Alkaloid-fullerene systems through photocycloaddition reactions

The photocycloaddition of tertiary amines to ?60fullerene (C(60)) is an interesting and useful reaction. We wished to extend the applications of this type of reaction through an investigation of the photoaddition of alkaloids to C(60) for the purpose of synthesizing novel and complex photoadducts that are difficult to obtain by usual methods. Irradiation of tazettine (2) or gramine (3) with C(60) in toluene leads to formation of one monoadduct (6 or 7), whereas scandine (1a) or 10-hydroxyscandine (1b) reacts with C(60) photochemically to give two products, the expected ?6,6 monoadduct (5a, 5b) and a new type of monoadduct with a bis-?6, 6 closed structure (4a, 4b). These new structures were characterized by UV-vis, FT-IR, (1)H NMR, (13)C NMR, (1)H-(1)H COSY, ROESY, HMQC (heteronuclear multiple-quantum coherence), and HMBC (heteronuclear multiple-bond connectivity) spectroscopy. The techniques of time-of-flight secondary ion MS (TOF-SIMS) and field desorption MS (FD-MS) were used for the mass determination. (3)He NMR analysis of the product mixture from photoaddition of 1a to C(60) containing a (3)He atom ((3)He@C(60)) led to two peaks at -9.091 and -11.090 ppm relative to gaseous (3)He, consistent with formation of a ?6, 6-closed monoadduct and a bis-?6,6 closed adduct. Presumably, the bis-?6, 6 closed adducts are formed by an intramolecular ?2 + 2 cycloaddition of the vinyl group to the adjacent 6,6-ring junction of C(60) after the initial photocycloaddition.     

Synthesis of Highly Fluorinated Chloroformates and Their Use as Derivatizing Agents for Hydrophilic Compounds and Drinking‐Water‐Disinfection By‐Products

A rapid, safe, and efficient procedure was developed to synthesize, on a small scale, fluorinated chloroformates often required to perform analytical derivatizations. This new family of agents allows straightforward derivatization of highly polar compounds (with multiple hydroxy, carboxy, and amino substituents) in the aqueous phase, compatible with GC and GC/MS analysis. A goal of this work was to develop a derivatization procedure that would enable the detection and identification of highly polar disinfection by‐products in drinking water.     

Developmental Responses of Amphibians to Solar and Artificial UVB Sources: A Comparative Study

Abstract— Many amphibian species, in widely scattered locations, currently show population declines and/or reductions in range, but other amphibian species show no such declines. There is no known single cause for these declines. Differential sensitivity to UVB radiation among species might be one contributing factor. We have focused on amphibian eggs, potentially the most UVB-sensitive stage, and compared their resistance to UVB components of sunlight with their levels of photolyase, typically the most important enzyme for repair of the major UV photoproducts in DNA, cyclobutane pyrimidine dimers. Photolyase varied 100-fold among eggs/oocytes of 10 species. Among three species–Hyla regilla, Rana cascadae, and Bufo boreas–for which resistance of eggs to solar UVB irradiance in their natural locations was measured, hatching success correlated strongly with photolyase. Two additional species, Rana aurora and Ambystoma gracile, now show similar correlations. Among the low-egg-photolyase species, R. cascadae and B. boreas are showing declines, and the status of A. gracile is not known. Of the two high-photolyase species, populations of H. regilla remain robust, but populations of R. aurora are showing declines. To determine whether levels of photolyase or other repair activities are affected by solar exposures during amphibian development, we have initiated an extended study of H. regilla and R. cascadae, and of Xenopus laevis, laboratory-reared specimens of which previously showed very low photolyase levels. Hyla regilla and R. cascadae tadpoles are being reared to maturity in laboratories supplemented with modest levels of UV light or light filtered to remove UVB wavelengths. Young X. laevis females are being reared indoors and outdoors. Initial observations reveal severe effects of both UVA and UVB light on H. regilla and R. cascadae tadpoles and metamorphs, including developmental abnormalities and high mortalities. Assays of photolyase levels in the skins of young animals roughly parallel previous egg/oocyte photolyase measurements for all three species.     

