Positron annihilation lifetime studies of changes in free volume on some biorelevant nitrogen heterocyclic compounds and their S-glycosylation.

A series of N-heterocyclic compounds was investigated by positron annihilation lifetime spectroscopy as well as Doppler broadening of annihilation radiation (DBAR) at room temperature. The results showed that the formation probability and life time of ortho-positronium in this series are structure and electron-donation character dependent, and can give more information about the structure. The DBAR provides direct information about the change of core and valance electrons as well as the number of defect types present in these compounds.

Insights on the relaxation of liposomes encapsulating paramagnetic Ln-based complexes.

PURPOSE: To describe and quantify the different relaxation mechanisms operating in suspensions of liposomes that encapsulate paramagnetic lanthanide(III) complexes. THEORY AND METHODS: The transverse relaxation rate of lanthanide-loaded liposomes receives contribution from the exchange between intraliposomal and bulk water protons, and from magnetic susceptibility effects. Phospholipids vesicles encapsulating different Ln(III)-HPDO3A complexes (Ln = Eu, Gd, or Dy) were prepared using the conventional thin film rehydration method. Relaxation times (T1 , T2 , and T2*) were measured at 14 Tesla (T) and 25 °C. The effect of compartmentalization of the paramagnetic agent inside the liposomal cavity was evaluated by means of an IRON-modified MRI sequence. RESULTS: NMR measurements demonstrated that Curie spin relaxation is the dominant contribution (> 90%) to the observed transverse relaxation rate of paramagnetic liposomes. This was further confirmed by MRI that showed the ability of the liposome entrapped lanthanide complexes to generate IRON-MRI positive contrast in a size dependent manner. CONCLUSION: The Curie spin relaxation mechanism is by far the principal mechanism involved in the T2 shortening of the water protons in suspension of paramagnetic liposomes at 14T. The access to IRON contrast extends the potential of such nanosystems as MRI contrast agents.

[New-type electrodeless excilamp for advanced treatment on nitrogen-heterocyclic compounds (NHCs) in aqueous solution].

A novel 206 nm excilamp generated by microwave-driven Kr/I2 mixtures was employed for nitrogen-heterocyclic compounds (NHCs) degradation in aqueous solution. The photodissociation efficiencies of indole and quinoline with 206 nm excilamp were estimated on the basis of removal efficiency of targeted compounds and the loss of total organic carbon (TOC). The results indicated that removal efficiency of 20 mg x L(-1) indole was as high as 62.0% after 80 min and TOC loss efficiency of 50.7% for 150 min. The irradiation time, initial concentration and pH value had some influences on quinoline degradation. Indole removal efficiency and TOC loss was markedly higher than that of quinoline under the same condition. The intermediates were identified qualitatively by gas chromatography/mass spectrum (GC/MS) with headspace sampling after they were extracted by rotary evaporator. GC/MS analysis indicated that indole and quinoline underwent ring-open dissociation under 206 nm irradiation, as a result, benzene, xylene, acetate, aldehyde, as well as ester compounds were formed, while indole aggregation reaction occurred during indole photodegradation. At last, degradation mechanisms of quinoline and indole in aqueous media with 206 nm excilamp were proposed on the basis of intermediates.

Ultrasound-promoted greener synthesis of benzoheterocycle derivatives catalyzed by nanocrystalline copper(II) oxide.

CuO nanoparticles provide an efficient, economic, and novel method for the synthesis of quinoxaline, benzoxazine, and benzothiazine under ultrasonic irradiation. The protocol offers advantages in terms of higher yields, short reaction times, and mild reaction conditions, with reusability of the catalyst.

Rapid and efficient synthesis of fused heterocyclic pyrimidines under ultrasonic irradiation.

Some fused heterocyclic pyrimidines have been synthesized in high yields using ultrasound irradiation in a one-pot, three-component and efficient process by condensation reaction of barbituric acids, aldehydes and a series of enamines in water. Prominent among the advantages of this new method are operational simplicity, good yields in short reaction times and easy work-up procedures employed.

