Non-Linear Expressions for Rolling Friction of a Soft Ball on a Hard Plane

A new set of expressions for the rollingfriction of a viscoelastic sphere rolling on a hard planeis derived. The new expressions take into considerationthe speed of rotation, the material relaxation time andother material characteristics. It is found that when therelaxation effect is not negligible, the relationshipbetween rolling friction and rolling speed is non-linear.The derivation of this model is based on the energy-equivalence method that gives a more comprehensiveconsideration of dominant parameters in the calculation.     

Rapid identification of Candida albicans in blood by combined capillary electrophoresis and fluorescence in situ hybridization

A CE method based on whole‐cell molecular labeling via fluorescence in situ hybridization was developed for the detection of Candida albicans in whole blood. Removal of potentially interfering red blood cells (RBC) with a simple hypotonic/detergent lysis step enabled us to detect and quantitate contaminating C. albicans cells at concentrations that were orders of magnitude lower than background RBC counts (∼7.0×10⁹ RBC/mL). In the presence of the lysed blood matrix, yeast cells aggregated without the use of a blocking plug to stack the cells. Short (15 min) hybridizations yielded bright Candida‐specific fluorescence in situ hybridization signals, enabling us to detect as few as a single injected cell. The peak area response of the stacked Candida cells showed a strong linear correlation with cell concentrations determined by plate counts, up to ∼10⁷ CFU/mL (or ∼1×10⁴ injected cells). This rapid and quantitative method for detecting Candida in blood may have advantageous applications in both human and veterinary diagnostics.     

Detection of Hydrogen Peroxide and Glucose Based on Immobilized C60‐Catalase Enzyme

The interaction between fullerene C60 and catalase enzyme was studied with a fullerene C60‐coated piezoelectric (PZ) quartz crystal sensor. The partially irreversible response of the C60‐coated PZ crystal sensor for catalase was observed by the desorption study, which implied that C60 could chemically react with catalase. Thus, immobilized fullerene C60‐catalase enzyme was synthesized and applied in determining hydrogen peroxide in aqueous solutions. An oxygen electrode detector with the immobilized C60‐catalase was also employed to detect oxygen, a product of the hydrolysis of hydrogen peroxide which was catalyzed by the C60‐catalase. The oxygen electrode/C60‐catalase detection system exhibited linear responses to the concentration of hydrogen peroxide and amount of immobilized C60‐catalase enzyme that was used. The effects of pH and temperature on the activity of the immobilized C60‐catalase enzyme were also investigated. Optimum pH at 7.0 and optimum temperature at 25 °C for activity of the insoluble immobilized C60‐catalase enzyme were found. The immobilized C60‐catalase enzyme could be reused with good repeatability of the activity. The lifetime of the immobilized C60‐catalase enzyme was long enough with an activity of 93% after 95 days. The immobilized C60‐catalase enzyme was also applied in determining glucose which was oxidized with glucose oxidase resulting in producing hydrogen peroxide, followed by detecting hydrogen peroxide with the oxygen electrode/C60‐catalase detection system.     

Purification and Characterization of Bowman‐Birk Protease Inhibitor from Rice Coleoptiles

A 15 kDa rice Bowman‐Birk inhibitor from fast elongating coleoptiles has been purified and identified using partial N‐terminal sequence, LC‐MS, and MALDI‐TOF MS as a 133 amino acid polypeptide (BBIrc 1). The kinetic study shows this protease inhibitor displays competitive inhibition toward trypsin with Ki of 4.0 × 10^?7 M and non‐competitive inhibition toward α‐chymotrypsin with Ki of 9.3 × 10^?6 M. The Western blotting results of the anti‐sera raised against this 15 kDa protein showed that this anti‐serum recognized two BBI proteins with molecular size around 15 kDa (BBIrc 1) and 25 kDa (BBIrc2) and the quantity of the expression of 15 kDa was nearly constant under both aerobic and hypoxia conditions; however, the 25 kDa expression was greatly up‐regulated when the fast elongating coleoptiles were transferred from hypoxia conditions to the aerobic conditions. The results indicate that the expression pattern of BBIs proteins correlated to the developmental stage in terms of morphological changes. The partial N‐terminal sequence of the first 9 amino acids of 25 kDa was AEAPPRPPK, which is the same as the amino acid sequence of 37th to 45th of RBBI3‐1 and LC‐MS study shows that several mass fragments fit to RBBI3‐1. The 25 kDa protein also shows specific binding to bovine trypsin. This expression pattern demonstrates for the first time that environmental factor, oxygen, can select and enhance specific BBI gene expression. The results of this study suggest BBI proteins might play multiple biological functions inside rice coleoptiles.     

