I/V characteristics of a molecular switch

We present a study of the conduction properties of a class of aromatic compounds, whose conformation can be modulated with a transverse electric field, with strong effects on the molecular transport properties. The theoretical method includes the molecule–electrode interaction in a simple, although effective way: the coupling matrix elements are considered independent from the energy of the continuum spectrum of the lead. This results in a simple expression for the molecular Green’s function with a significant simplification in the expression of the transmission function. The effects of the voltage bias on the electronic molecular density is included through a uniform effective electric field. A simplified but accurate method for the evaluation of the molecular response to the field, which spares lengthy computations for each value of the voltage, is presented. The proposed method is calibrated on the widely studied benzene-1,4-dithiol molecule. The calculations on the selected molecular wire (a tetracyano derivative of 4,4′-di(mercaptoethynyl)tolan) show that conductivity is low for perpendicular rings, whereas conduction is allowed for the planar conformation, which corresponds to the equilibrium geometry in the absence of the transverse electric field.     

Construction of a novel Mo/Cu/S cluster with a closed double-cubane-like polyhedron and a chain polymer of W/Cu/S clusters

Reaction of [MoOS(3)](2)(-) and [WS(4)](2)(-) with Cudtp (dtp = diethyl dithiophosphate) gave rise to the clusters [Bu(4)N](2)[(MoOS(3))(4)Cu(12)(dtp)(6)], 1, and [Et(4)N][(WS(4)Cu(4))(dtp)(3)], 2, respectively. In cluster 1, the dtp- ligands act as both monodentate and bidentate ligands that bridge between Cu atoms and link together a closed double-cubane-like [Mo(2)O(2)S(6)Cu(6)](2+) core and two incomplete cubane-like [MoOS(3)Cu(3)]+ units. In cluster 2, the [WS(4)Cu(4)](2+) fragments were connected via bidentate and doubly bridging dtp- bridges to give a chain polymeric anion. Cluster 1 is the first example of a Mo/Cu/S cluster that contains a closed double-cubane-like structure. Compound 2 is also rare and the first W/Cu/S polymer with dtp- linkages.     

Equation of state for hydrofluorocarbon refrigerant mixtures of HFC-125/143a,HFC-125/134a,HFC-134a/143a and HFC-125/134a/143a

Equations of state (EOSs) in the form of dimensionless Helmholtz free energy have been developed for the binary hydrofluorocarbon (HFC) refrigerant mixtures HFC-125/143a, HFC-125/134a, HFC-134a/143a and for the ternary refrigerant mixture HFC-125/134a/143a in the present work. These EOSs are effective in the temperature and pressure ranges where the experimental measurements covered, i.e., 200 K⩽T⩽413 K, P⩽35 MPa for HFC-125/143a and HFC-125/134a; 243 K⩽T⩽413 K, P⩽17 MPa for HFC-134a/143a and HFC-125/134a/143a. Experimental measurements in both single-phase and two-phase regions are represented by the present EOSs within their estimated uncertainties.     

PB/Au/CILE的制备与应用

混合离子液体(N-丁基吡啶六氟磷酸盐,[BuPy][PF6])与石墨粉,制备了离子液体碳糊电极(CILE),再采用电沉积法制得PB/Au/CILE修饰电极,研究了该修饰电极的电化学行为及其对H2O2的电催化,建立了H2O2的计时安培测定新方法。结果表明:在该修饰电极上PB产生了一对准可逆的氧化还原峰,并对H2O2表现出良好电催化作用,安培法测定H2O2的线性范围为5.0×10-6～1.55×10-4mol/L,检出限为1.0×10-6mol/L(S/N=3)。连续10次测定5.0×10-6mol/L H2O2峰电流的RSD为2.1%。     

Structure of salvigenolide,a novel diterpenoid with a rearranged neo-clerodane skeleton from salviafulgens

From the aerial parts of Salvia fulgens Cav. (Labiatae) a new diterpenoid with a rearranged neo-clerodane skeleton was isolated. This novel compound named salvigenolide, showed a six-seven A/B ring system with a trans fussion. A probable biogenetic route is proposed. Its structure and relative stereochemistry as in $\text{1}$, were established by spectroscopic means and X-ray diffraction analysis.     

