The reaction of 2-(3-sydnonyl)phenylmethanol with sulfonyl chlorides. A one pot conversion to the chloro congener

The interesting transformation of 2-(3-sydnonylphenylmethanol ( 1 ) to its chloro congener 2 , in moderate to good yield using sulfonyl chlorides, is described. A mechanism for the transformation is suggested.     

ACTION SPECTRUM AND THRESHOLD SENSITIVITY OF ENTRAINMENT OF ORCADIAN RUNNING ACTIVITY IN THE COCKROACH PERIPLANETA AMERICANA

Abstract— The interaction between the compound eye and the circadian timing system for running activity in the cockroach, Periplaneta americana , has been investigated by measuring the action spectrum for entrainment of such behavior by imposed photic stimuli. Test wavelengths were selected which spanned the spectral range of the dichromatic retina of this insect and intensities of such lights for which half of a population of animals failed to be entrained (threshold) were determined. Stimuli were presented either with a 12:12 light–dark regime or for 12h/day on a continuous background of orange light. The latter procedure altered the balance of sensitivity in the two groups of color receptors in the eye. A comparison of the resulting action spectra and the spectral sensitivities of receptors and visual interneurons measured under similar conditions suggest that the entrainment mechanism is dominated by the receptor group most sensitive to long wavelength light. Furthermore, the eye-clock mechanism shows an extraordinarily high sensitivity to such stimuli. We estimate that a mean flux of about 5 photons/eye/s is sufficient to entrain the behavior. The implications of these results are discussed.     

In vivo EXPOSURE TO ULTRAVIOLET RADIATION ENHANCES PATHOGENIC EFFECTS OF MURINE LEUKEMIA VIRUS, LP-BMS, IN MURINE ACQUIRED IMMUNODEFICIENCY SYNDROME

LP-BM5 murine leukemia virus (MuLV) induces an immunodeficiency syndrome (MAIDS) in C57BL/6 mice which resembles immunological abnormalities observed in early stages of human AIDS. In our study, MAIDS virus-infected mice were exposed to low doses of ultraviolet radiation (UVR) before and after virus inoculation and compared with MAIDS-infected but not UVR-exposed mice. In all tested parameters (blood IgM levels; mitogenic responses to PHA, ConA, LPS and anti-mu; MLR; antigenic response to SRBC; enlargement and histopathologic changes of the spleen) we observed the same trend: changes due to MAIDS infection were more pronounced in the UVR-exposed group than in the unexposed group. Statistically significant differences between these two groups were seen for mitogenic responses at two different time points after virus inoculation. These results demonstrate that in vivo UVR exposure enhances the immunosuppressive effects of a retroviral infection. UVR exposure may affect the progression of AIDS in a similar manner.     

PHOTODYNAMIC SENSITIZERS FROM CHLOROPHYLL:PURPURIN–18 AND CHLORINp6

Abstract— Two easily prepared derivatives of chlorophyll,purpurin–18 and chlorin p ₆, are potent sensitizers of cell killing by low-intensity red light. The internal anhydride group inpurpurin–18 provides the potential of covalently linking in one step the chlorin to cell targeting agents such as antibodies.     

A new germanium tetracobalt carbonyl: GeCo4(CO)14

The room-temperature reaction of NaCo(CO)₄ with halogermanes, or Co₂(CO)₈ with GeH₄, gives GeCo₄(CO)₁₄ which is assigned a Ge[Co₂(CO)₇]₂ structure on infrared evidence. This new species eliminates one CO at 50°C to give (CO)₄CoGeCO₃(CO)₉ and adds further CO(CO)₄^- to give anionic [GeCo₆(CO)_n]^2-.     