Nonlinear optical polyimides consisting of chromophore‐containing dendrons with site‐isolation effect

To investigate the dendritic structure effects on the electro‐optical (EO) coefficients and thermal stability of the nonlinear optical (NLO) active materials, a bifunctional compound, IDD (4‐isocyanato‐4′(3,3‐dimethyl‐ 2,4‐dioxo‐acetidino)‐diphenylmethane) was used as a building block to synthesize a series of novel NLO chromophore‐containing dendritic structures including Generation 0.5 (G0.5) to Generation 3 (G3). The glass transition temperatures (T_g) of G1–G3 dendrons were in the range of 76–116°C, whereas only the G0.5 dendron exhibited a melting temperature (T_m), 98°C. Moreover, a series of NLO‐active guest–host systems ranging from polyimide‐G0.5 (PI‐G0.5) to polyimide‐G3 (PI‐G3) were prepared by blending 20 wt% chromophore‐containing dendron with a high T_g polyimide. EO coefficients ranged from 6.1 to 12.9 pm/V. The r₃₃/dye content ratio increased with increasing generation of dendron‐containing polyimide samples. Particularly, the improvement in r₃₃/dye content ratio of PI‐G2.5 sample tripled as compared to that of the guest–host sample with Disperse Red 1. Excellent temporal stability of PI‐G0.5 and PI‐G1.5 at 80°C was obtained. Moreover, waveguide properties for NLO polymers containing higher generation dendrons (3.1–3.6 dB/cm at 830 nm) were also obtained. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman Spectroscopy of Galactosemic Rat Lens Crystalline: Correlation of Microscopic Changes of Lens Proteins at Molecular Levels with Gross Cataractous Alteration

Near‐Infrared Fourier trans form (near‐IR FT) Raman spectros copy has been used to study the structural changes of lens proteins both in cortex and nucleus of galactosemic rat lenses. It was found that tyrosine doublet ratio of Raman bands, I₈₃₂/I₈₅₅, in creased more rapidly in the cortex than in the nucleus during a 5‐week period of galactose feeding, i.e., from 0.86 to 1.1 for the cortex and 0.88 to 0.92 for the nucleus. The ratio obtained for lens nucleus suggests that a lower ratio of less than 1 does not necessarily reflect the apparent transparent state of lens morphology. More over our results for the in crease of tyrosine doubletratio with the extent of cataract formation in galactosemic lens appear to indicate that there is more hydration in crystallins of the cortex than the nucleus since the in creased ratio of tyro sine doublet has been shown to be due to the hydrogen‐bond formation of hydroxyl groups in various tyrosines of proteins with water. The tryptophan band ratio at 880 cm^?1 and 757 cm^? (I₈₈₀/I₇₅₇) under went a precipitous de crease in the cortex and a rather gradual de crease in the nucleus, suggesting buried tryptophan residues become more exposed in the cortex than in the nucleus during galactose‐induced cataractogenesis. Based on the changes of the two ratios, I₈₃₂/I₈₅₅ and I₈₈₀/I₇₅₇, the change of lens protein environment induced by galactosemic feeding appeared to take place in the cortex first, which was consistent with the observation that the development of an opaque lens be gins in the cortex. While no sulfhydryl (‐SH) signal was detected, there was a slow in crease of disulfide (‐S‐S‐) signal in the cortex of galactose‐fed lenses as compared to control lenses with out galactose. This suggested that a loss of lens glutathione occurred early and oxidation of cysteines in crystallins started in the first week, i.e., be fore the onset of cortical cataract. In contrast, for nucleus of galactosemic lenses the signal of the‐SH group was detected and yet the ‐S‐S‐signal of crystallins could not be found. In this study, we have conclusively demonstrated using Raman vibrational band shift that galactosemic cataract be gins in the cortex, and that the lens cortex suffers more structural alteration in crystallins than the nucleus.     

