Influence of photo-initiators in the preparation of methacrylate monoliths into poly(ethylene-co-tetrafluoroethylene) tubing for microbore HPLC.

In this study, poly(butyl methacrylate-co-ethyleneglycol dimethacrylate) polymeric monoliths were in situ developed within 0.75 mm i.d. poly(ethylene-co-tetrafluoroethylene) (ETFE) tubing by UV polymerization via three different free-radical initiators (α,α'-azobisisobutyronitrile (AIBN), 2,2-dimethoxy-2-phenylacetophenone (DMPA) and 2-methyl-4'-(methylthio)-2-morpholinopropiophenone (MTMPP). The influence of the nature of each photo-initiator and irradiation time on the morphological features of the polymer was investigated by scanning electron microscopy, and the chromatographic properties of the resulting microbore columns were evaluated using alkyl benzenes as test substances. The beds photo-initiated with MTMPP gave the best performance (minimum plate heights of 38 µm for alkyl benzenes) and exhibited a satisfactory reproducibility in the chromatographic parameters (RSD < 11%). These monolithic columns were also successfully applied to the separation of phenylurea herbicides, proteins and a tryptic digest of ß-casein.

Pore-Filled Scintillating Membrane as Sensing Matrix for α-Emitting Actinides.

Pore-filled membranes with scintillating properties have been synthesized for sensing α-emitting radionuclides. The membranes have been prepared by in situ UV-initiator-induced polymerization of monomer bis[2-(methacryloxy)ethyl] phosphate in pores of the host membranes, poly(propylene) and poly(ethersulfone). The polymerization has been carried out in the presence of scintillating molecules, 2,5-diphenyloxazole. These scintillating molecules are physically trapped in the thus formed microgel in the membrane. Much higher α-scintillation efficiency has been obtained for the (241)Am-loaded poly(ethersulfone)-based grafted membrane compared to poly(propylene)-based membrane. This was attributed to the aromatic backbone of the poly(ethersulfone) membrane. The scintillation response of poly(ethersulfone)-based membranes has been found to be linear over the range of (241)Am activity studied. The pore-filled scintillating membranes have been found to be selective toward Pu(4+) ions at higher HNO3 concentration compared to Am(3+). The analytical performance of the pore-filled scintillating membranes has been evaluated. The membranes have been found to be stable and reusable. The scintillating membrane with optimized composition has been applied for quantification of Pu in a soil sample.

Visible light-promoted metal-free sp(3)-C-H fluorination.

Photoexcited acetophenone can catalyze the fluorination of unactivated C(sp(3))-H groups. While acetophenone, a colorless oil, only has a trace amount of absorption in the visible light region, its photoexcitation can be achieved by irradiation with light generated by a household compact fluorescent lamp (CFL). This operational simple method provides improved substrate scope for the direct incorporation of a fluorine atom into simple organic molecules. CFL-irradiation can also be used to promote certain classic UV-promoted photoreactions of colorless monoarylketones and enones/enals.

An efficient and selective way to new highly functionalized coronands or spiro derivatives using ultrasonic irradiation.

A new, selective, straightforward and general method for preparation of highly functionalized coronands or spiro derivatives bearing 1,2-dihydroxyacetophenone unit, under conventional conditions and ultrasonic irradiation, is reported. The reaction setup involves only one step, acylation of an α-chloro-3,4-dihydroxyacetophenone with phthaloyl dichloride derivatives. 1,3- and 1,4-Phthaloyl dichloride derivatives leads to coronands only, while 1,2-phthaloyl dichlorides lead either to coronands or to spiro derivatives. A feasible explanation for the different behavior between conventional and ultrasound methods could be the different reaction mechanism involved in the two procedures: tetrahedral nucleophilic substitution under conventional conditions and radical substitution under ultrasound. Ultrasound induces a remarkable acceleration of the reactions (from days to minutes) and, most significantly, the yields are twice as high. A feasible explanation for the efficiency of the reactions under ultrasonic irradiation is presented.

