三重态SiCP2异构体的结构和稳定性的理论研究

采用DFT,QCISD和CCSD(T)等理论计算方法对三重态SiCP2异构体的结构和稳定性进行了理论研究.在B3LYP/6-311G(d)水平下,共计算得到由17个过渡态相连接的15个异构体.在CCSD(T)/6-311 +G(2df)//QCISD/6-311G(d)水平下,考虑重点振动能相对能量最低的三元环状异构体P-cCSiP 8(0.0 kJ/mol)及四元环状结构的cPCSiP 4具有相当大的动力学稳定性,在一定的实验室和星际条件下可能被检测到.另外,对它们的成键性质也进行了分析.     

Ab initio and pseudopotential calculations on the singlet and triplet states of the disilyne isomers

Ab initio SCF as well as pseudopotential calculations were performed for determining equilibrium structures and relative stabilities of several disilyne isomers. For the singlet state there are only two structures, the bridged and the silavinylidene carbene, which correspond to minima on the energy hypersurface. The most stable of the six isomeric structures investigated is the bridged conformer in the ¹A₁ electronic state, followed by the silavinylidene carbene in the ¹A₁ and ³A₂ electronic states. Inclusion of electron correlation by MRD-CI calculations has no qualitative influence on the relative stabilities found in the SCF calculations.     

Low-lying isomers and finite temperature behavior of (H2O)6 -

(H2O)(6) (-) appears as a "magic" number water cluster in (H2O)(n) (-) mass spectra. The structure of the (H2O)(6) (-) isomer dominating the experimental population has been established only recently [N. I. Hammer et al., J. Phys. Chem. A 109, 7896 (2005)], and the most noteworthy characteristic of this isomer is the localization of the excess electron in the vicinity of a double-acceptor monomer. In the present work, we use a quantum Drude model to characterize the low-energy isomers and the finite temperature properties of (H2O)(6) (-). Comparison with ab initio calculations shows that the use of a water model employing distributed polarizabilities and distributed repulsive sites is necessary to correctly reproduce the energy ordering of the low-lying isomers. Both the simulations and the ab initio calculations predict that there are several isomers of (H2O)(6) (-) significantly lower in energy than the experimentally observed species, suggesting that the experimental distribution is far from equilibrium.     

Laser-induced temperature dependent triplet state lifetime of rubreneperoxide

A number of photophysical properties of three different types of rubreneperoxides have been measured experimentally by flash spectroscopy technique, including the two-photon absorption, fluorescence, delayed fluorescence and temperature dependent triplet-triplet absorption spectra. Excited singlet and triplet state lifetimes are temperature dependent. Lowest triplet state lifetimes were measured from 77 K to 50 degrees C. Experimental observations showed that as we decreased the temperature of rubreneperoxides, most of the molecules migrate to the lowest vibrational and rotational energy levels of the ground electronic state. Similar migration is also observed for the lowest triplet state. Therefore at 77 K, we can get the clean absorption an emission spectra and decay curves for the lowest triplet state. At 50 degrees C, due to the P- and/or E-type of delayed fluorescences, decay of T(1) state, in other words disappearance of the T(1) state is becoming faster than at low temperature (below room temperature).     

Effect of subambient temperature on RP-HPLC of β-carotene isomers

Summary (E)-β-carotene and three mono-(Z)-isomers (9(Z)-, 13(Z)-, 15(Z)-) were eluted isocratically on a VYDAC 201TP54 column, using column temperatures between +30°C and −7°C. In this temperature range, their elution order changed dramatically with decreasing temperature. Nearly baseline separation of the four isomers within one hour was achieved at −7°C. For laboratory routine, temperatures of 9±2°C can be recommended. Thus, a good resolution of β-carotene- and lycopene-isomers (e.g. in tomato products) within 30 minutes is possible.     

Chemometric deconvolution of gas chromatographic unresolved conjugated linoleic acid isomers triplet in milk samples

A generally known problem of GC separation of trans-7;cis-9; cis-9,trans-11; and trans-8,cis-10 CLA (conjugated linoleic acid) isomers was studied by GC–MS on 100 m capillary column coated with cyanopropyl silicone phase at isothermal column temperatures in a range of 140–170 °C. The resolution of these CLA isomers obtained at given conditions was not high enough for direct quantitative analysis, but it was, however, sufficient for the determination of their peak areas by commercial deconvolution software. Resolution factors of overlapped CLA isomers determined by the separation of a model CLA mixture prepared by mixing of a commercial CLA mixture and CLA isomer fraction obtained by the HPLC semi-preparative separation of milk fatty acids methyl esters were used to validate the deconvolution procedure. Developed deconvolution procedure allowed the determination of the content of studied CLA isomers in ewes’ and cows’ milk samples, where dominant isomer cis-9,trans-11 is eluted between two small isomers trans-7,cis-9 and trans-8,cis-10 (in the ratio up to 1:100).     

