2)O(2) Schiff base ligands were synthesized and characterized. The general synthetic procedure involved reaction of [NBu(4)][ReOCl(4)] with a tetradentate Schiff base ligand (L(1) = N,N'-ethylenebis(acetylacetoneimine), (acac(2)en) or L(2) = N,N'-propylenebis(acetylacetoneimine) (acac(2)pn)) in ethanol solution to generate complexes of the form trans-ReOX(L) where X = Cl(-), MeO(-), ReO(4)(-), or H(2)O. The product isolated from the reaction was found to be dependent on the reaction conditions, in particular the presence or absence of water and/or base. The mu-oxo-Re(2)O(3)(L)(2) dimers were synthesized and characterized for chemical and structural comparison to the related monomers. Conversion of the monomer to its dimer analogue was followed qualitatively by spectrophotometry. The complexes were characterized by (1)H and (13)C NMR, UV-vis, and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. The crystallographic data reported for the structures are as follows: trans-[ReO(OH(2))(acac(2)en)]Cl (H(20)C(12)ClN(2)O(4)Re) 1, triclinic (Ponemacr;), a = 7.2888(6) A, b = 9.8299(8) A, c = 10.8195(9) A, alpha = 81.7670(10) degrees, beta = 77.1510(10) degrees, gamma = 87.6200(10) degrees, V = 747.96(11) A(3), Z = 2; trans-[ReO(OReO(3))(acac(2)en)] (H(18)C(12)N(2)O(7)Re(2)) 2, monoclinic (P2(1)/c), a = 7.5547(4) A, b = 8.7409(5) A, c= 25.7794(13) A, beta = 92.7780(10) degrees, V = 1700.34(16) A(3), Z = 4; trans-[ReOCl(acac(2)pn)] (H(20)C(13)N(2)O(3)ClRe) 3, monoclinic (P2(1)/c), a = 8.1628(5) A, b = 13.0699(8) A, c = 28.3902(17) A, beta = 97.5630(10) degrees, V = 3002.5(3) A(3), Z = 8; trans-[ReO(OMe)(acac(2)pn)] (H(23)C(14)N(2)O(4)Re) 4, monoclinic (P2(1)/c), a = 6.7104(8) A, b = 27.844(3) A, c = 8.2292(9) A, beta = 92.197(2) degrees, V = 1536.4(3) A(3), Z = 4; trans-[mu-oxo-Re(2)O(3)(acac(2)en)(2)] (H(36)C(24)N(4)O(7)Re(2)) 5, monoclinic (P2(1)/n), a = 9.0064(5) A, b = 12.2612(7) A, c = 12.3695(7) A, beta = 90.2853(10) degrees, V = 1365.94(13) A(3), Z = 2; and trans-[mu-oxo Re(2)O(3)(acac(2)pn)(2)] (H(40)C(26)N(4)O(7)Re(2)) 6, monoclinic (P2(1)/n), a = 9.1190(5) A, b = 12.2452(7) A, c = 12.8863(8) A, beta = 92.0510(10) degrees, V = 1438.01(14) A(3), Z = 2.