Direct spectrophotometric determination of ruthenium in aqueous streams of nuclear reprocessing

A fiber optic aided spectrophotometric technique has been developed for determination of ruthenium in nitric acid medium. The developed method is simple, accurate and applicable to aqueous streams of nuclear reprocessing. The system obeys Lambert–Beer’s law at 468 nm in the concentration range of 30–360 μg/mL of ruthenium. The molar absorption coefficient, detection limit and Sandell’s sensitivity are 68.477 L Mol^?1 cm^?1, 31 μg/mL and 0.0124 μg/cm² respectively. Relative standard deviation was less than 2 % and correlation coefficient was 0.9998. The results obtained by the developed procedure are in good agreement with those obtained by the standard ICP-OES method. Fission products like zirconium and strontium are not interfering. Uranium is interfering and needs prior separation by solvent extraction method. The developed method is adaptable for remote operation and on-line monitoring.     

Stereoselective Total Synthesis of Rugulactone

The stereoselective synthesis of the naturally occurring dihydropyranone rugulactone has been accomplished starting from 3‐phenylpropan‐1‐ol employing Maruoka allylation and ring‐closing metathesis as the key steps.     

Ionic liquid-controlled J- versus H-aggregation of cyanine dyes

Cyanine dyes are triggered to form fluorescent H-aggregates in IL [C(n)mim][BF(4)], whereas J-aggregates are observed to form in ILs with other anions as 2 wt% 1 M aqueous NaOH is added at room temperature; difference in hydrolytic properties of [BF(4)](-) ILs over other ILs is hypothesized to be the reason.     

Assembly of a dinuclear silver complex containing an Ag2S2 motif from a phosphorus-supported trishydrazone ligand. P=S→Ag(I) coordination

The reaction of the phosphorus trihydrazide, (S)P[N(Me)-NH(2)](3) (1) with quinoline-2-carboxaldehyde (C(9)H(6)N-2-CHO) in a 1:3 ratio afforded a trishydrazone, (S)P[N(Me)-N=CH-2-C(9)H(6)N](3) (2). Crystals of 2 were grown in three different solvent media affording an unsolvated (2, monoclinic, P2(1)/n) and two solvated (2·3H(2)O, trigonal, R3 and 2·2CH(3)OH, triclinic, P ?1) crystal forms. Each of these, while possessing an essentially similar molecular structure, adopt different crystal packing giving rise to supramolecular structures mediated by a variety of weak interactions: O-H-N, O-H-O, C-H-N, C-H-O, C-H-S, C-H-π, π-π, N-π and S-π. The reaction of 2 with Ag(ClO(4))(2)·6H(2)O in methanol afforded a dinuclear cationic cage [Ag{(S)P[N(Me)-N=CH-2-C(9)H(6)N](3)}·ClO(4)](2) (3). The molecular structure of 3 reveals a dimeric structure consisting of two Ag(I) ions that are held together by two ligands. Only two arms of the tris hydrazone ligand are involved in coordination while an unprecedented P=S→Ag(I) coordination is seen. This results in the formation of an Ag(2)S(2) dimer that is encapsulated by two trishydrazone ligands. Both compounds 2 and 3 are photoluminescent.     

Improvement of Regio-Specific Production of Myricetin-3-O-α-l-Rhamnoside in Engineered Escherichia coli

Myricetin is an important flavonol whose medically important properties include activities as an antioxidant, anticarcinogen, and antimutagen. The solubility, stability, and other biological properties of the compounds can be enhanced by conjugating aglycon with sugar moieties. The type of sugar moiety also plays a significant role in the biological and physical properties of the natural product glycosides. Reconstructed Escherichia coli containing thymidine diphosphate-α-l-rhamnose sugar gene cassette and Arabidopsis-derived glycosyltransferase were used for rhamnosylation of myricetin. Myricetin (100 μM) was exogenously supplemented to induced cultures of engineered E. coli. The formation of target product—myricetin-3-O-α-l-rhamnoside—was confirmed by chromatographic and NMR analyses. The yield of product was improved by using various mutants and methylated cyclodextrin as a molecular carrier for myricetin in combination with E. coli M3G3. The maximal yield of product is 55.6 μM (3.31-fold higher than the control E. coli MG3) and shows 55.6 % bioconversion of substrate under optimized conditions.     

Cyclizations of Some Terminally Substituted a,c-Biladienes

Several examples of 1′,8′-disubstituted a,c-biladiene salt cyclizations, using copper(II) or iodine/bromine in hot o-dichlorobenzene, to give meso-substituted porphyrins are described.     

