Synthesis of novel poly[(2,5-dimethoxy-p-phenylene)vinylene] precursors having two eliminatable groups: An approach for the control of conjugation length

Poly[(2,5-dimethoxy-p-phenylene)vinylene] (DMPPV) of varying conjugation length was synthesized by selective elimination of organic soluble precursor polymers that contained two eliminatable groups, namely, methoxy and acetate groups. These precursor copolymers were in turn synthesized by competitive nucleophilic substitution of the sulfonium polyelectrolyte precursor (generated by the standard Wessling route) using methanol and sodium acetate in acetic acid. The composition of the precursor copolymer, in terms of the relative amounts of methoxy and acetate groups, was controlled by varying the composition of the reaction mixture during nucleophilic substitution. Thermal elimination of these precursor copolymers at 250 degrees C, yielded partially conjugated polymers, whose color varied from light yellow to deep red. FT-IR studies confirmed that, while essentially all the acetate groups were eliminated, the methoxy groups were intact and caused the interruption in conjugation. Preliminary photoluminescence studies of the partially eliminated DMPPV samples showed a gradual shift in the emission maximum from 498 to 598 nm with increasing conjugation lengths, suggesting that the color of LED devices fabricated from such polymers can, in principle, be fine-tuned.

Thermodynamics of ligand (substrate end product) binding to endoxylanase from Chainia sp. (NCL-82-5-1): isothermal calorimetry and fluorescence titration studies

The binding of xylo-oligosaccharides to Chainia endoxylanase resulted in a decrease in fluorescence intensity of the enzyme with the formation of 1:1 complex. Equilibrium and thermodynamic parameters of ligand binding were determined by fluorescence titrations and titration calorimetry. The affinity of xylanase for the oligosaccharides increases in the order X-2 < X-3 < X-4 less than or equal to X-5. Contributions from the enthalpy towards the free energy change decreased with increasing chain length from X-2 to X-4, whereas an increase in entropy was observed, the change in enthalpy and entropy of binding being compensatory. The entropically driven binding process suggested that hydrophobic interactions as well as hydrogen bonds play a predominant role in ligand binding.

Indium clusters on the Ge (5× 5) wetting layer of Si (111)- 7× 7

The adsorption of In on the Si(111)−Ge(5×5) surface reconstruction has been studied with scanning tunneling microscopy and ab initio calculations to investigate the possibility of using this reconstruction as a template for cluster formation. As with In adsorption on Si(111)−7×7 at low substrate temperatures and low In fluences, the In adatoms are found to preferentially adsorb on the faulted half-unit cell. However, in contrast to In adsorption on Si(111)−7×7, the In adatoms are also frequently found in the unfaulted half-unit cell at low coverages. The filling of unfaulted unit cell halves is primarily due to the formation of large clusters that span multiple substrate half-unit cells. Moreover, many of the faulted half-unit cells have a streaked appearance that indicates that surface atoms within them are mobile.

Bridged systems via radical cyclization reactions. Stereospecific synthesis of chiral tricyclo[6.2.1.0(1,5)]undecanes

The application of radical-mediated cyclizations and annulations in organic synthesis has grown in importance steadily over the years to reach the present status where they are now routinely used in the strategy-level planning.2 The presence of a quaternary carbon atom is frequently encountered in terpenoid natural products, and it often creates a synthetic challenge when two or more quaternary carbon atoms are present in a contiguous manner.3 Even though creation of a quaternary carbon atom by employing a tertiary radical is very facile, creation of a quaternary carbon atom (or a spiro carbon atom) via radical addition onto a fully substituted olefinic carbon atom is not that common but of synthetic importance. For example, the primary radical derived from the bromide 1 failed to cyclize to generate the two vicinal quaternary carbon atoms and resulted in only the reduced product 2.4 The tricyclic carbon framework tricyclo[6.2.1.01,5]undecane (3) is present in a number of sesquiterpenoids e.g. zizzanes, prelacinanes, etc.5

A rapid and highly selective method for the estimation of pyro-,tri- and orthophosphates