Identification of the reactive intermediates produced upon photolysis of p-azidoacetophenone and its tetrafluoro analogue in aqueous and organic solvents: implications for photoaffinity labeling.

Photolysis of p-azidoacetophenone (1a) or 2,3,5,6-tetrafluoro-p-azidoacetophenone (1b) releases the corresponding singlet nitrenes 2a and 2b. In aqueous solutions singlet nitrenes relax (1.1 ps and 43 ns, respectively) to the lower energy triplet nitrenes 3a and 3b, intermediates which do not react to form cross-links or adducts with typical amino acids and nucleic acids. In a hydrophobic environment singlet nitrene 2a partitions between forming triplet nitrene 3a and an acyl-substituted didehydroazepine 4a, which can be detected by LFP and time-resolved IR spectroscopy. The absolute rate constant of reaction of didehydroazepine 4a with water, in acetonitrile, was determined (3.5 x 10(4) M-1 s-1) by laser flash photolysis (LFP) techniques with IR detection at ambient temperature. Photolysis of tetrafluoro azide 1b releases singlet nitrene 2b, which has a lifetime of 172 ns in benzene and can readily be intercepted by pyridine to form ylide 10b (lambdamax = 415 nm). Singlet nitrene 2b reacts with the unactivated CH bonds of cyclohexane to form adduct 8b in 46% yield. Absolute rate constants of reaction of 1b with N-methylimidazole, phenol, dibutyl sulfide, indole, methanol, and dimethyl sulfoxide were determined using the pyridine ylide probe method. It is concluded that photolysis of p-azidoacetophenone (1a) will not lead to cross-link formation but that tetrafluorinated azide 1b can form useful singlet nitrene derived adducts upon photolysis.

Influence of initiator and different polymerisation conditions on performance of molecularly imprinted polymers.

A set of polymers was imprinted with (-)-ephedrine using two different initiators. A chemometrics approach was used to optimise experiments aimed at analysis of the interplay of parameters such as polymerisation time, temperature and percentage of initiator. The results presented demonstrate the importance of keeping the right balance between these various parameters of polymerisation conditions. It is shown that enhancing one single parameter such as polymer rigidity does not necessarily improve polymer performance. In general it could be concluded that MIPs should be synthesised over a long period of time using low concentration of initiator and low temperature. The best selectivity was achieved for polymers prepared by photo-initiation with 2,2-dimethoxy-2-phenylacetophenone as initiator.

Multistate/multifunctional behaviour of 4'-hydroxy-6-nitroflavylium: a write-lock/read/unlock/enable-erase/erase cycle driven by light and pH stimulation.

We have investigated the network of reactions observed for the photochromic 4'-hydroxy-6-nitroflavylium compound in aqueous solutions upon pH changes (including pH jump and stopped flow experiments) and light excitation. The changes observed in the NMR and UV/Vis spectra allowed identification of ten different forms in which this compound can be transformed depending on the experimental conditions. Equilibrium and kinetic constants have been determined. Compared with other members of the flavylium family, 4'-hydroxy-6-nitroflavylium is characterized by a large cis-->trans isomerization barrier, and a very efficient hydration reaction. These peculiar features allow writing, reading, storing and erasing photonic information on 4'-hydroxy-6-nitroflavylium by a novel cyclic process that involves the following steps: write-lock/read/unlock/enable-erase/erase.

New phototriggers: extending the p-hydroxyphenacyl pi-pi absorption range.

