Novel stereoselective control over cis vs trans opening of benzo[c]phenanthrene 3,4-diol 1,2-epoxides by the exocyclic N(2)-amino group of deoxyguanosine in the presence of hexafluoropropan-2-ol

We describe a novel and efficient synthesis (62-84% yields) of the eight possible, diastereomerically pure, cis and trans, R and S O(6)-allyl-protected N(2)-dGuo phosphoramidite building blocks derived through cis and trans opening of (+/-)-3alpha,4beta-dihydroxy-1beta,2beta-epoxy-1,2,3,4-tetrahydrobenzo[c]phenanthrene [BcPh DE-1 (1)] and (+/-)-3alpha,4beta-dihydroxy-1alpha,2alpha-epoxy-1,2,3,4-tetrahydrobenzo[c]phenanthrene [BcPh DE-2 (2)] by hexafluoropropan-2-ol (HFP)-mediated addition of O(6)-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine (3) at C-1 of the epoxides. Simply changing the relative amount of HFP used in the reaction mixture can achieve a wide ratio of cis/trans addition products. Thus, the observed cis/trans adduct ratio for the reaction of DE-1 (1) in the presence of 5 equiv of 3 varied from 17/83 to 91/9 over the range of 5-532 equiv of HFP. The corresponding ratios for DE-2 (2) varied from 2/98 to 61/39 under the same set of conditions. When 1 or 2 was fused with a 20-fold excess of 3 at 140 degrees C in the absence of solvent HFP, almost exclusive trans addition (>95%) was observed for the both DEs. Through the use of varying amounts of HFP in the reaction mixture as described above, each of the eight possible phosphoramidite oligonucleotide building blocks (DE-1/DE-2, cis/trans, R/S) of the BcPh DE N(2)-dGuo adducts can be prepared in an efficient fashion. To rationalize the varying cis-to-trans ratio, we propose that the addition of 3 to 1 or 2 in the absence of solvent or in the presence of small amounts of HFP proceeds primarily via an S(N)2 mechanism to produce mainly trans-opened adducts. In contrast, increasing amounts of HFP promote increased participation of an S(N)1 mechanism involving a relatively stable carbocation with two possible conformations. One of these conformations reacts with 3 to give mostly trans adduct, while the other conformation reacts with 3 to give mostly cis adduct.     

A simple molecular model for N-SmAd-NdRe-N1Re-SmA1 phase sequence in highly polar compounds

Our earlier model of re-entrant liquid crystalline phases exhibited by highly polar compounds, in which the mutual orientation of near-neighbour molecules can change from an antiparallel to a parallel configuration, has been extended to include both nematic and smectic interactions. We show that, as the McMillan parameter alpha is decreased, the SmA_d-SmA₁ line goes over to the SmA_d-N_1Re line, finally becoming the N_dRe-N_1Re transition line, the latter ending in a critical point. This sequence is in agreement with the predictions of Prost's Landau model as well as with an experimental result. The phase sequence N-SmA_d-N_dRe-N_1Re-SmA₁ is obtained on cooling for a range of alpha_A values.     

Ecofriendly synthesis and biological evaluation of 4-(4-nitro-phenyl)-2-phenyl-1,4-dihydro-benzo[4,5]imidazo[1,2-a]pyrimidine-3-carboxylic acid ethyl ester derivatives as an antitubercular agents

An ecofriendly route has been investigated for the synthesis of 4-(4-nitro-phenyl)-2-phenyl-1,4-dihydro-benzo[4,5]imidazo[1,2-a]pyrimidine-3-carboxylic acid ethyl ester derivatives by one-pot, three-component condensation of ethyl benzoylacetate, aromatic aldehydes, and 2-amino benzimidazole using 260?mol% of citric acid as reaction mediator. Citric acid is an inexpensive, nontoxic, and green medium with smoothly activates the rate of reaction. The synthesized compounds were assessed for in vitro antimycobacterial activity against Mycobacterium tuberculosis H₃₇RV strain using the microplate alamar blue assay (MABA). The results indicate that among all the synthesized compound series, P-4 and P-9 compounds illustrate effective activity with a minimum inhibitory concentration of 25?µg/ml.     

