Experimental and theoretical studies of rate coefficients for the reaction O(3P)+C2H5OH at high temperatures

Rate coefficients of the reaction O(3P)+C2H5OH in the temperature range 782-1410 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO2 at 193 nm with an ArF excimer laser; their concentrations were monitored via atomic resonance absorption. Our data in the range 886-1410 K are new. Combined with previous measurements at low temperature, rate coefficients determined for the temperature range 297-1410 K are represented by the following equation: k(T)=(2.89+/-0.09)x10(-16)T1.62 exp[-(1210+/-90)/T] cm3 molecule(-1) s(-1); listed errors represent one standard deviation in fitting. Theoretical calculations at the CCSD(T)/6-311+G(3df, 2p)//B3LYP/6-311+G(3df) level predict potential energies of various reaction paths. Rate coefficients are predicted with the canonical variational transition state (CVT) theory with the small curvature tunneling correction (SCT) method. Reaction paths associated with trans and gauche conformations are both identified. Predicted total rate coefficients, 1.60 x 10(-22)T3.50 exp(16/T) cm3 molecule(-1) s(-1) for the range 300-3000 K, agree satisfactorily with experimental observations. The branching ratios of three accessible reaction channels forming CH3CHOH+OH (1a), CH2CH2OH+OH (1b), and CH3CH2O+OH (1c) are predicted to vary distinctively with temperature. Below 500 K, reaction 1a is the predominant path; the branching ratios of reactions 1b,c become approximately 40% and approximately 11%, respectively, at 2000 K.     

Crystal Structure Analysis of 1′,2′,3′,4′‐tetrahydro‐1,3‐diphenyl‐4‐chlorospiro[2‐pyrazoline‐5,2‐napthalen]1′one

The crystal structure of the title compound “1′,2′,3′,4′‐tetrahydro‐1,3‐diphenyl‐4‐chlorospiro[2‐pyrazoline‐5,2‐napthalen] 1′one” has been determined. The structure consists of a pyrazoline ring, three aromatic rings and a tetralone moiety. All the aromatic rings are planar while the cyclohexonone ring of the tetralone moiety is in the distorted sofa conformation. The molecular packing is stabilized by C‐H…O and C‐H…π type inter molecular interactions.     

A regioselective 1,3‐dipolar cycloaddition of 2‐arylidene‐1‐tetralones with DPNI

Synthesis of a series of novel 1,3‐diphe nyl‐4‐arylspiropyrazolines[5.2¹]‐1¹‐tetralones has been accomplished in good yield by regioselective 1,3‐dipolar cycloaddition of diphenylnitrilimine with (E)‐2‐arylidene‐1‐tetralones. X‐ray crystal structure analysis of one of the products 4b confirms the structure and the regiochemistry of cycloaddition. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 331–336, 1999     

Neutron depolarization study on the magnetic correlation length of nickel ferrite with different packing densities

The magnetic correlation length of a mixed nickel ferrite powder was studied by a newly commissioned depolarized neutron beamline at the W3 port of Tsing Hua Open Pool Reactor (THOR). In this work, Ni ferrite powder samples with different packing densities were studied. The magnetic correlation lengths of the sample were observed to be 2 μm at virgin state and about 3.1 μm at remanent state from the packing density of 20–60%. This magnetic domain size is smaller than particle size. No significant change of domain size at this packing density implies the domain wall motion is hindered by the porosity effectively up to at least 60% of packing density.     

Influence of pH on inactivation of aquatic microorganism with a gas–liquid pulsed electrical discharge

Inactivation of Escherichia coli in water was experimentally studied, with pulsed electrical discharges in a hybrid gas–liquid reactor. The pH was dramatically decreased from 7 to ～3 within 60 min, accompanying with a 6-log reduction. To evaluate the contribution of pH on inactivation, a set of experiments were designed and tested. Results indicate that the contribution of low pH to the inactivation could be neglected compared to that of electrical discharges. On the other hand, the decrease of pH could be eased as carbonate or phosphate buffer was added to the treated water. However, the inactivation efficiency was greatly reduced because the buffers could deplete the active species formed in electrical discharges. Besides, a new finding is addressed in this paper that the water after plasma treatment still owns a certain extent of inactivation ability, functioning like the free chlorine residual. The environmental adaptation ability of E. coli to electrical discharges was also investigated.     

Microwave-assisted cycloadditions of 2-alkynylbenzonitriles with sodium azide: selective synthesis of tetrazolo[5,1-a]pyridines and 4,5-disubstituted-2H-1,2,3-triazoles

Under microwave irradiation (75 W), treatment of 2-alkynylbenzonitriles with 1.5 equiv of sodium azide in DMSO at 140 °C gave 4,5-disubstituted-2H-1,2,3-triazoles in 60-99% yields. Additionally, adding 8 equiv of ZnBr₂ and using 8 equiv of sodium azide in DMF at 100 °C lead to the formation of tetrazolo[5,1-a]isoquinolines up to 87% yield.     

