新型两亲性混配钌配合物的合成及其对Hg2+的选择性“肉眼”识别

采用与文献不同的路线合成了4,4′-二(p-甲基苯基)-2,2′-二联吡啶,与文献结果相比,总收率由4.0%提高至15.3%.该化合物和4,4′-二羧基-2,2′-二联吡啶组成混合配体与金属钌配位,合成了两亲性、混配型配合物cis-N,N-4,4′-二(p-甲基)苯基-2,2′-二联吡啶-N,N-4,4′-二羧基-2,2′-二联吡啶-N,N-二异硫氰钌配合物,并用IR,UV-Vis,NMR和Maldi-TOF等手段进行表征.将该两亲性混配钌配合物首次用于对Hg2+的识别中,发现此配合物对Hg2+表现出灵敏的选择性“肉眼”识别:在DMF/乙醇溶液(体积比1∶9)中加入Hg2+后,MLCT态吸收由530nm蓝移到485nm.该配合物与Hg2+以1∶1(摩尔比)结合,检测限可低至0.5×10-6mol/L.     

细胞色素C在离子液体修饰电极上的电化学行为

分别合成了疏水和亲水性咪唑类离子液体,并制备了相应的两种离子液体修饰的玻碳电极。循环伏安法测量结果显示,细胞色素C在离子液体修饰的玻碳电极上的电子传递过程为一扩散控制的准可逆反应,表明咪唑类离子液体也可用作细胞色素C电子传递的有效促进剂。电化学交流阻抗谱的测量结果得到了与循环伏安相同的结论。     

Asymmetric Cu-catalyzed 1,6-conjugate addition of dialkylzinc reagents to 5-(3-aryl-2-propenylidene) Meldrum’s acids

The asymmetric synthesis of tertiary and quaternary stereocentres has been successfully achieved through Cu-catalyzed 1,6-addition of dialkylzinc reagents to 5-(3-aryl-2-propenylidene) Meldrum’s acid derivatives in the presence of a phosphoramidite ligand.     

Synthesis of fluorinated imines and carbodiimides from azides via aza-Wittig reaction

The Staudinger reaction of fluoroalkylazides were studied. A series of N-fluoroalkylimines were synthesized via aza-Wittig reaction of N-fluoroalkyliminophosphoranes. The N,N′-difluoroalkylated carbodiimide was also synthesized via the reaction of N-fluoroalkyliminophosphoranes with carbon dioxide or carbon disulfide.     

The study of nafion/xanthine oxidase/au colloid chemically modified biosensor and its application in the determination of hypoxanthine in myocardial cells in vivo

A novel hypoxanthine (Hx) microsensor was constructed. In this work, Nafion xanthine oxidase (XOD) and Au colloid were immobilized onto the surface of a Pt microelectrode. The enzyme biosensor displayed a quick and sensitive response to Hx. Under physiological conditions, a low detection limit, with high selectivity and sensitivity for Hx determination were obtained. The oxidation current [investigated using current-time (I-t) plots] was linear with Hx concentration ranging from 2.0 x 10(-7) to 2.0 x 10(-5) mol L(-1) with a calculated detection limit of 1.0 x 10(-7) mol L(-1) (S/N of 3). The biosensor should be promising for in vivo measurement of Hx without interferences and fouling. The change of Hx concentration in cardiac myocytes stimulated by L-arginine (L-Arg) and acetylcholine (Ach) was also studied.     

LOCALIZED PATTERNS OF THE CUBIC-QUINTIC SWIFT-HOHENBERG EQUATIONS WITH TWO SYMMETRY-BREAKING TERMS

Homoclinic snake always refers to the branches of homoclinic orbits \mbox{near} a heteroclinic cycle connecting a hyperbolic or non-hyperbolic equilibrium and a periodic orbit in a reversible variational system. In this paper, the normal form of a Swift-Hohenberg equation with two different symmetry-breaking terms (non-reversible term and non-k-symmetry term) are investigated by using multiple scale method, and their bifurcation diagrams are initially studied by numerical simulations. Typically, we predict numerically the existence of so-called round-snakes and round-isolas upon particular two symmetric-breaking perturbations.     

Valuation perspectives and decompositions for variable annuities with GMWB riders

The guaranteed minimum withdrawal benefit (GMWB) rider, as an add on to a variable annuity (VA), guarantees the return of premiums in the form of periodic withdrawals while allowing policyholders to participate fully in any market gains. GMWB riders represent an embedded option on the account value with a fee structure that is different from typical financial derivatives. We consider fair pricing of the GMWB rider from a financial economic perspective. Particular focus is placed on the distinct perspectives of the insurer and policyholder and the unifying relationship. We extend a decomposition of the VA contract into components that reflect term-certain payments and embedded derivatives to the case where the policyholder has the option to surrender, or lapse, the contract early.     

Mathematical modeling of electromagnetic wave propagation in heterogeneous lossy coaxial cables with variable cross section

In this work, we focus on the time-domain simulation of the propagation of electromagnetic waves in non-homogeneous lossy coaxial cables. The full 3D Maxwell equations, that described the propagation of current and electric potential in such cables, are classically not tackled directly, but instead a 1D scalar model known as the telegraphist's model is used. We aim at justifying, by means of asymptotic analysis, a time-domain “homogenized” telegraphist's model. This model, which includes a nonlocal in time operator, is obtained via asymptotic analysis, for a lossy coaxial cable whose cross section is not homogeneous.     

Coronal multi-walled silicon nanotubes

By means of first-principles density functional theory(DFT) calculations and molecular dynamics(MD) simulations,a series of coronal multi-walled silicon nanotubes(MWSiNTs) without or with hydrogen terminations are systematically identified.Notably,coronal MWSiNTs,where the interaction between the walls is preferable through covalent bonds rather than weak interaction,show better stability than CNT-like SiNTs. Moreover,they exhibit good elasticity with small Young’s modulus.The investigation of the electronic structure demonstrates that they present metallic characteristics,which is in striking contrast to bulk silicon.Thus,the MWSiNTs may find important applications in electronic devices.     

Improved measurement of electron antineutrinodisappearance at Daya Bay

We report an improved measurement of the neutrino mixing angle θ₁₃ from the Daya Bay Reactor Neutrino Experiment. We exclude a zero value for sin² θ₁₃ with a significance of 7.7 standard deviations. Electron antineutrinos from six reactors of 2.9 GW_th were detected in six antineutrino detectors deployed in two near （flux-weighted baselines of 470 m and 576 m） and one far （1648 m） underground experimental halls. Using 139 days of data, 28909 （205308） electron antineutrino candidates were detected at the far hall （near halls）. The ratio of the observed to the expected number of antineutrinos assuming no oscillations at the far hall is 0.944±0.007（stat.）±0.003（syst.）. An analysis of the relative rates in six detectors finds sin² θ₁₃ =0.089±0.010（stat.）±0.005（syst.） in a three-neutrino framework.