Changing selectivity of DNA oxidation from deoxyribose to Guanine by ligand design and a new binuclear copper complex

A dinuclear copper complex [CuII2(PD'O)(H2O)2]3+ (1) (where PD'OH is a pyridylalkylamine containing binucleating ligand) promotes guanine oxidation in single-stranded DNA in the presence of 3-mercaptopropionic acid and dioxygen. This reaction is detected after subsequent piperidine treatment. Little spontaneous strand scission indicative of deoxyribose oxidation is observed in contrast to the results known for other copper complexes. Chemical characterization and nanospray ionization mass spectrometry analysis of oligodeoxynucleotides treated with 1 suggest conversion of guanine residues to their 2,6-diamino-5-formamidino-4-hydroxypyrimidine (+18 amu) and possibly 5,8-dihydroxy-7,8-dihydroguanine (+34 amu) derivatives. The selectivity toward nucleobase rather than deoxyribose oxidation is discussed in terms of the specific nature of the dicopper (hydro)peroxo species formed with the PD'OH ligand versus the intermediates formed in the presence of other binucleating ligands.     

Solid-state structural properties of 2,4,6-trimethoxybenzene derivatives, determined directly from powder X-ray diffraction data in conjunction with other techniques

Structural properties of 2,4,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzyl alcohol and 2,4,6-trimethoxyacetophenone have been determined directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm (GA) technique for structure solution followed by Rietveld refinement. Structural similarities and contrasts within this family of materials are elucidated. The work illustrates the value of utilizing information from other sources, including spectroscopic data and computational techniques, as a means of augmenting the structural knowledge established from the powder X-ray diffraction data.     

Fructose production

Amyloglucosidase, pullulanase, and glucose isomerase were coimmobilized onto granular chicken bone (BIOBONE^TM). Enzyme ratios showing optimum glucose and fructose production (0.7:10:22.3 U amyloglucosidase: pullulanase: glucose isomerase) resulted in 14.4±1.9% of activity bound relative to an equal amount of free enzyme. The estimated specific activity for these enzymes decreased 4.6-fold with immobilization. Reaction_pH strongly influenced the yield and ratio of glucose and fructose produced. Net hexose production from the immobilized system was optimal at_pH 6.5 and 55°C with a fructose yield of about 20%.     

Hydrogen bonding: Part 19. IR and NMR study of the lower hydrates of choline fluoride and acetylcholine chloride

Acetylcholine chloride, like choline chloride, forms a liquid salt dihydrate, and a crystalline monohydrate that only exists at reduced pressure; at atmospheric pressure the monohydrate disproportionates into liquid dihydrate and anhydrous acetylcholine chloride. Both choline and acetylcholine chlorides give endothermic dissolution in water. In contrast, choline fluoride gives exothermic dissclution in water, and forms an extra-ordinarily stable monohydrate in which choline cation hydroxyls form strong hydrogen bonds to an H₄O₂F^2?₂ cluster anion. Since the hydration behavior of choline fluoride is like that of unsubstituted tetraalkylammonium fluorides, the unusual hydration behavior of choline and acetyline chlorides results from the presence of chloride ion, and is not an intrinsic property of cholinergic cations.     

Pharmaceutical applications of variable-angle synchronous scanning fluorescence spectroscopy

The development of variable-angle synchronous scanning (v.a.s.s.) in fluorescence spectrometry is reported, based on a computer-aided spectrofluorimeter. The technique permits a linear path to be scanned at any preselected angle through the emission-excitation matrix defined by (I_em, λ_em, λ_ex), by effectively scanning the emission and the excitation monochromators at different speeds under computer control. When applied to pharmaceutical dosage forms, v.a.s.s. gave good selectivity for chlorpromazine in the presence of its principal degradation product, chlorpromazine sulphoxide, and for oxytetracycline in the presence of the additives vitamin C, thiamine, nicotinamide and riboflavin. Good calibration linearity, precision and recovery were observed for both principal drug components. The angle of the scan trajectory can also be varied continuously through the emission-excitation matrix, to describe any desired path under computer control. This novel technique of non-linear v.a.s.s. can provide an improved method for generating diagnostic profiles of drugs, degradation products and metabolites.