[equation--see text] Introducing 3-methoxy or 3,5-dimethoxy substituents on the 4-hydroxyphenacyl (pHP) photoremovable protecting group has been explored with two excitatory gamma-amino acids, L-glutamic acid and gamma-amino butyric acid (GABA). These substituents significantly extend the absorption range of the pHP chromophore, e.g., the tail of absorption bands of 2a,b extend above 400 nm, well beyond the absorptions of aromatic amino acids and nucleotides. Irradiation releases the amino acids with rate constants of approximately 10(7) s(-)(1) and appearance efficiencies (Phi(app)) of 0.03-0.04. The photoproducts are formed through the pHP excited triplet and are primarily products of photoreduction and photohydrolysis. 1a,b also rearranged to the phenylacetic acid 3.

Study of photodynamic reactions of p-nitroacetophenone using ESR and optical techniques.

The photosensitizing properties of p-nitroacetophenone (PNAP), a well-known radiosensitizer, have been studied in near UV region. The mechanism of PNAP photosensitization has been investigated by testing the efficiency of singlet oxygen production using photooxidation of 2,2,6,6-tetramethylpiperidine (TEMP) and photodegradation of guanosine. In both the cases, the enhancement effect of deuterated solvents has been observed. Results of these experiments suggest the significant role of type II mechanisms in PNAP photosensitization.

The oxygen dependence of the reduction of nitroimidazoles in a radiolytic model system.

Radiation chemical reductions using eaq- and CO2- have been carried out in the presence of oxygen with metronidazole, p-nitroacetophenone, misonidazole and three other 2-nitroimidazoles. Low concentrations of oxygen were found to effectively inhibit the reduction of the first two compounds while much higher concentrations of oxygen were required for all of the 2-nitroimidazoles. These results parallel in vitro and in vivo experiments with metronidazole and misonidazole which also indicate that the reduction of the latter is significantly less inhibited by oxygen. Kinetic modelling of the radiochemical system suggests that the explanation for the differences lies in different reactions of the nitro radical anions; it appears that the anion derived from metronidazole undergoes disproportionation while that derived from misonidazole undergoes a unimolecular decay.

Action spectra for ultraviolet photosensitized killing of mammalian cells by misonidazole and para-nitroacetophenone.

V-79 Chinese hamster fibroblasts in monolayer culture were exposed to ultraviolet radiation at 313, 334, 365, 380, and 405 nm in the presence of either misonidazole or para-nitroacetophenone, drugs which act as both photosensitizers and radiosensitizers of cell killing. Survival was measured by a colony-forming assay. The resulting action spectra for cell death photosensitized by the drugs (the reciprocals of the exposures required at each wavelength to reduce cell survival to a given level) closely match their absorption spectra over a range of three orders of magnitude. These results demonstrate that cells can be killed upon excitation of misonidazole or para-nitroacetophenone in the absence of any other types of energy deposition or biomolecular damage.

The rates of electron transfer from ClUra- and ClUraH-to p-nitroacetophenone.

Pulse-radiolysis experiments demonstrate that both the radical ion CIUra-/- and the protonated radical CIUraH- Of chlorouracil will transfer electrons to p-nitroacetophenone (PNAP). The reaction of CIUraH- is complicated by unknown reaction with PNAP below pH 4-4. Rate constants measured for reactions (2) and (3) are kappa2=5-3 x 109 and kappa3=3-3 x 109 M-1 sec -1. See article. An independent determination of the rate-constant for dissociation of the radical ion (equation (1)) was also obtained (kappa1=0-7 x 105 sec -1). See article.

P-Azidophenacyl bromide, a versatile photolabile bifunctional reagent. Reaction with glyceraldehyde-3-phosphate dehydrogenase.

The synthesis of the photochemically labile bifunctional reagent p-azidophenacyl bromide (1) is described. This compound may be covalently attached to a known site of an enzyme or other macromolecule by nucleophilic displacement at the alpha-bromo ketone moiety. Subsequent irradiation of the bound reagent gives a nitrene which may insert into a second portion of the enzyme forming a cross-link. Regeant 1 proved to be an excellent inhibitor of rabbit muscle glyceraldehyde-3-phosphate dehydrogenase.