催化动力学光度法测定痕量铜的研究

本研究了在氨水介质中铜（Ⅱ）催化过氧化氢氧化亮黄的褪色反应及其动力学条件，建立了一种超高灵敏、高选择性的测定环境试样中痕量铜的新方法，可测定０．００４～０．５μｇ／２５ｍＬ范围内的铜（Ⅱ）。     

傅里叶变换技术在紫外可见光谱区的应用

本文评述了傅里叶变换在紫外可见光谱区的应用，探讨了傅里叶变换在紫外可见光谱学以及信号处理两方面的内容。详细介绍了傅里叶变换在紫外可见区遇到的问题、主要优点和发展前景。     

Study on fluorescence property of dopamine and determination of dopamine by fluorimetry

In this study, a rapid and sensitive high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) determination of primary As species in fish tissues and urine is reported. The separation was achieved on an Altima C18 column with a mobile phase containing citric acid and hexanesulfonic acid (pH 4.5). As(V), monomethylarsonic acid (MMA), As(III), dimethylarsinic acid (DMA) and arsenobetaine (AsB) were separated in less than 4 min with retention times of 83, 99, 130, 166 and 208 s, respectively. This separation of five species in less than 4 min should be attractive to those interested in As speciation. The quantification limits were 44, 56, 94, 64, 66 ng l(-1) and the relative standard deviations (R.S.D.) for day-to-day injections of As at 2 mug l(-1) were 2.0, 3.1, 2.4, 3.8 and 4.0%. The procedure was tested using two reference materials (DORM-2 dogfish muscle tissue, NIST SRM 2670 Freeze-dried Urine, normal level) and then applied to real-world samples. The results obtained demonstrate the suitability of the procedure for screening and quantification at physiological levels of primary As species in biological samples.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.     

Synthesis,crystal structure and ferro-magnetic interaction of a binuclear copper(II) complex with the 1,4-dinitro-2,3,5,6-tetracarboxylatobenzenic anion as bridging ligand

A binuclear complex [Cu₂(DTB)(DMF)₄(H₂O)]·2DMF (DTB = 1,4-dinitro-2,3,5,6-tetracarboxylatobenzenic anion; DMF = N,N-dimethylformamide) has been synthesized and its crystal structure determined by X-ray crystallography. In the complex Cu ion is located in a distorted square pyramidal environment with two oxygen atoms O(1) and O(3) from two carboxylate groups, another two oxygen atoms O(7) and O(8) from terminal ligands of two DMF molecules, and a fifth coordinated oxygen atom O(9) from the terminal ligand of one H₂O molecule, in which the O(8) atom is situated in the apex of the pyramid. DTB as bridging ligand coordinates two Cu ions through its four carboxylate groups. The variable-temperature magnetic susceptibility of the complex was measured in the 5–300 K range. The magnetic coupling parameter is consistent with a ferromagnetic exchange between the two copper(II) centers and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator ( = -2J₁₂, ₁ = ₂= 1/2), giving the ferromagnetic coupling parameter of 2J = 1.80 cm^{- 1}. This is the first example of a tetracarboxylatobenzenic bridging complex exhibiting ferromagnetic interaction.     

Spectroscopic evidence for triplet excitation energy transfer among carotenoids in the LH2 complex from photosynthetic bacterium <Emphasis Type="Italic">Rhodopseudomonas palustris</Emphasis>

The LH2 complex from Rhodopsudomonas (Rps.) palustris is unique in the heterogeneous carotenoid compositions. The dynamics of triplet excited state Carotenoids (³Car* has been investigated by means of sub-microsecond time-resolved absorption spectroscopy both at physiological temperature (295 K) and at cryogenic temperature (77K). Broad and asymmetric T _n ←T ₁ transient absorption was observed at room temperature following the photo-excitation of Car at 532 nm, which suggests the contribution from various carotenoid compositions having different numbers of conjugated C=C double bonds (N_c=c). The triplet absorption bands of different carotenoids, which superimposed at room temperature, could be clearly distinguished upon decreasing the temperature down to 77 K. At room temperature the shorter-wavelength side of the main T_n04T₁ absorption band decayed rapidly to reach a spectral equilibration with a characteristic time constant of ∽1 μs, the same spectral dynamics, however, was not observed at 77 K. The aforementioned spectral dynamics can be explained in terms of the triplet-excitation transfer among heterogeneous carotenoid compositions. Global spectral analysis was applied to the time-resolved spectra at room temperature, which revealed two spectral components peaked at 545 and 565 nm, and assignable to the T_n04 T₁ absorption of Cars with Nc=c=11 and Nc=c=13, respectively. Surprisingly, the decay time constant of a shorter-conjugated Car, i.e. 0.72 ώs (aerobic) and 1.36 ώs (anaerobic), is smaller than that of a longer-conjugated Car, i.e. 2.12 us (aerobic) and 3.75 ώs (anaerobic), which is contradictory to the general rule of carotenoids and relative polyenes. The results are explained in terms of triplet-excitation transfer among different types of Cars. It is postulated that two Cars with different conjugation lengths coexist in an α, β-subunit in the LH2 complex.     

NBR/ORGANOMODIFIED BENTONITE INTERCALATED HYBRIDS AND THEIR EFFECTS ON THE TOUGHNESS OF PVC

Hybrids of intercalative nitrile-butadiene rubber/organomodified bentonite (NBR/OMB) were prepared by thelatex intercalation technique. Investigation of their mechanical properties and the microstructore of NBR/OMB showed thatthe organomodified bentonite is an effective toughener for NBR. Transmission electronic microscopy (TEM) and X-rnydiffraction (XRD) tests showed that the NBR macromolecule could be intercalated into the galleries of bentonite.Incorporation of NBR/OMB hybrids as tougheners into poly(vinyl chloride) (PVC) results in a substantial increase in theimpact strength of PVC, but little decrease in its tensile strength and flexural strength, compared to the unmodified PVC.     

Synthesis,characterization and interaction of mixed polypyridyl ruthenium(II) complexes with calf thymus DNA

New mixed polypyridyl {HPIP = 2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline, phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, dmb = 4,4-dimethyl-2,2-bipyridine} ruthenium(II) complexes [Ru(phen)₂(HPIP)]²⁺, [Ru(dmp)₂(HPIP)]²⁺ and [Ru(dmb)₂(HPIP)]²⁺ were synthesized and characterized by elemental analyses ¹H-n.m.r., u.v.–vis. spectroscopy and cyclic voltammetry. Their DNA-binding properties were demonstrated by absorption, luminescence titrations, steady-state emission quenching and viscosity measurements. The results suggested that all the examined complexes bind with CT-DNA intercalatively. Methyl groups substituted at the 4,4-positions of bpy has no obvious effect on its DNA binding, whereas substituents at the 2- and 9-positions of phen have an impressive effect on its DNA-binding, as revealed by the decreased binding affinity.     

铅在铂电极上的还原电位溶出分析法

研究了以亚铁氰化钾为还原剂铅在铂电极上的还原电位溶出法；讨论了电极的预处理、阳极富集和随后的还原电位溶出及铅测定的干扰。