Endoplasmic Reticulum-Targeted Ratiometric N-Heterocyclic Carbene Borane Probe for Two-Photon Microscopic Imaging of Hypochlorous Acid.

The naphthoimidazolium borane 4 is shown to be a selective probe for HOCl over other reactive oxygen species. Unlike other boronate-reactive oxygen species (ROS) fluorogenic probes that are oxidized by HOCl through a nucleophilic borono-Dakin oxidation mechanism, probe 4 is distinguished by its electrophilic oxidation mechanism involving B-H bond cleavage. Two-photon microscopy experiments in living cells and tissues with the probe 4 demonstrate the monitoring of endogenous HOCl generation and changes in HOCl concentrations generated in the endoplasmic reticulum during oxidative stress situations.

Novel magnetically separable silver-iron oxide nanoparticles decorated graphitic carbon nitride nano-sheets: A multifunctional photocatalyst via one-step hydrothermal process.

Development of photocatalytic materials with magnetic and antibacterial properties is highly desirable in wastewater treatment. In this study, a novel magnetically separable silver-iron oxide nanoparticles (Ag-Fe3O4 NPs) decorated graphitic carbon nitride (g-C3N4) nanocomposite via hydrothermal treatment has been presented for the multifaceted applications. The physiochemical properties of the as-synthesized ternary nanocomposite were characterized by the field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) studies. The experimental results showed that loading of Ag on Fe3O4/g-C3N4 nanocomposite significantly improved the catalytic activity of the composite material in terms of photocatalytic degradation of methylene blue (Mdestruction of Escherichia coli (E. coli) bacteria. More importantly, the as-synthesized silver-iron oxide nanoparticles decorated graphitic carbon nitride (Ag-Fe3O4/g-C3N4) nanocomposite catalyst could be recovered by an applied external magnet and reused without the loss of photocatalytic activity. The obtained results showed that the synthesized material has potential as an economically friendly photocatalyst for environmental and energy applications.

Lewis-acid-catalyzed photodimerization of coumarins and N-methyl-2-quinolone.

The BF(3)-catalyzed photodimerization of parent coumarin (1), three 6-alkylcoumarins (2-4) and N-methyl-2-quinolone (5) in dichloromethane was studied by time-resolved UV-vis spectroscopy. The lowest triplet state properties in the absence and presence of BF(3) were outlined, in particular the effect of self-quenching which initiates dimerization. The quantum yield of intersystem crossing (Phi(isc)) of 1-4 increases with BF(3) concentration, approaching Phi(isc) = 0.3. Phi(isc) and the relative quantum yield of dimerization go along, thereby favoring an overall triplet mechanism in both the direct and BF(3)-catalyzed photodimerization. The product ratio of 5 changes strongly with the BF(3) concentration from 100%anti-hh for the free quinolone to 100%syn-ht for the 1:1 complex.

Abiotic degradation of triphenylborane pyridine (TPBP) antifouling agent in water.

The abiotic degradation of the new antifouling agent, triphenylborane pyridine (TPBP), was investigated in buffer solutions having different pH values (pH 5, 7, and 9), and in artificial and natural seawater to estimate environmental fate of TPBP. The TPBP in these waters was decomposed by a seven-day hydrolysis process at 50 degrees C both in the dark and a photolysis process under UV-A irradiation using a high-pressure mercury lamp for periods up to 24h. TPBP hydrolysis was significantly enhanced by acidic pH solutions. The photolysis rate of TPBP was higher in acidic pH solutions than in neutral or basic pH solutions, and was highest in natural seawater, which could have contained naturally dissolved organic matter. Two degradation products, phenol and an unknown substance (Peak #1), were observed during the hydrolysis and photolysis studies of TPBP. The concentration of these substances after a one-day photolysis treatment was higher than after a seven-day hydrolysis treatment. The degradation rate of TPBP in the five test water samples was related to the simultaneous photolysis formation of phenol and Peak #1. However, the degradation rate of TPBP was not related to the formation of the hydrolysis products. Therefore, it is suggested that photodegradation of TPBP follows a different pathway to the hydrolysis degradation of TPBP. Our results indicate the chemical and photochemical reaction of TPBP in water occurs in natural aquatic environments.

19F spectroscopy and relaxation behavior of trifluorovinyldichloroborane.

The 19F NMR spectra and spin-lattice relaxation rate, R1, of trifluorovinyldichloroborane as shown in were studied as a function of temperature, T, and magnetic field, B. All logR1 vs 1/T plots show a minimum at 299K indicating the presence if dipolar relaxation at lower T and spin-rotation relaxation at higher T. The R1 values increase with increasing B due to chemical shift anisotropy relaxation. Estimates of the fluorine chemical shift values for F3 (cf. Fig. 1) suggest that there is pi character in the F-C bond. The other two C-F bonds are largely single bonded. No evidence was found for intermolecular exchange of the trifluorovinyl group. Two of the three fluorine atoms show large increases in their NMR linewidth with increasing temperature while the third shows only a small increase but the activation energy for the process is the same for all. The increase in linewidths is due to scalar coupling to the boron atoms. The boron linewidths were measured between 253 and 363K and decreased with increasing temperature. A plot of logR2, where R2 is the linewidth of the boron as a function of 1/T shows some curvature indicating a second relaxation mechanism. This is ascribed to spin-rotation but not enough data are available to be conclusive. In all cases there is a second small set of fluorine peaks that are due to 10B interactions separated from the 11B peaks by amounts varying from 1 to 4 ppm depending on the field and fluorine atom.

Evaluation of the potential of p-boronophenylalaninol as a boron carrier in boron neutron capture therapy, referring to the effect on intratumor quiescent cells.

C57BL mice bearing EL4 tumors and C3H / He mice bearing SCC VII tumors received 5-bromo-2'-deoxyuridine (BrdU) continuously for 5 days via implanted mini-osmotic pumps to label all proliferating (P) cells. Three hours after oral administration of l-p-boronophenylalanine-(10)B (BPA), or 30 min after intraperitoneal injection of sodium borocaptate-(10)B (BSH) or l-p-boronophenylalaninol (BPA-ol), a newly developed (10)B-containing alpha-amino alcohol, the tumors were irradiated with thermal neutron beams. For the combination with mild temperature hyperthermia (MTH) and / or tirapazamine (TPZ), the tumors were heated at 40 degrees C for 30 min immediately before neutron exposure, and TPZ was intraperitoneally injected 30 min before irradiation. The tumors were then excised, minced and trypsinized. The tumor cell suspensions thus obtained were incubated with cytochalasin-B (a cytokinesis blocker), and the micronucleus (MN) frequency in cells without BrdU labeling ( = quiescent (Q) cells) was determined using immunofluorescence staining for BrdU. Meanwhile, 6 h after irradiation, tumor cell suspensions obtained in the same manner were used for determining the apoptosis frequency in Q cells. The MN and apoptosis frequency in total (P + Q) tumor cells were determined from tumors that were not pretreated with BrdU. Without TPZ or MTH, BPA-ol increased both frequencies most markedly, especially for total cells. However, as with BPA, the sensitivity difference between total and Q cells was much larger than with BSH. On combined treatment with both MTH and TPZ, this sensitivity difference was markedly reduced, similarly to when BPA was used. MTH increased the (10)B uptake of all (10)B-compounds into both tumor cells. BPA-ol has good potential as a (10)B-carrier in neutron capture therapy, especially when combined with both MTH and TPZ.