Salvifarinin A,a neo-clerodane diterpenoid with a 6/5/7 tricyclic skeleton from Salvia farinacea

Salvifarinin A (1), a rearrangement product of Languidulane-type clerodane diterpenoids with a 6/5/7 tricyclic ring skeleton fused with γ-lactone ring and furan ring, and two new biogenetically related diterpernoids, salvifarinins B (2) and C (3), were isolated from the aerial parts of Salvia farinacea. The absolute configuration of 1 was elucidated by extensive spectroscopic methods, and confirmed by single crystal X-ray diffraction and bio-inspired semisynthesis. The plausible biogenetic pathway was also proposed. Compound 2 displayed a potent effect on reducing hepatic steatosis.     

Temperature-resistivity characteristics of a segregated conductive CB/PP/UHMWPE composite

A carbon black (CB)/polypropylene (PP)/ultrahigh-molecular-weight polyethylene (UHMWPE) composite with a segregated structure was fabricated by using binary polymer granules as matrices. In preparation, an ethanol-assisted dispersion method was employed to disperse CB particles on the surface of the two polymer granules. The segregated conductive network was then constructed by hot compaction based on the volume exclusion effect of the polymer matrices. The conductive composite shows an ultralow percolation threshold of 0.34 vol.%. In temperature-resistivity test, a double positive temperature coefficient (PTC) effect was observed. In addition, the negative temperature coefficient (NTC) effect was eliminated significantly. These interesting temperature-resistivity behaviors were ascribed to the introduction of the binary polymer matrices and the mobility limitation of CB particles located at the PP/UHMWPE interface. These characteristics were probed by in situ morphology observation in heating process. The present paper provides a novel route for preparing conductive composites with an ultralow percolation threshold, a wider PTC region, and a zero NTC effect.     

Fabrication of a novel glucose biosensor based on a highly electroactive polystyrene/polyaniline/Au nanocomposite

A novel nanocomposite with a core-shell structure containing polystyrene (PS), polyaniline (PANI), and Au nanoparticles (NPs) was synthesized. The nanocomposite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). Cyclic voltammetric experiments indicated that the nanocomposite had excellent redox ability in a wide range of pH values. The existence of Au NPs resulted in a higher electrical conductivity of the nanocomposite. As a model, glucose oxidase (GOD) was entrapped onto the nanocomposite-modified glassy carbon electrode (GCE) and applied to construct a sensor. The immobilized GOD showed a pair of well-defined redox peaks and high catalytic activity for the oxidation of glucose.     

Efficient Synthesis of Quinolines via a Knoevenagel/Staudinger/aza-Wittig Sequence

A simple and efficient method for the construction of quinoline derivatives from 2-azidobenzaldehyde and various carbonyl compounds was developed. The process involves a Knoevenagel condensation of 2-azidobenzaldehyde with carbonyl compound and subsequently an intramolecular normal Staudinger/aza-Wittig reaction to form the quinolone ring in satisfactory yields.     

What is the shape of a cis-fused cyclohexane bearing a pseudoequatorial t-butyl group?

N,2α-Dimethyl-8α-t-butyl-cis-decahydroquinoline (I) picrate crystallizes as a double chair with an equatorial t-butyl group and an axial N-methyl group. N,2α-Dimethyl-8β-t-butyl-cis-decahydroquinoline (II) picrate crystallizes with the equatorially substituted heterocylic ring adopting a chair conformation. The strained A ring gives evidence that a distorted twistboat form may be nearly as favorable as a flattened chair form.     

Performance and scaling of a 1.2 V/1.5 Ah nickel/metal hydride cell to a 6 V/1.5 Ah battery

A 1.2 V/1.5 Ah positive-limited nickel/metal hydride cell has been studied to determine its charge-discharge characteristics at different rates in conjunction with its AC impedance data. The faradaic efficiency of the cell is found to be maximum at ∼70% charge input. The cell has been scaled to a 6 V/1.5 Ah battery. The cycle-life data on the battery suggest that it can sustain a prolonged charge-discharge schedule with little deterioration in its performance. Received: 17 November 1998 / Accepted: 5 February 1999     

Molecular structure and fluorescence behaviour of a benzoquinone/porphyrin/benzoquinone sandwich-molecule

For the benzoquinone/porphyrin/benzoquinone sandwich-molecule 1 a highly symmetrical structure with parallel ring planes and interplanar distances of 342 pm was derived from X-ray analysis. 1 shows, in comparison to 2, a very strong quenching of fluorescence indicating intramolecular electron transfer.     

