IR, MS studies on (+/-)-1-[3-(2-methoxyphenoxy)-2-hydroxypropyl]-4-[(2,6-dimethylphenyl)aminocarbonylmethyl]piperazine dihydrochloride salt

The vibration spectrum and FAB mass spectrum of (+/-)-1-[3-(2-methoxyphenoxy)-2-hydroxypropyl]-4-[(2,6-dimethylphenyl)aminocarbonylmethyl]piperazine dihydrochloride salt was studied. By comparing with the spectra of free base, different bands of IR were found in the NH+ stretching, the NH+ deformation motion, the CH2 of NCH2 group symmetric stretching, the CH2 of N-CH2 group twisting and the CN stretching. FAB shows the basic peak is M + H. Other m/e peaks are consistent with the structure.     

Block copolymer from α,ω-dihydroxyl polystyrene and polyethylene glycol

α,ω-Dihydroxyl polystyrene was synthesized by the addition of styrene oxide to polystyryl dianion initiated with sodium naphthalene. Diglyme was found to be an unsuitable solvent for the preparation of low molecular weight compounds. Block copolymerization of the α,ω-dihydroxyl polystyrenes (M?_n = 2250, 3140, and 6200) with poly(ethylene glycols) (M?_n = 404, 1960, and 5650) was pursued by introducing urethane linkages with 4,4′-diphenylmethane diisocyanate. The mechanical, thermal, and viscoelastic properties, solution viscosity, molecular weight distribution, and moisture absorption of the block copolymers obtained were examined. Incorporation of styrene blocks was found to disturb the crystallization and fusion of poly(ethylene glycol) blocks. Films cast from benzene solution were soft and elastic and absorbed up to 5.8% moisture.     

Different reaction routes found in acid-catalyzed glycosylation of endo- and exo-glycals: competition between Ferrier rearrangement and protonation

Acid-mediated glycosylations of endo- and exo-glycals have been carried out in good to excellent yields, in which a mixture of two products is often obtained resulting from Ferrier rearrangement and protonation. The former reaction exclusively takes place with the t-butyl carbonate or hydroxyl substituent at the C3 position of endo-glycals, while the latter mainly occurs in the glycosylation of exo-glycals with allyl benzyl ether or acetate. In addition to the substituent effect, protecting groups are critical to determine the activity and favored reaction pathway. Furthermore, the method is applicable to O-, C-, and N-nucleophiles.     

Electron Paramagnetic Resonance Study of Radical Pairs and Isolated Radicals Trapped in Irradiated Long-Chain Hydrocarbons at Low Temperatures

The intrinsic characteristics of radical pairs produced in squalane and in cetane receiving high gamma-dose are extensively studied with the EPR technique at temperatures from 77°K up to 150°K. The spectra of the paired radicals occur at g=4 with a very low transition probability in contrast to that of isolated radicals which appear at g=2 A well-resolved hyperfine spectrum corresponding to the species (CH₃CH₂.CH₂CH₃) is observed in cetane. The isothermal decay rates of radical pairs in cetane below 100°K are significantly slow; however, the decay kinetics at 150°K is first order with rate constant=1.86 min^?1. A relatively slower decay rate is obtained for isolated radicals suggesting that the decay mechanism of paired radicals is through geminate recombination. The relative inter-radical distance in radical pairs is known from a decay curve as a function of temperature. The yields of radical pairs are low in both matrices, only few percents of those of isolated radicals. The formation mechanisms of paired radicals with direct radiolytic bond scission process are discussed in connection with the experimental observations.     

Increased throughput in quantitative bioanalysis using parallel-column liquid chromatography with mass spectrometric detection

The feasibility of quantitative bioanalysis by parallel-column liquid chromatography in conjunction with a conventional single-source electrospray mass spectrometer has been investigated using plasma samples containing a drug and its three metabolites. Within a single chromatographic run time, sample injections were made alternately onto each of two analytical columns in parallel at specified intervals, with a mass spectrometer data file opened at every injection. Thus, the mass spectrometer collected data from two sample injections into separate data files within a single chromatographic run time. Therefore, without sacrificing the chromatographic separation or the selected reaction monitoring (SRM) dwell time, the sample throughput was increased by a factor of two. Comparing the method validation results obtained using the two-column system with those obtained using the corresponding conventional single-column approach, the methods on the two systems were found to be equivalent in terms of accuracy and precision. The parallel-column system is simple and can be implemented using existing laboratory equipment with no additional capital outlays. A parallel-column system configured in this manner can be used not only for the within-a-run analysis of two samples containing two different sets of chemical entities, but also for the within-a-run analysis of two samples containing the same set of chemical entities.     

Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons

A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.     