An Efficient Synthesis of Coumestans-A Probable Biogenetic Approach

A probable biogenetic type synthesis of coumestans by coupling in-situ generated o-quinones by mushroom tyrosinase oxidation of catechol and 4-hydroxy coumarins is reported.     

PhSeSiR(3)-Catalyzed Group Transfer Radical Reactions

A novel design for initiating radical-based chemistry in a catalytic fashion is described. The design of the concept is based on the phenylselenyl group transfer reaction from alkyl phenyl selenides by utilizing PhSeSiR(3) (1) as a catalytic reagent. The reaction is initiated by the homolytic cleavage of -C-Se- bond of an alkyl phenyl selenide by the in situ generated alkylsilyl radical (R(3)Si(*)), obtained by the mesolysis of PhSeSiR(3)](*)(-)( )()(1(*)(-)). The oxidative dimerization of counteranion PhSe(-) to PhSeSePh functions as radical terminator. The generation of 1(*)(-) is achieved by the photoinduced electron transfer (PET) promoted reductive activation of 1 through a photosystem comprising of a visible-light (410 nm)-absorbing electron rich DMA as an electron donor and ascorbic acid as a co-oxidant (Figure 1). The optimum mole ratio between the catalyst 1 and alkyl phenyl selenides for successful reaction is established to be 1:10. The generality of the concept is demonstrated by carrying out variety of radical reactions such as cyclization (10, 15-18), intermolecular addition (25), and tandem annulations (32).     

Pharmacokinetics of ICG and HPPH-car for the detection of normal and tumor tissue using fluorescence, near-infrared reflectance imaging: a case study

We present in vivo fluorescent, near-infrared (NIR), reflectance images of indocyanine green (ICG) and carotene-conjugated 2-devinyl-2-(1-hexyloxyethyl) pyropheophorbide (HPPH-car) to discriminate spontaneous canine adenocarcinoma from normal mammary tissue. Following intravenous administration of 1.0 mg kg-1 ICG or 0.3 mg kg-1 HPPH-car into the canine, a 25 mW, 778 nm or 70 mW, 660 nm laser diode beam, expanded by a diverging lens to approximately 4 cm in diameter, illuminated the surface of the mammary tissue. Successfully propagating to the tissue surface, ICG or HPPH-car fluorescence generated from within the tissue was collected by an image-intensified, charge-coupled device camera fitted with an 830 or 710 nm bandpass interference filter. Upon collecting time-dependent fluorescence images at the tissue surface overlying both normal and diseased tissue volumes, and fitting these images to a pharmacokinetic model describing the uptake (wash-in) and release (wash-out) of fluorescent dye, the pharmacokinetics of fluorescent dye was spatially determined. Mapping the fluorescence intensity owing to ICG indicates that the dye acts as a blood pool or blood persistent agent, for the model parameters show no difference in the ICG uptake rates between normal and diseased tissue regions. The wash-out of ICG was delayed for up to 72 h after intravenous injection in tissue volumes associated with disease, because ICG fluorescence was still detected in the diseased tissue 72 h after injection. In contrast, HPPH-car pharmacokinetics illustrated active uptake into diseased tissues, perhaps owing to the overexpression of LDL receptors associated with the malignant cells. HPPH-car fluorescence was not discernable after 24 h. This work illustrates the ability to monitor the pharmacokinetic delivery of NIR fluorescent dyes within tissue volumes as great as 0.5-1 cm from the tissue surface in order to differentiate normal from diseased tissue volumes on the basis of parameters obtained from the pharmacokinetic models.     

Synthesis,spectroscopic and thermal studies on ruthenium(III), rhodium(III) and iridium(III) complexes with hydrazones derived from 2,6-diacetylpyridine and different aromatic hydrazides

Summary The reactions of MCl₃·3H₂O (M=Ru, Rh or Ir) with hydrazones have been studied by three different methods and complexes of the types [M(LH₂)(H₂O)₂]Cl₃, [M(L)Cl(H₂O)] and [M(LH₂)Cl₂]Cl·H₂O have been isolated. Tentative structural conclusions are drawn for these products based upon elemental analysis, electrical conductance, magnetic moment, and i.r. and¹H n.m.r. data. The thermal stability and mode of decomposition for the complexes have been studied by t.g.a., d.t.g. and d.s.c. techniques.