Oxidative cyclization of a seco-cladiellane diterpenoid

A short and efficient synthesis of a diterpenoid with a 1,2-seco-cladiellane carbon skeleton is described, starting from geraniol and carvone. One-step oxidative cyclization with a RuO₂/NaIO₄ system leads to two diastereomeric, bicyclic triols, which contain six stereogenic centers and will be helpful in the synthesis of eleutherobin. The stereochemical outcome of this cyclization has been determined by X-ray analysis.     

Regiospecific synthesis of a benanomicinone/pradimicinone analogue

[reaction: see text] Condensation of a phenylsulfinyl naphthoate with an ortho-quinone monoketal has been used to accomplish a total synthesis of a benanomicinone/pradimicinone analogue.     

Synthesis and Complexation of a New vic -Dioxime Ligand

 A new vic-dioxime ligand, N,N′-bis-(8-salicylideneimino-1-naphthyl)-diaminoglyoxime, has been synthesized from anti-dichloroglyoxime and 1-amino-8-salicylideneiminonaphthalene which has been prepared via the condensation product of 1,8-diaminonaphthalene and salicylaldehyde. The vic-dioxime ligand forms trinuclear complexes with Cu(II), Ni(II), Co(II), and Pd(II). The uranyl complex of this ligand has a 2:1 metal-ligand ratio and a binuclear structure with μ-hydroxo bridges.     

Evaluation of a rotary valve/cold trap/reinjection system for capillary columns

This paper describes a cold trap/reinjection system for capillary columns which utilizes a flow switching rotary valve. Sample enrichment is performed in a liquid nitrogen-cooled glass trap attached to the valve. Evaporation of enriched compounds is carried out with the aid of an electric heating coil. Parameters such as cryogenic trapping efficiency, reinjection rates, transference of sample, and adsorption, as well as overall performance, are examined. In addition, a comparison is made between the cold trap/reinjection technique and injection with a gas-tight syringe.     

Hard/soft heterometallic network complex of a macrocycle with endo/exocyclic coordination

One-pot assembly reactions of an S(2)O(4) macrocycle with CuI in the absence and presence of KI afforded an emissive one-dimensional looped coordination polymer linked with a cubane-type copper iodide cluster and an endocoordinated potassium(I) coordination polymer linked with a ribbon-type copper iodide cluster, respectively.     

Mechanical characterization of a new Kevlar/Flax/epoxy hybrid composite in a sandwich structure

Natural fibers are inexpensive, biodegradable, and have similar specific properties to some synthetic fibers. Hardly any previous investigations exist of a composite made of multiple layers of pure Kevlar fiber fabric and pure Flax fiber fabric in a “sandwich structure”, but it only measured impact properties. The composite was made of 12 Flax/epoxy layers at the core in 3 possible configurations (i.e. [0]_12F, [0/90]_6F, or [±45]_6F) that were sandwiched by 2 Kevlar/epoxy layers (i.e. plain weave) on each side. This study showed maximum change in the mechanical properties with respect to Flax/Epoxy for tension (+137.85% in E_T, and +171.22% in σ_UT), compression (+171.22% in E_c, and −10.6% in σ_UC), 3-point bending (−11.54% in E_B, and +2.19 in σ_UB), torsion (−5.31% in G, and 395.82% in τ), and water absorption (60.04%). This novel hybrid composite may be useful for research and industry applications.     

Synthesis of 1,2,4,5-tetrasubstituted imidazoles by a sequential aza-Wittig/Michael/isomerization reaction

Carbodiimides 4, obtained from aza-Wittig reactions of iminophosphorane 3 with aryl isocyanates, reacted with secondary amines in the presence of a catalytic amount of sodium alkoxide to give 1,2,4,5-tetrasubstituted imidazoles 7 in good yields. However, 4-acylimidazoles 11 were obtained, as phenols were used in the presence of a catalytic amount of potassium carbonate due to further air oxidation of the expected products 10.     

Calculation of raman intensities by a modified cndo/2/indo method

Line intensities in Raman spectra determined by means of a modified CNDO/2 and a modified INDO method [1,2] give perturbation terms which are inserted into the Hartree—Fock operator used in the CNDO/2 and INDO theory [3, 4] to yield the induced dipole moment as a function of the normal co-ordinate Q, from which the polarizability change upon Q is obtained. The results for ethylene, tetrafluoroethylene, tetrachloroethylene, dichloromethane and phosgene are discussed. Calculated intensities agree well with experimental intensities obtained from Raman spectra.