Effects of radiation on the NMR relaxation effects of aqueous solutions of gadolinium contrast agents.

We investigate the effects of radiation on aqueous solutions of two common MRI contrast agents based on paramagnetic gadolinium chelates. Aqueous solutions of Gd-DTPA (gadolinium diethylenetriaminepentaacetic acid) and Gd-HP-DO3A (gadoteridol), as well as Gd-DTPA in the presence of concentrations of several common metabolites (N-acetylaspartate, Choline, Creatine and myo-inositol) typical of conditions in vivo, were irradiated at dose levels up to 30 Gy using a 6 MV linear accelerator and imaged using a 1.5 T MRI system. In addition, the effects of radiation dose on solution relaxation rates were compared with the effects of temperature by subjecting the same samples to varying temperatures over a range of 4 K using the same experimental conditions and imaging sequences. Radiation caused small increases (1% or less at a dose of 20 Gy) in the relaxivity of solutions. The effects of radiation on relaxivities were orders of magnitude smaller than the effects of temperature over the range in this study.

Efficient green solar cells via a chemically polymerizable donor-acceptor heterocyclic pentamer.

In this contribution, we report on bulk-heterojunction solar cells using a solution-processable neutral green conjugated copolymer based on 3,4-dioxythiophene and 2,1,3-benzothiadiazole as the donor and [6,6]phenyl-C61 butyric acid methyl ester (PCBM) as the acceptor. We have found that the short-circuit current is very sensitive to the composition of the donor-acceptor blend and it increases with increasing acceptor concentration. The device with a donor-acceptor ratio of 1:8 gives the best performance with a short-circuit current of 5.56 mA/cm(2), an open-circuit voltage of 0.77 V, and a power conversion efficiency of 1.9% under AM 1.5 solar illumination. The incident photon-to-current efficiency (IPCE) of the green solar cells shows two bands, one with a maximum of 57% in the UV region corresponding to absorption of PCBM and a second one with a maximum of 42% at longer wavelengths corresponding to the absorption of the green polymer.

Field strength dependence of R1 and R2* relaxivities of human whole blood to ProHance, Vasovist, and deoxyhemoglobin.

This study has measured the longitudinal and transverse (T2* relaxivity curves for ProHance (Gadoteridol), Vasovist (Gadofosveset) and deoxyhemoglobin at 1.5, 3.0, and 7.0 Tesla. The plots of R(1) versus both contrast agent and deoxyhemoglobin concentration were linear. The plots of R2* versus deoxyhemoglobin concentration showed a quadratic dependence. R2* versus contrast agent concentration showed a parabolic dependence with a minimum occurring at contrast agent concentrations of approximately 1.5 mM, corresponding to an accessible concentration in vivo. Monte Carlo simulations were performed to support the hypothesis that the minimum results from the susceptibility of the red blood cells being matched to the susceptibility of the plasma. Relaxivity values (s(-1)mM(-1)) for R2* and R1 for all agents and all three field strengths are given.

The macrocyclic effect and vasodilation response based on the photoinduced nitric oxide release from trans-[RuCl(tetraazamacrocycle)NO](2+).

Irradiation of trans-[RuCl(cyclam)(NO)](2+), cyclam is 1,4,8,11-tetraazacyclotetradecane, at pHs 1-7.4, with near UV light results in the release of NO and formation of trans-[Ru(III)Cl(OH)(cyclam)](+) with pH dependent quantum yields (from approximately 0.01 to 0.16 mol Einstein(-1)) lower than that for trans-[RuCl([15]aneN(4))(NO)](2+), [15]aneN(4) is 1,4,8,12-tetaazacyclopentadecane, (0.61 mol Einstein(-1)). After irradiation with 355 nm light, the trans-[RuCl([15]aneN(4))(NO)](2+) induces relaxation of the aortic ring, whereas the trans-[RuCl(cyclam)(NO)](2+) complex does not. The relaxation observed with trans-[RuCl([15]aneN(4))(NO)](2+) is consistent with a larger quantum yield of release of NO from this complex.