The influence of vibronic interactions on the chiroptical spectra of dissymmetric pseudo tetragonal metal complexes

The influence of vibronic interactions on the chiroptical spectra associated with a threesome of nearly degenerate electronic excited states in a dissymmetric molecular system is examined on a formal theoretical model. The model considers two vibrational modes to be effective in promoting pseudo Jahn-Teller (PJT) type interactions between the three closely spaced electronic excited states. Formal expressions are developed for the rotatory strengths of individual vibronic levels derived from the coupled electronic states. Two mode (vibrational)-three state (electronic) vibronic Hamiltonians are constructed (basis set size, 63–108, depending upon interaction parameters used) and diagonalized for a large number of different parameter sets representative of various vibronic coupling strengths, electronic energy level spacings, oscillator (vibrational mode) frequencies, and electronic rotatory strengths. Diagonalization of these vibronic Hamiltonians yields vibronic wave functions and energies which are then used to calculate rotatory strength spectra for the model system. The calculated results demonstrate the profound influence which vibronic interactions of the PJT type may have on the sign patterns and intensity distributions within the rotatory strength spectrum associated with a set of nearly degenerate electronic states. The implication of these results for the interpretation of circular dichroism spectra of chiral transition metal complexes with pseudo tetragonal symmetry are discussed.     

Measurement ofD meson production in 200 GeV π−-Be interactions

We have measured the differential and total cross sections ofD meson production in 200 GeV π^?-beryllium interactions, using a sample of 48 fully reconstructed and nearly background-freeD mesons in the decay channelsK ^?π^±,K ^?π^±π^± andK ^?π^?π^±π^±. A single electron trigger has been used to select events containing a pair of charmed particles. A vertex telescope of 6 silison microstrip detectors allowed the reconstruction of tracks of charged secondaries and the reconstruction of primary and decay vertices with high precision. The ratio of branching fractions for \(\mathop {D^0 }\limits^{( - )} \to K^ \mp \pi ^ \pm \) to \(\mathop {D^0 }\limits^{( - )} \to K^ \mp \pi ^ \mp \pi ^ \pm \pi ^ \pm \) , and an upper limit for \(D^0 - \bar D^0 \) mixing are presented.     

Aging and degradation of polyolefins. IV. Thermal and photodecompositions of model peroxides

There appear to be no unusual effects of phase change or near-ultraviolet radiation on the reactions of alkoxy radical models for atactic polypropylene. The oxidation of purified atactic polypropylene by singlet oxygen is not an important process at 50°. Photochemical and thermal cleavages of tert-amyloxy radicals, a model for polypropylene oxy radicals, give nearly the same ratio of k_a/k_d at 50°C. Photochemical cleavage of the model compound 1,1-dinonylethyl hydroperoxide (10-methyl-10-nonadecyl hydropenoxide) gives exclusive cleavage of a nonyl group both in solution and in polypropylene film at 50°C.     

The effect of biotin on the production of succinic acid byAnaerobiospirillum succiniciproducens

Applied Biochemistry and Biotechnology - The effect of biotin at 50 mg/L on the production of succinic acid byA. succiniciproducens has been studied. Biotin improved glucose consumption, cell...     

Synthesis of 5-Oxo and 7-Oxopyrido[2,3-d]pyrimidines

The synthesis of 4-amino-2-methylthio-5-oxopyrido[2,3-d]pyrimidine 4 and its isomer, 4-amino-2-methyl-thio-7-oxopyrido[2,3-d]pyrimidine 6 is described. The regiochemistry of the reaction of 4,6-diamino-2-methyl-thiopyrimidine 9 and diethyl ethoxymethylene malonate 12 is discussed.