Bacterial pyomyositis: MRI and clinical correlation

OBJECTIVE: To characterize the findings of magnetic resonance imaging (MRI) of bacterial pyomyositis (PM) and correlate these data with the clinical information. MATERIALS AND METHODS: Eighty-one patients were diagnosed with PM in our institute between 1997 and 2003. Of these, 40 patients (21 male, 19 female; mean age, 53 years) also underwent MRI examination. The clinical manifestation underlying medical problems and the characteristics of MRI were analyzed. Thirty of the patients received surgical intervention or image-guided drainage/aspiration of the abscess along with administration of antibiotics, while the remaining 10 patients were promptly treated solely with antibiotics. RESULTS: Thirty-one of 40 patients had underlying medical problems. These involved diabetes mellitus (DM, n = 16), malignancies including cervical cancer, prostate cancer, non-Hodgkin's lymphoma and acute lymphocytic leukemia (n = 10, one case also had DM), autoimmune disease or asthma with long-term steroid usage (n = 4, one case also had DM), liver cirrhosis (n = 2) and chronic renal insufficiency (n = 1). Four patients had no abscess formation at presentation (invasive or early purulent stage), while the remaining 36 cases presented with at least one abscess (purulent stage). Patients older than 40 years or DM patients tended to have larger abscess(s) (P < .05). Gadolinium-enhanced images demonstrated either thick (n = 12) or thin rim enhancement (n = 24) of the abscess wall. For those 10 patients promptly treated solely with antibiotics, nine demonstrated thin rim enhancement of the abscess (P < .05). CONCLUSION: Magnetic resonance imaging plays an important role in the early recognition of bacterial PM. By precisely demarcating the extent of the disease, MRI can allow planning prompt antibiotic treatment combined with or without interventional procedures.     

Efficient reduction of graphene oxide catalyzed by copper

We report that copper thin films deposited on top of graphene oxide (GO) serve as an effective catalyst to reduce GO sheets in a diluted hydrogen environment at high temperature. The reduced GO (rGO) sheets exhibit higher effective field-effect hole mobility, up to 80 cm(2) V(-1) s(-1), and lower sheet resistance (13 kΩ □(-1)) compared with those reduced by reported methods such as hydrazine and thermal annealing. Raman and XPS characterizations are addressed to study the reduction mechanism on graphene oxide underneath copper thin films. The level of reduction in rGO sheets is examined by Raman spectroscopy and it is well correlated with hole mobility values. The conductivity enhancement is attributed to the growth of the graphitic domain size. This method is not only suitable for reduction of single GO sheets but also applicable to lower the sheet resistance of Langmuir-Blodgett assembled GO films.     

Microstructure and lubricating property of ultra-fast laser pulse textured silicon carbide seals

Most previous studies have employed surface patterning to improve the performance of lubrication systems. However, few have experimentally analyzed improved effects on friction reduction in SiC mechanical seals by ultra-fast laser pulse texturing. This work applies surface texturing on a non-contact mechanical seal and analyzes the characteristics of the resultant surface morphology. A femtosecond laser system is employed to fabricate micro/nanostructures on the SiC mechanical seal, and generates microscale-depth stripes and induces nanostructures on the seal surface. This work examines the morphology and cross section of the SiC nanostructures that correspond to the different scanning speeds of the laser pulse. Results show that varying the scanning speed enables the application of nanostructures of different amplitudes and widths on the surface of the seal. The friction coefficient of the introduced SiC full-textured seal is about 20% smaller than that of a conventional SiC mechanical seal. Hence, femtosecond laser texturing is effective and enables direct fabrication of the surface micro/nanostructures of SiC seals. This technique also serves as a potential approach to lubricating applications.     

Aza‐BODIPY Derivatives: Enhanced Quantum Yields of Triplet Excited States and the Generation of Singlet Oxygen and their Role as Facile Sustainable Photooxygenation Catalysts

A new series of aza‐BODIPY derivatives ( 4 a – 4 c , 5 a , c , and 6 b , c ) were synthesized and their excited‐state properties, such as their triplet excited state and the yield of singlet‐oxygen generation, were tuned by substituting with heavy atoms, such as bromine and iodine. The effect of substitution has been studied in detail by varying the position of halogenation. The core‐substituted dyes showed high yields of the triplet excited state and high efficiencies of singlet‐oxygen generation when compared to the peripheral‐substituted systems. The dye 6 c , which was substituted with six iodine atoms on the core and peripheral phenyl ring, showed the highest quantum yields of the triplet excited state (Φ_T=0.86) and of the efficiency of singlet‐oxygen generation (Φ_Δ=0.80). Interestingly, these dyes were highly efficient as photooxygenation catalysts under artificial light, as well as under normal sunlight conditions. The uniqueness of these aza‐BODIPY systems is that they are stable under irradiation conditions, possess strong red‐light absorption (620–680 nm), exhibit high yields of singlet‐oxygen generation, and act as efficient and sustainable catalysts for photooxygenation reactions.