The polarized electronic spectra and electric field spectra of benzo-diazoles. II. 2,1,3-benzothiadiazole

The S₁ ← S₀ absorption spectra of 2,1,3-benzothiadiazole (BTD) have been measured at 4.2 K in four different host crystals: naphthalene, durene, p-dichlorobenzene (DCB) and p-dibromobenzene. Detailed vibrational analyses are given for BTD imbedded in napthalene and DCB. The polarization measurements show that the S₁ state has B₂ symmetry, like its selenium analogue (BSD). The transition is dominated by a single totally symmetric mode - 484 cm^?1. The Herzberg-Teller coupling contributes only a very small fraction of the total intensity. The Stark measurements of a DCB sample containing both BTD and BSD enabled us to compare the charge distribution of BTD and BSD in the state S₁. The Stark splittings of BTD are 17% greater than the splittings of BSD. Reorganization of the σ-core during the excitation is used to explain the difference. The drastic change in dipole moment upon excitation implies that the S₁←S₀ transitions of BTD and BSD are not localized in the six-membered ring as suggested by previous workers. Weak phosphorescence of BTD in napthalene and DCB and singlet-triplet absorption spectrum of neat BTD have been observed. The heavy atom effect of spin-orbit coupling is to explain the ST absorption intensity of BTD and BSD.     

The study and characterization of nucleosides by mass spectrometry—I: The mass spectra of pyrimidine 2,2′-anhydronucleosides and their derivatives

The mass spectra of 2,2′-anhydrouridine, 2,2′-anhydrothymidine and 2,2′-anhydro-4-thiouridine are reported. The acetyl, trifluoroacetyl, trityl, pivaloyl and trimethylsilyl ether derivatives were also studied. Deuterium labeling in acetyl and trimethylsilyl groups aided characterization of many ions in the spectra, as well as helping to clarify hydrogen migration processes. The anhydronucleosides and their derivatives are readily distinguished from natural nucleosides by the presence of an ion containing the base moiety plus the anhydro-ring plus one hydrogen atom from the rest of the molecule. As for natural nucleosides the [base + H]⁺ and [base + 2H]⁺ ions are usually prominent, but in contrast to natural nucleosides, ions characteristic of the sugar moiety do not retain the 2′-oxygen atom (i.e. the oxygen atom of the anhydro-ring). The mass spectra of deuterium labeled derivatives suggest a test for the presence of a 3′-O-acetyl function (the O-acetyl group is lost from the molecular ion much more readily from the 3′- than from the 5′-carbon atom). The trimethylsilyl derivatives showed evidence in their mass spectra for migration of trimethylsilyl groups in addition to hydrogen atoms.     

UV-ENHANCED REACTIVATION IN MAMMALIAN CELLS: INCREASE BY CAFFEINE

Abstract— It has been reported that caffeine decreases UV-enhanced reactivation of UV-irradiated Herpes simplex virus in CV-1 monkey kidney cells. That occurred when there was no delay between cell irradiation and virus infection. In the present study, virus infection was delayed following cell irradiation to allow an 'induction'period separate from the 'expression'period which occurs during the virus infection. Thus, the effects of caffeine on 'induction'and 'expression'could be determined separately. Caffeine increased the expression of UV-enhanced reactivation, while causing a small decrease in the 'induction'of enhanced reactivation.     

Skin Necrosis due to Photodynamic Action of Benzoporphyrin Depends on Circulating Rather than Tissue Drug Levels: Implications for Control of Photodynamic Therapy

In an ideal world, photodynamic therapy (PDT) of abnormal tissue would reliably spare the surrounding normal tissue. Normal tissue responses set the limits for light and drug dosimetry. The threshold fluence for necrosis (TFN) was measured in normal skin following intravenous infusion with a photosensitizer, benzoporphyrin derivative monoacid ring A (BPD-MA) Verteporfin as a function of drug dose (0.25-2.0 mg/kg), wavelength of irradiation (458 and 690 nm) and time interval (0–5h) between drug administration and irradiation. The BPD-MA levels were measured in plasma and skin tissue to elucidate the relationship between TFN, drug kinetics and biodistribution. The PDT response of normal skin was highly reproducible. The TFN for 458 and 690 nm wavelengths was nearly identical and the estimated quantum efficiency for skin response was equal at these two wavelengths. Skin phototoxicity, quantified in terms of 1/ TFN, closely correlated with the plasma pharmacokinetics rather than the tissue pharmacokinetics and was quadratically dependent on the plasma drug concentration regardless of the administered drug dose or time interval between drug and light exposure. This study strongly suggests that noninvasive measurements of the circulating drug level at the time of light treatment will be important for setting optimal light dosimetry for PDT with liposomal BPD-MA, a vascular photosensitizer.