A kinetic method for <Emphasis Type="Italic">para</Emphasis>-nitrophenol determination based on its inhibitory effect on the catalatic reaction of catalase

The inhibitory effect of para-nitrophenol on the catalytic reaction of catalase was investigated. Michaelis-Menten kinetic parameters were determined from Lineweaver-Burk plots obtained in the absence or in the presence of the inhibitor. The inhibitor pattern, revealed by the Lineweaver-Burk plots, suggested a fully mixed inhibition mechanism. Spectrophotometric monitoring of the indicator reaction: in conjunction with initial rate measurements was employed for the kinetic determination of the inhibitor. Calibration plots of initial rate vs. para-nitrophenol concentration were linear in the concentration range 0.9·10⁻⁵–2.5·10⁻⁵ mol/L and the detection limit was 3·10⁻⁶ mol/L (417 μg/L) para-nitrophenol. Interferences from other phenolic compounds like orto-cresole, meta-and orto-nitrophenol were observed.     

Reaction of porous silicon with both end-functionalized organic compounds bearing alpha-bromo and omega-carboxy groups for immobilization of biomolecules

Both end-functionalized (alpha-bromo and omega-carboxy) compounds were first tested for the radical reaction on the silicon-hydride (Si-H) terminated porous silicon (PSi) with/without the presence of diacyl peroxide initiator under microwave irradiation. Then the carboxylic acid monolayers (CAMs) assembled on PSi through the robust Si-C bonds were converted to amino-reactive linker, N-hydroxysuccinimide (NHS)-ester, terminated monolayers. And finally two proteins of bovine serum albumin (BSA) and lysozyme (Lys) were immobilized through amide bonds. The optimum PSi membrane for protein immobilization without collapse, with parameters of porous radii 4-10 nm and depth 0.2-4.6 mum, was prepared from the (100)-oriented p-type silicon wafer. The chemically converted surface products were monitored with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM).     

Reactions of substituted furo[3,2-<Emphasis Type="Italic">b</Emphasis>]pyrrole-5-carboxhydrazides and their biological activity

The reactions of substituted furo[3,2-b]pyrrole-5-carboxhydrazides 1 with 5-arylfuran-2-carboxaldehydes 2, 4,5-disubstituted furan-2-carboxaldehydes 3 and thiophene-2-carboxaldehyde 4 has been studied. The advantage of microwave irradiation on some of these reactions was reflected in the reduced reaction time and increased yields. Reactions of 1 with 4-substituted 1,3-oxazol-5(4H)-ones 11 led to diacylhydrazines 13 or to imidazole derivatives 14 depending on the temperature. 1,2,4-Triazole-3-thione 17 was synthesized by two-step reaction of 1 with phenylisothiocyanate and subsequent base-catalyzed cyclization of thiosemicarbazide 16. The effects of hydrazones 5–10 on inhibition of photosynthetic electron transport in spinach chloroplasts and chlorophyll content in the antialgal suspensions of Chlorella vulgaris were investigated.     

Synthesis,crystal structure and two-photon property studies on a series of complexes derived from a novel Schiff base ligand

A new Schiff base ligand derived from S-benzyldithiocarbazate and 4-[N-hydroxy ethyl-N-(methyl)amino]benzaldehyde (HL, where H is a dissociable proton) and its Ni^II, Cu^II, Zn^II and Pd^II complexes were prepared and fully characterized. The structures of HL and Ni(L)₂ were determined by X-ray diffraction analysis, which revealed that the geometry of the Ni^II ion is square-planar with two equivalent Ni=N and Ni=S bonds, and that the two neighboring molecules in two layers have weak contact. The electronic spectra and solution fluorescence of the ligand and the complexes were studied, and the quantum yields of single-photon fluorescence for the compounds were determined. The compounds possess two-photon absorption (t.p.a.) character and the t.p.a. coefficient and t.p.a. cross-section were determined by the Z-scan technique. Especially, the Zn(L)₂complex and the HL ligand exhibit intensive two-photon fluorescence (t.p.f.) at 800 nm laser pulses in the femtosecond regime.     

Dielectric properties and frequency response of self-assembled monolayers of alkanethiols

This paper presents dielectric properties of alkanethiol self-assembled monolayers (SAMs) under an ac electric field. Using a Hg-SAM/SAM-Hg junction, we measured the ac impedance of alkanethiol SAMs using a sinusoidal perturbation of 30 mV (peak-to-peak) with frequency ranging from 1 Hz to 1 MHz at zero bias. Semicircles at higher frequencies and at middle frequencies along with Warburg lines at lower frequencies were observed in complex plane impedance plots, that is, Nyquist plots. The frequency response of SAMs was analyzed by modeling the junction using an equivalent circuit and fitting the Nyquist plots. The semicircles at higher frequencies are attributed to the effect of the SAM/SAM interfaces, and the ones at middle frequencies are attributed to the effect of alkanethiol SAMs. The comparison in the plots of the imaginary part of the impedance Z against frequency for the bare Hg electrodes (in pure ethanal) and the SAM-covered Hg electrodes (in alkanethiol solution) supports the analysis. The Warburg lines are attributed to a certain ionic impurity. The dielectric loss spectra are further analyzed. Chain-length-dependent peaks, which correspond to different relaxation mechanisms, at higher frequencies and middle frequencies were observed in the spectra of the dissipation factor (tan delta vs frequency). The peaks move to small frequency with the increase of chain length of alkanethiols. Using a correlation of peak position with the chain length, we then derived active energies of 39-99 meV for alkanethiol SAMs of C7-C18 under an ac electric field.     

Theoretical study on the structure and property relationship of the cationic conjugated polyelectrolytes

A theoretical study using density functional theory was performed to understand the structure/property relationship of the cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined.     

Electrodeposition of nanocrystalline zinc from acidic sulfate solutions containing thiourea and benzalacetone as additives

Nanocrystalline zinc coatings were produced by pulse electrodeposition in acid sulfate bath containing thiourea and benzalacetone additives and characterized by X-ray diffraction and scanning electron microscopy techniques. The influence of benzalacetone concentration and pulse peak current density on the grain size and crystallographic orientation of zinc deposits was investigated. Zinc electrodeposited from additive-free solutions or with one of the two additives is not composed of nanosized crystals. The mixture additives of thiourea and benzalacetone give rise to the formation of particle-like nanocrystalline zinc with a (10ī1) random orientation. A change in peak current density from 2 to 1 A/cm² only increases the grain size from 60 to 62 nm.     

Energy transfer rates and impact sensitivities of two classes nitramine explosives molecules

Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed previously. The number of doorway modes in the regions of 200–700 cm⁻¹ was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13 nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm⁻¹.     

芴取代的有机膦化合物的合成及发光性能

合成了以芴为取代基，P原子为核的一类新型有机膦化合物．此类化合物的HOMO值在-5．35～-5．24eV之间．在二氯甲烷中的最大紫外吸收光谱峰值在313～351nm之间，荧光光谱峰值在334～397nm之间．利用此类小分子与纯聚芴进行掺杂，制作了有机电致发光器件．低HOMO值有机膦化合物的引入有效地降低了聚芴发光器件的开启电压，提高了器件的发光效率．     

Light- and temperature-assisted spin state annealing: accessing the hidden multistability

Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.

Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂], revealing the hidden multistability of spin states.