Use of chromatographic pre-concentration for routine uranium bioassay analysis by ICP-MS

Routine monitoring of urine is an effective way to detect occupational intake of radioactive material. Historically, determinations of uranium isotopic ratios have been performed by radiochemical separation followed by alpha spectrometry. With recent advancements in technology, inductively coupled plasma-mass spectrometry (ICP-MS) has become widely available for the determination of trace metals as well as radioactive nuclides with long half-lives, such as ²³⁸U in urine. Furthermore, ICP-MS measurements of ²³⁸U do not require radiochemical separation since the number of atoms in the sample is determined instead of the number of alpha particles emitted. However, this method does not provide good sensitivity for the determination of ²³⁵U due to its shorter half-life. An improved procedure using pre-concentration of uranium and determination by ICP-MS decreases the detection limit by a factor of ten or greater with only slight increase in total analysis time. The method also has the capability of accurately determining the isotopic ratio of the sample, which is very important in cases where enriched or depleted uranium is involved.     

EPR and optical absorption study of Cr doped diammonium hexaaqua magnesium sulphate single crystal

EPR measurements of Cr³⁺ doped diammonium hexaaqua magnesium sulphate single crystals are made at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular orientations. The value of g=1.9763±0.0002 and are evaluated. On the basis of EPR data the site symmetry of Cr³⁺ in the crystal is discussed. Optical absorption studies of single crystals are also carried out at room temperature. The orbital energies of the chromium ion are estimated from the optical absorption spectrum. The different bonding parameters are obtained by correlating optical and EPR data and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are obtained as B=676,C=3371, , h=1.258 and k=0.21.     

Total Stereospecific Synthesis of (3E,7Z)-Tetradecadienyl Acetate,the Major Sex Pheromone Component of the Potato Pest Symmetrischema tangolias

Chemistry of Natural Compounds - (3E,7Z)-Tetradecadienyl acetate, the major sex pheromone component of the potato pest Symmetrischema tangolias (Gyen), was stereoselectively synthesized from the...     

Alternate method of source preparation for alpha spectrometry: no electrodeposition,no hydrofluoric acid

Journal of Radioanalytical and Nuclear Chemistry - An alternate method of preparing actinide alpha counting sources was developed in place of electrodeposition or lanthanide fluoride...     

A characterization of the logistic distribution by a sample median

Summary A functional form of the characteristic function of the sample median of three variates is shown to characterize the logistic distribution. A consequence of this is a characterization of the logistic in terms of the Laplace distribution. Research sponsored in part by the Air Force Office of Scientific Research, Air Force Systems Command, USAF under Grant No. AFOSR-77-3360. The United States Govenment is authorized to reproduce and distribute reprints for governmental purposes notwith-standing any copyright notation hereon.     

Fluorescence Quenching Studies of the Interaction Between Riboflavin and Norfloxacin and Analytical Application in the Determination of Vitamin B<Subscript>2</Subscript>

The binding of riboflavin (RBF) to norfloxacin (NF) was investigated by spectroscopic techniques. The results revealed that RBF caused the fluorescence quenching of NF by complex formation. The binding parameters and corresponding thermodynamic parameters ΔH, ΔG and ΔS at different temperatures were calculated. The negative enthalpy (ΔH) and positive entropy (ΔS) values indicated that both hydrogen bond and hydrophobic forces played major roles in the binding of RBF to NF. The distance r between donor (NF) and acceptor (RBF) was obtained according to the Forster’s theory of non-radiative energy transfer. The method of quenching was successfully applied for the determination of riboflavin from pharmaceutical samples.     

Power spectra and spatial pattern dynamics of a ring laser

Experimental measurements of power spectra of a single longitudinal and transverse mode ring dye laser are presented that reveal the critical slowing down of the laser near threshold. External pump noise serves as a probe of the frequency response of the dye laser. Detailed comparisons of the spectral characteristics with computer simulations and an approximate analytic theory are given. The dynamics of spatial pattern formation in a multimode dye laser is examined through measurements of first-passage-time distributions. A comparison of the experiments with computer simulations based on a simple theoretical model of the two-mode laser shows qualitative agreement. These measurements indicate that there are a variety of complex phenomena associated with the transverse mode pattern formation dynamics that need to be addressed theoretically and studied further experimentally.