A comparison of microwave-accelerated and conventionally heated iodination reactions of some arenes and heteroarenes, using ortho-periodic acid as the oxidant.

A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method.

Low-energy (5-40 eV) electron-stimulated desorption of anions from physisorbed DNA bases.

We present the results of experiments on anion desorption from the physisorbed DNA bases adenine, thymine, guanine and cytosine induced by the impact of low-energy (5-40 eV) electrons. Electron bombardment of DNA base films induces ring fragmentation and desorption of H(-), O(-), OH(-), CN(-), OCN(- ) and CH(2)(-) anions through either single or complex multibond dissociation. We designate the variation of the yield of an anion with electron energy as the yield function. Below 15 eV incident electron energy, bond cleavage is controlled mainly by dissociative electron attachment. Above 15 eV, the portion of a yield function that increases linearly is attributed to nonresonant processes, such as dipolar dissociation. A resonant structure is superimposed on this signal around 20 eV in the anion yield functions. This structure implicates dissociative electron attachment and/or resonant decay of the transient anion into the dipolar dissociation channel, with a minimal contribution from multiple inelastic electron scattering. The yields of all desorbing anions clearly show that electron resonances contribute to the damage of all DNA bases bombarded with 5-40 eV electrons. Comparison of the ion yields indicates that adenine is the least sensitive base to slow electron attack. Electron-irradiated guanine films exhibit the largest yields of desorbed anions.

Effect of microwave pretreatment on heterocyclic aromatic amine mutagens/carcinogens in fried beef patties.

To investigate a method to reduce the amount of mutagenic/carcinogenic heterocyclic aromatic amines formed during frying of ground beef, the mutagenic activity in Salmonella strain TA98 was assessed and the amount of known heterocyclic amines was determined by solid-phase extraction and HPLC. The beef patties received microwave treatment for various times before frying. Microwave pretreatment for 0, 1, 1.5, 2 or 3 min before frying at either 200 degrees C or 250 degrees C for 6 min per side reduced heterocyclic aromatic amine precursors (creatine, creatinine, amino acids, glucose), water, and fat up to 30%, in the patties and resulted in a decrease in mutagenic activity up to 95%. The sum of the four heterocyclic aromatic amines shown to be present--2-amino-3,8-dimethylimidazo[4,5-f]-quinoxaline (MeIQx), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3,4,8-trimethylimidazo-[4,5-f]quinoxaline (DiMeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)--decreased three- to nine-fold compared with control, non-microwaved beef patties fried under identical conditions.

Photobiological studies with dioxetanes in isolated DNA, bacteria, and mammalian cells.

1,2-Dioxetanes, efficient chemical sources of triplet excited carbonyl compounds, were observed to be genotoxic in isolated DNA, bacteria, and cultured mammalian cells. In superhelical DNA of bacteriophage PM2, various alkyl- and hydroxyalkyl-substituted dioxetanes (1) induced predominantly endonuclease-sensitive base modifications and only few single strand breaks. With a specific endonuclease a small fraction of the base modifications was identified as pyrimidine dimers. The psoralen dioxetane (2a) or PsD bound photochemically to calf thymus DNA at the alpha-pyrone ring of psoralen (fluorescence measurements). Photobinding was also observed when calf thymus DNA was incubated with psoralen and 3-hydroxymethyl-3,4,4-trimethyl-1,2-dioxetane. In Syrian hamster embryo fibroblasts and HL-60 cells, dioxetanes induced DNA single strand breaks. The alkyl- and hydroxyalkyl-substituted dioxetanes 1 and 2 were efficiently inactivated by cysteine, glutathione, ascorbic acid, tocopherol, NADH and FADH2. While dioxetanes 1 and 2 were not mutagenic in Salmonella typhimurium strain TA100, benzofuran dioxetanes 3 exhibited substantial effects. Further data imply that presumably a mutagenic intermediate with a lifetime of a few minutes is produced from the benzofuran dioxetane.