Room temperature phosphorimetric determination of cyanide based on triplet state energy transfer

The determination of cyanide ions in water samples by room temperature phosphorescence (RTP) detection is described. The method is based on the measurement of the RTP emission of α-bromonaphthalene (BrN). The principle of the RTP cyanide determination involves the energy transfer (ET) from the BrN phosphor molecule insensitive to the presence of cyanide (acting as a donor) to a cyanide-sensitive dye (acceptor).The RTP emission spectrum of BrN overlaps significantly with the absorption spectrum of the complex formed between copper and Cadion 2B, giving rise to a non-radiative ET from the phosphor molecules to the metal complex. The sensing of cyanide ions is based on the displacement by cyanide of the copper ions from its complex with Cadion 2B (the free chelating molecule presents a low absorbance in the region of maximum emission of the BrN phosphor). An increase in the concentration of cyanide causes a decrease on the concentration of the Cadion 2B-copper complex (acceptor) with the subsequent decrease of the absorbance in the overlapping region with the RTP spectra, resulting in higher RTP emission signals measured. Both, RTP intensities and triplet lifetimes of the BrN increased with the increase of the cyanide concentration.The calibration graphs were linear up to a concentration of 500 mg l⁻¹ cyanide and a precision of ±2 and ±0.5% for five replicates of 50 μg l⁻¹ of cyanide has been obtained when measuring intensities and triplet lifetimes values, respectively. A detection limit of 3 μg l⁻¹ of cyanide was achieved under optimal reaction conditions and pH 11. The use of phosphorescence measurements (low background noise signals) resulted in an important improvement on the sensitivity of the cyanide detection higher than eight times as compared to the molecular absorption spectrophotometric method for cyanide detection based on the use of Cadion 2B-copper as cyanide-indicator.Interference studies were performed with cations and anions present in drinking water samples which could affect the analytical response. Finally, the method has been successfully applied to the determination of trace levels of labile cyanide in spiked drinking water samples.     

Theoretical study on structures and stability of triplet SiC<Subscript>3</Subscript>O isomers

Various levels of calculations are carried out~for exploring the potential energy surface (PES) of triplet SiC₃O, a molecule of potential interest in interstellar chemistry. A total of 38 isomers are located on the PES including chain-like, cyclic and cage-like structures, which are connected by 87 interconversion transition states at the DFT/B3LYP/6-311G(d) level. The structures of the most relevant isomers and transition states are further optimized at the QCISD/6-311G(d) level followed by CCSD(T)/6-311+G(2df) single-point energy calculations. At the QCISD level, the lowest lying isomer is a linear SiCCCO 1 (0.0 kcal/mol) with the ³ ∑ electronic state, which possesses great kinetic stability of 59.5 kcal/mol and predominant resonant structure . In addition, the bent isomers CSiCCO 2 (68.3 kcal/mol) and OSiCCC 5 (60.1 kcal/mol) with considerable kinetic stability are also predicted to be candidates for future experimental and astrophysical detection. The bond natures and possible formation pathways in interstellar space of the three stable isomers are discussed. The predicted structures and spectroscopic properties for the relevant isomers are expected to be informative for the identification of SiC₃O and even larger SiC _n O species in laboratory and interstellar medium. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Differing adsorption behavior of environmentally important cyanophenol isomers at the air-water interface

Vibrational sum-frequency spectroscopy and surface tensiometry have been used to study the adsorption of m- and p-cyanophenol at the air-water interface. Spectra of the cyano (CN) group under different polarization schemes are utilized to determine its hydrogen bonding environment and orientation. For both isomers, it is found that the cyano group is hydrogen bonded at the interface but that the CN orientation is independent of surface density. The average CN tilt angle (theta(0)), however, is found to differ between the isomers, such that the CN group points down toward the aqueous phase for m-cyanophenol (theta(0) = 96-106 degrees ) but points up toward the vapor phase for the p-cyanophenol (theta(0) = 65-80 degrees ). In addition, this average tilt angle is distributed over a narrow range, sigma(0) < 10 degrees for the meta isomer and sigma(0) < 16 degrees for the para isomer.     

