New and highly efficient synthesis of cis- and trans-opened Benzo[a]pyrene 7,8-diol 9,10-epoxide adducts at the exocyclic N(2)-amino group of deoxyguanosine

We describe a new and facile method for the synthesis of both cis- and trans-opened N(2)-deoxyguanosine (dG) adducts of (+/-)-7alpha, 8beta-dihydoxy-9beta,10beta-epoxy-7,8,9,10-tetra hydrobenzo[a]pyrene and (+/-)-7alpha,8beta-dihydoxy-9alpha,10alpha -epoxy-7,8,9, 10-tetrahydrobenzo[a]pyrene at C-10. The key step in our approach is the direct coupling of O(6)-allyl-3', 5'-di-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine with these epoxides followed by the separation of the mixtures of cis- and trans-diastereomers produced. Overall coupling yields ranged from 45 to 65%. Stereochemistry of addition of the N(2)-exocyclic amino group of dG (cis-trans, approximately 1:1) was assigned by NMR, and the absolute configuration of the dG adducts was unequivocally assigned by CD spectroscopy after separation of each individual diastereomer and cleavage of the allyl protecting group. A strong CD band at 279 nm in the O(6)-protected adduct was found to be diagnostic for configuration at C-10, with a negative band correlating with 10R configuration. The synthetic methodology described allows easy access to cis- and trans-opened N(2)-dG adducts which are valuable building blocks for the synthesis of adduct-containing oligonucleotides for physical and biochemical studies.     

Magnetic behavior and Mossbauer spectra of spin-crossover pyrazolate bridged dinuclear diiron(II) complexes: X-ray structures of high-spin and low-spin [(Fe(NCBH3)(py))2(mu-bpypz)2

The synthesis and characterization of new spin-crossover pyrazolato bridged dinuclear [(FeII(NCS)(py))2(mu-bpypz)2] and the corresponding cyanotrihydroborato-kappaN complexes are described together with the X-ray crystal analysis of the latter in both the high-spin and low-spin states as well as the variable temperature magnetic susceptibility and/or Mossbauer spectra demonstrating the spin-crossover which exhibits an one-step process, but not a two-step one characteristic of the known bpym bridged dinuclear complexes.     

Determination of nanogram amounts of cadmium in water by electrothermal atomic absorption spectrometry after flotation separation

A method is described for the flotation an determination of ng-levels of cadmium in water. Cadmium in a 1-l sample of water is coprecipitated with hydrated zirconium oxide at pH 9.1 ± 0.1. The precipitate is floated with the aid of a surfactant solution and small air bubbles, separated and dissolved in dilute hydrochloric acid. The cadmium content is determined by electrothermal atomic absorption spectrophotometry. The method is applied to the determination of ng l^?1 levels of cadmium in fresh water. The time required for preconcentration of cadmium from a 1-l sample is 20 min per sample, after 20 min stirring.     

A new internal standard method for activation analysis and its application. Determination of Co,Ni, Rb,Sr in pepperbush by means of photon activation

A new internal standard method for activation analysis has been developed. This method is characterized by that a suitable element present originally in the sample is used as an internal standard and the comparative standard is prepared by applying the standard addition method to the duplicated sample. When a sample under examination contains W_ag of trace element A to be determined together with a known amount of element B which is usable as an internal standard, and when the comparative standard is prepared by adding W _a ^* g of accurately known small amount of the element A to the duplicated sample, even if the sample and comparative standard are irradiated separately by particles with different fluxes, W_a can be determined, easily by using the following equation: W_a=W _a ^* /[(A _R ^* /A_R)-1] Where A_R and A _R ^* are counting ratios of gamma-rays emitted by two radioactive nuclides produced from the element A and B in the sample and comparative standard, respectively. Neither correction of the inhomogeneities of flux between the sample and comparative standard, nor that of, the self-shielding effects are necessary for the present method. The usefulness of the method was examined through the determination of Co, Ni, Rb and Sr in pepperbush by means of photon activation, and the precision and accuracy of the method were proved to be valid.     

A new internal conversion electron spectrometer and its application to determine the240Pu to239Pu isotope ratio

An internal conversion electron spectrometer with high energy resolution has been constructed by using a windowless Si(Li) detector. After its characteristics were examined fundamentally, it was applied to determine the²⁴⁰Pu to²³⁹Pu isotope ratio. As a result, the energy resolution realized was demonstrated to be satisfactory.     

Determination of isotopic ratios of plutonium and curium by internal conversion electron spectrometry

The isotopic ratios²⁴⁰Pu/²³⁹Pu in plutonium samples purified freshly and allowed to stand for a long time were determined by using a high resolution internal conversion electron spectrometer. As a result, it was proved that the above ratios can be determined accurately and precisely. The method was also examined further through a similar determination with curium samples.     

Chemiluminescence of NS radical produced by the reaction of active nitrogen with sulfur vapor and sulfur chloride

Kinetics of NS (B² Π → X²Π) emission produced by the reaction of active nitrogen with sulfur vapor or sulfur chloride (S₂Cl₂) has been studied as a function of the total pressure and of the concentrations of atomic nitrogen and sulfur. The B ²Π state of NS is selectively formed by the three-body recombination reaction of N ans S atoms, N(⁴S) + S(³P) + M →. NS(B ²Π) + M. The highest vibrational level of the B ²Π state observed is ν′ = 12, which gives a lower bound for the dissociation energy of 4.93 eV.     

4-Nitro-9,10-di­hydro­phenanthrene and a polymorphic form of 4-nitro­phenanthrene

The crystal structures of 4-nitro-9,10-di­hydro­phenanthrene, C₁₄H₁₁NO₂, (I), and 4-nitro­phenanthrene, C₁₄H₉NO₂, (II), the latter having two crystallographically independent mol­ecules, show that the mol­ecules are not planar. The dihedral angles between the phenyl rings of the bi­phenyl skeletons are 28.64 (8)° for (I), and 10.34 (15) and 11.75 (13)° for the two mol­ecules of (II). The differences in the dihedral angles have an effect on the photochemical reactivity of the mol­ecules.     

Conical support for double-stage diamond anvil apparatus

ABSTRACT

Both micro-paired and conical support type double-stage diamond anvil cells (ds-DAC) were tested using a newly synthesized ultra-fine nano-polycrystalline diamond (NPD). Well-focused X-ray sub-micron beam and the conically supported 2nd stage anvils (micro-anvils) with 10?μm culet enable us to obtain good quality X-ray diffraction peaks from the sample at around 400?GPa. The relationship between confining pressure and sample pressure depends heavily on the initial height (thickness) of micro-anvils, the difference of a few micrometers leads to a quite different compression path. The conical support type is a solution to retain both enough thickness and strength of micro-anvils at higher confining pressure conditions. All conical support ds-DAC experiments terminated by the failure of the 1st stage anvil instead of 2nd one. The combination of ultra-fine NPD 2nd stage anvil and NPD 1st stage anvil opens a new frontier for measurement of the X-ray absorption spectrum above 300?GPa.