A rapid, highly selective and simple method has been developed for the quantitative determination of pyro-, tri- and orthophosphates. The method is based on the formation of a solid complex of bis(ethylenediamine)cobalt(III) species with pyrophosphate at pH 4.2-4.3, with triphosphate at pH 2.0-2.1 and with orthophosphate at pH 8.2-8.6. The proposed method for pyro- and triphosphates differs from the available method, which is based on the formation of an adduct with tris(ethylenediamine)cobalt(III) species. The complexes have the composition [Co(en)(2)HP2O7]4H(2)O and [Co(en)(2)H2P3O10]2H(2)O, respectively. The precipitation is instantaneous and quantitative under the recommended optimum conditions giving 99.5% gravimetric yield in both cases. There is no interferences from orthophosphate, trimetaphosphate and pyrophosphate species in the triphosphate estimation up to 5% of each component. The efficacy of the method has been established by determining pyrophosphate and triphosphate contents in various matrices. In the case of orthophosphate, the proposed method differs from the available methods such as ammonium phosphomolybdate, vanadophosphomolybdate and quinoline phosphomolybdate, which are based on the formation of a precipitate, followed by either titrimetry or gravimetry. The precipitation is instantaneous and the method is simple. Under the recommended pH and other reaction conditions, gravimetric yields of 99.6-100% are obtainable. The method is applicable to orthophosphoric acid and a variety of phosphate salts.

Synthesis of 2-(5-((5-(4-chlorophenyl)furan 2-yl)methylene)-4-oxo-2-thioxo-thiazolidi n-3-yl)acetic acid derivatives and evaluation of their cytotoxicity and induction of apoptosis in human leukemia cells

In order to explore the anticancer effect associated with the thiazolidinone framework, several 2-(5-((5-(4-chlorophenyl)furan-2-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl)acetic acid derivatives 5(a-1) were synthesized. Variation in the functional group at C-terminal of the thiazolidinone led to set of compounds bearing amide moiety. Their chemical structures were confirmed by H-1 NMR, IR and Mass Spectra analysis. These thiazolidinone compounds containing furan moiety exhibits moderate to strong antiproliferative activity in a cell cycle stage-dependent and dose dependent manner in two different human leukemia cell lines. The importance of the electron donating groups on thiazolidinone moiety was confirmed by MTT and Trypan blue assays and it was concluded that the 4th position of the substituted aryl ring plays a dominant role for its anticancer property. Among the synthesized compounds, 5e and 5f have shown potent anticancer activity on both the cell lines tested. To rationalize the role of electron donating group in the induction of cytotoxicity we have chosen two molecules (5e and 5k) having different electron donating group at different positions. LDH assay, Flow cytometric analysis and DNA fragmentation suggest that 5e is more cytotoxic and able to induce the apoptosis. (C) 2009 Elsevier Ltd. All rights reserved.

Nutritional rehabilitation in cystic fibrosis: A 5 year follow-up study

Previously, we reported catch-up weight gain, growth, and improved lung function in a group of malnourished cystic fibrosis (CF) children receiving aggressive nutritional supplementation for 1 year compared with a forced expiratory volume in 1 s (FEV1)-, height-, and sex-matched comparison group receiving standard therapy. To evaluate long-term effects, the clinical progress of both groups has been studied over a 5 year period. The supplemented group (n = 10) received supplements for a median of 1.35 years to achieve nutritional rehabilitation. Compared with the nonsupplemented group (n = 14), the previously supplemented group had lower mortality (2 vs. 4, N.S.) and significantly greater weight and height z scores at 4 and 5 years. The progression of pulmonary function abnormalities as measured by FEV, and forced vital capacity (FVC) slopes was greater at 3 years in the nonsupplemented group (FEV1, p < 0.05) but no significant differences in rates of deterioration of pulmonary function were seen after 5 years in the two groups of survivors. We conclude that intensive nutritional support for 1 year has both short-and long-term effects on nutrition and growth, still evident some years after the cessation of this therapeutic modality. Supplementation for periods of longer than 1 year may produce greater gains and possibly prolong the improvement in pulmonary function observed in the earlier study. © 1992 Raven Press, Ltd., New York.

3,3,6,6-Tetramethyl-9-phenyl-3,4,5,6-tetrahydro-9H-xanthene-1,8(2H,7H)-dione

In the title compound, C23H26O3, the three six-membered rings of the xanthene system are non-planar, having total puckering amplitudes, QT, of 0.443 (2), 0.202 (2) and 0.449 (2) Å. The central ring adopts a boat conformation and the outer rings adopt sofa conformations. The crystal structure is stabilized by van der Waals interactions.

2.5-dimensional solution of the advective accretion disk:a self-similar approach

We provide a 2.5-dimensional solution to a complete set of viscous hydrodynamical equations describing accretion- induced outflows and plausible jets around black holes/compact objects. We prescribe a self-consistent advective disk-outflow coupling model, which explicitly includes the information of vertical flux. Inter-connecting dynamics of an inflow-outflow system essentially upholds the conservation laws. We provide a set of analytical family of solutions through a self-similar approach. The flow parameters of the disk-outflow system depend strongly on the viscosity parameter α and the cooling factor.