Studies on the Reaction of α‐Chloroformylarylhydrazine Hydrochloride with Imidazole and 1,2,4‐Triazole

α‐Imidazolformylarylhydrazine 2 and α‐[1,2,4]triazolformylarylhydrazine 3 have been synthesized through the nucleophilic substitution reaction of 1 with imidazole and 1,2,4‐triazole, respectively. 2,2′‐Diaryl‐2H,2′H‐[4,4′]bi[[1,2,4]‐triazolyl]‐3,3′‐dione 4 was obtained from the cycloaddition of α‐chloroformylarylhydrazine hydrochloride 1 with 1,2,4‐triazole at 60 °C and in absence of n‐Bu₃N. The inducing factor for cycloaddition of 1 with 1,2,4‐triazole was ascertained as hydrogen ion by the formation of 4 from the reaction of 3 with hydrochloric acid. 4 was also acquired from the reaction of 3 with 1 and this could confirm the reaction route for cycloaddition of 1 with 1,2,4‐triazole. Some acylation reagents were applied to induce the cyclization reaction of 2 and 3.1 possessing chloroformyl group could induce the cyclization of 2 to give 2‐aryl‐4‐(2‐aryl‐4‐vinyl‐semicarbazide‐4‐yl)‐2,4‐dihydro‐[1,2,4]‐triazol‐3‐one 6. 7 was obtained from the cyclization of 2 induced by some acyl chlorides. Acetic acid anhydride like acetyl chloride also could react with 2 to produce 7D . 5‐Substituted‐3‐aryl‐3H‐[1,3,4]oxadiazol‐2‐one 8 was produced from the cyclization reaction of 3 induced by some acyl chlorides or acetic acid anhydride. The 1,2,4‐triazole group of 3 played a role as a leaving group in the course of cyclization reaction. This was confirmed by the same product 8 which was acquired from the reaction of 1 , possessing a better leaving group: Cl, with some acyl chlorides or acetic acid anhydride.     

Stimuli‐Responsive NO Release for On‐Demand Gas‐Sensitized Synergistic Cancer Therapy

Featuring high biocompatibility, the emerging field of gas therapy has attracted extensive attention in the medical and scientific communities. Currently, considerable research has focused on the gasotransmitter nitric oxide (NO) owing to its unparalleled dual roles in directly killing cancer cells at high concentrations and cooperatively sensitizing cancer cells to other treatments for synergistic therapy. Of particular note, recent state‐of‐the‐art studies have turned our attention to the chemical design of various endogenous/exogenous stimuli‐responsive NO‐releasing nanomedicines and their biomedical applications for on‐demand NO‐sensitized synergistic cancer therapy, which are discussed in this Minireview. Moreover, the potential challenges regarding NO gas therapy are also described, aiming to advance the development of NO nanomedicines as well as usher in new frontiers in this fertile research area.     

The Decomposition Reaction of 4‐Acetylsydnones Arylhydrazones

The acidic decomposition of 4‐acetylsydnones arylhydrazones 2 results in the formation of 4‐arylhydrazo‐1,2‐pyrazolin‐5‐ones 3 and 4‐arylamino‐1,2,3‐triazoles 4 , respectively. The reactions of 4‐acetylsydnones 1 with arylhydrazines 5 afford compounds 3 as the only products in the absence of solvent.