苯二酚异构体电迁移行为预测与研究

系统研究了邻、间、对苯二酚3种异构体在毛细管区带电泳中的迁移行为,从理论上分析了解离常数、缓冲液pH与迁移行为之间的关系,进行了定量预测。通过实验讨论了缓冲溶液类型及浓度、缓冲溶液的pH、分离电压等因素对三种异构体分离的影响,获得了优化的分离条件。结果表明,使用未涂层石英毛细管柱(50μmi.d.,50 cm,有效长度为45 cm),在检测波长225 nm,硼砂缓冲溶液30 mmol/L,pH为8.5~9.15,分离电压为10~25 kV的条件下,苯二酚3种异构体均可按对、间、邻的顺序得到基线分离,实验结果与理论预测相符。     

Retention behavior of dipeptide isomers in reversed-phase high-performance liquid chromatography

Summary The effects of eluent pH and organic modifier concentration on the capacity factor (k) and selectivity of dipeptide isomers were investigated. It has been observed that the variation in the logarithm of the capacity factor of the dipeptide isomers is linearly dependent on the organic modifier concentration (C_b), however, the selectivity is almost independent of it. Both capacity factor and selectivity were seriously affected by the pH of the eluent. Both the capacity factor and the intercept of the ln k vs. C_b plot increased with increasing van der Waals volume of the non-polar amino acid subunit of the dipeptides.     

萘酚异构体在乙炔黑修饰电极上的电化学行为及测定

制备了乙炔黑修饰电极(AB/GCE),运用交流阻抗法研究了电极表面的特性。研究了1-萘酚(α-N)和2-萘酚(β-N)在该修饰电极上的循环伏安行为,探讨了修饰剂用量、底液种类及pH、浓度和扫速对伏安行为的影响。在pH6.0的B-R缓冲液中,α-N和β-N均出现一明显的不可逆氧化峰。在60~240mV·s-1扫速范围内,二者氧化峰电流与扫速均呈线性关系,表明该电极过程是受吸附控制的不可逆过程。计算了电极过程的部分动力学参数。运用线性扫描伏安法结合半微分技术对α-N和β-N进行了同时定量测定,发现α-N和β-N的半微分氧化峰电流值与其浓度在5.00×10-5~6.50×10-4mol·L-1范围内呈良好的线性关系(rα-N=0.996;rβ-N=0.997)。α-N和β-N的检出限(S/N=3)分别为5.04×10-7mol·L-1,6.69×10-7mol·L-1。加标回收率分别为97.20%~100.20%和95.40%~102.50%。     

Influence of triplet—triplet excitation transfer on the decay function of donor luminescence

The triplet—triplet electronic excitation transfer from benzophenone to naphthalene in rigid solutions has been investigated by measuring the non-exponential decay curve of benzophenone photphorescence using a laser pulse for excitation. The results of measurements were satisfactorily reproduced by Inokuti—Hirayama's formula based on Dexter's theory of exchange interaction.     

Pressure and temperature effects on the conformational equilibria between the rotational isomers of sec- and iso-butyl halides

The conformational changes of iso-butyl halides and sec-butyl halides in pure liquid state have been analyzed by Raman spectroscopy as a function of temperature and pressure. The enthalpy and volume differences in the conformer of these halogenoalkanes have been obtained. The relation between ΔH and ΔV was discussed according to the thermodynamical consideration and the configurational entropy difference of each rotational isomer in liquid state was estimated by combining the spectroscopic and ultrasonic relaxation data reported in the literature.     

Photon upconversion based on sensitized triplet–triplet annihilation

Photon upconversion, the process wherein light of long wavelength is frequency converted to photons of higher energy, is readily achieved at low incident power through sensitized triplet–triplet annihilation (TTA) in various chromophore combinations spanning the UV to the near-IR. This emerging wavelength-shifting technology truly represents a viable route towards converting low energy terrestrial solar photons into light adequate to drive electron transfer in operational photovoltaics. Generalized molecular design constraints, all operational examples reported to date, and measurement techniques applied to these low power nonlinear processes are reviewed in this contribution. In many instances, direct visualization of this phenomenon is presented in solution and within various polymeric host materials.     

A triplet carbene surviving a week in solution at room temperature

A stable triplet carbene, having a lifetime at 25 degrees C of 14.5 days in a dilute benzene solution, was realized by simply changing the substituent at the 10 position of the previously most persistent carbene, di[9-(10-phenyl)anthryl]carbene, from a phenyl to a 2,6-dimethyl-4-tert-butylphenyl group.