General practitioner utilisation amongst urban Aboriginal and Torres Strait Islander children aged less than 5 years

Aim There are limited studies documenting the frequency and reason for attendance to primary health care services in Australian children, particularly for urban Aboriginal and Torres Strait Islander children. This study describes health service utilisation in this population in an urban setting. Methods An ongoing prospective cohort study of Aboriginal and Torres Strait Islander children aged <5 years registered with an urban Aboriginal and Torres Strait Islander primary health care centre in Brisbane, Australia. Detailed demographic, clinical, health service utilisation and risk factor data are collected by Aboriginal researchers at enrolment and monthly for a period of 12 months on each child. The incidence of health service utilisation was calculated according to the Poisson distribution. Results Between 14 February 2013 and 31 October 2014, 118 children were recruited, providing data for 535 child-months of observation. Ninety-one percent of children were Aboriginal, 4% Torres Strait Islander and 5% were both Aboriginal and Torres Strait Islander. The incidence of presentations to see a doctor for any reason was 43.9 episodes/100 child months (95%CI 38.4 – 49.9) The most common reasons for presentation were for immunisations (23%), respiratory illnesses (19%) and for Australian Government funded Indigenous child health check (16%). The primary health services used, for majority of these visits were Aboriginal and Torres Strait Islander specific medical services (61%). Conclusions Within a cultural-specific service for an urban Aboriginal and Torres Strait Islander people, there is a high frequency of childhood attendance at for primary health care services. Well-health checks and respiratory illnesses were the most common reasons. The high proportion of visits for well child services suggests a potential for opportunistic health promotion, education and early interventions across a range of child health issues.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Structure of 5'-O-acetyl-2',3'-O-isopropylideneuridine, C14H18N2O7

M r = 326.3, monoclinic, P21, a --= 6.510 (2), b=8.432 (2), c= 15.114 (2),a, /~= 101.42 (3) ° , Z = 2, V= 813.15 A 3, D x = 1-33 Mg m -3, F(000) = 172, 2(Cu Ka) = 1.5418/~,, g(Cu Ka) = 0.906 mm -~, final R = 6.4% for 1924 observed counter reflections. The conformation about the glycosidic bond is syn [torsion angle C(6)-N(1)-C(1')-O(4')=-103.9(3)°]. The sugar pucker is C(2')-exo,C(3')-endo (3Tz). The conformation about the C(4')-C(5') bond is gauche-trans. An uncommon intermolecular hydrogen bond involving the ribose-ring oxygen O(1') and the base-nitrogen N(3) stabilizes the crystal structure.

Studies in terpenoids. Part 42. Synthesis of 3-(2-hydroxyisopropyl)5,8-dimethyl-1,2-naphthoquinone (emmotin-H)

Emmotin-H, a naturally occurring sesquiterpenoid 1,2-naphthoquinone pigment (1) has been synthesised in a four step sequence starting from the known 5,8-dimethyl-4-oxotetralin-2-carboxylic acid (3a). Selenium dioxide oxidation of its methyl ester (3b) gives 3-methoxycarbonyl-5,8-dimethyl-1,2-naphthoquinone (4) which on reductive acetylation affords the corresponding diacetoxynaphthalene ester (5). Its reaction with excess of methylmagnesium iodide is accompanied by aerial oxidation during work-up and furnishes emmotin-H (1).

Studies in metal-ammonia reduction-5: Reduction and reductive methylation of some naphthoic acids

Birch reductio and reductive methylations of some substituted naphtholic acids have been examined. The factors influencing the mechanism of reduction process have been discussed. Some of the reduced naphthoic acids are useful synthons for synthesis.

Dialkyl (3-Aryl- 1,2,4-oxadiazol-5-yl)phosphonates: Synthesis and Thermal Behavior-Evidence for Monomeric Alkyl Metaphosphate

Dialkyl (3-aryl-l,2,4-oxadiazol-5-yl)phosphonate6sa -h have been obtained by 1,3-dipolar cycloaddition of arenenitrile oxides 5a-f to dialkyl phosphorocyanidates (4a and 4b) in yields ranging between 30% and 58%. A standardized method for obtaining cyanidates 4a and 4b has been established. The diethyl thiophosphorocyanidate (4c) is less reactive than 4a and 4b, only the 3-(4'-nitrophenyl) derivative 6i being obtainable. While the IR and NMFt spectra of 6a-i were unexceptional, their UV spectra showed evidence of conjugative interaction in high degrees between the phosphonate and heterocyclic moieties as well as a varying conjugative interaction between the heterocyclic and aryl moieties. The oxadiazoles 6a-h are thermally labile and yield trialkyl phosphates 7 as the only identifiable products. A mechanism based on the intermediacy of monomeric alkyl metaphosphate 11 in the formation of trialkyl phosphate was postulated, and supportive evidence in the form of trapping the metaphosphate with acetophenone has been obtained.