Thermal decomposition of transition metal carboxylates

Dynamics of changes in microstresses during thermal decomposition of Cu(HCOO)₂ crystals and their effect on the thermal decomposition kinetics were studied by IR spectroscopy at 105 to 120 °C. The formation of solid intermediate HCOOCu was observed, and the dynamics of its accumulation was followed. Kinetic regularities of transformation of HCOO groups were compared with those for gas evolution.For Communication 1, see Ref. 1.Translated from Izvestiya va Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–354, February, 1996.     

Pattern formation in diffusion-limited reactions

The conditions for macroscopic segregation ofA andB in a steady-stateA+B 0 reaction are studied in infinite systems. Segregation occurs in one and two dimensions and is marginal ford=3. We note the dependence of these results on the precise experimental conditions assumed in the theory. We also note the difference between these results and our earlier ones for finite systems where the critical dimension isd=2.     

Rate processes on fractals: Theory,simulations, and experiments

Heterogeneous kinetics are shown to differ drastically from homogeneous kinetics. For the elementary reaction A + A products we show that the diffusion-limited reaction rate is proportional tot ^– h[A]² or to [A]^x, whereh=1- d _s/2, X=1+2/d _s =(h-2)(h-1), andd _s is the effective spectral dimension. We note that ford = d _s =1, h =1/2 andX = 3, for percolating clustersd _s = 4/3,h = 1/3 andX = 5/2, while for dust ds <1, 1 >h > 1/2 and >X > 3. Scaling arguments, supercomputer simulations and experiments give a consistent picture. The interplay of energetic and geometric heterogeneity results in fractal-like kinetics and is relevant to excitation fusion experiments in porous membranes, films, and polymeric glasses. However, in isotopic mixed crystals, the geometric fractal nature (percolation clusters) dominates.     

Poly(decyl methacrylate)-based fluorescent PEBBLE swarm nanosensors for measuring dissolved oxygen in biosamples

150-250 nm Poly(decyl methacrylate)(PDMA) fluorescent ratiometric nanosensors for dissolved oxygen have been developed. Platinum octaethylporphine ketone (PtOEPK), the oxygen-sensitive dye, and octaethylporphyrin (OEP), the oxygen-insensitive dye, have been incorporated into PDMA nanoparticles to make the sensors ratiometric. Based on the corresponding Stern-Volmer plot, these nanosensors exhibit almost complete linearity over the whole range of dissolved molecular oxygen from 0 to 42.5 ppm (deoxygenated to pure oxygen-bubbled water). The overall quenching response is up to 97.5%, the best so far for all dissolved oxygen optical sensors. These PEBBLE nanosensors also show very good reversibility and stability to leaching and photobleaching, as well as very short response times and no perturbation by proteins. In human plasma they demonstrate a robust oxygen sensing capability, little affected by light scattering and autofluorescence. Potential applications include intracellular oxygen imaging and microresolved pressure profiles in biological and other heterogenous environments.     

Heparan sulfate, heparin, and heparinase activity detection on polyacrylamide gel electrophoresis using the fluorochrome tris(2,2'-bipyridine) ruthenium (II)

The paper shows the ability of the fluorochrome tris(2,2'-bipyridine) ruthenium (II) (Rubipy) to detect heparan sulfate, heparin, and heparinase activity of M3 murine mammary adenocarcinoma cells as well as bacterial heparinases I, II, and III in native polyacrylamide gel electrophoresis (PAGE). The technique is based on the electrophoretic mobility of high molecular weight heparins and subsequent staining with Rubipy (50 micrograms/mL). The minimum content of heparin detected by fluorescence in a UV transilluminator was 25-50 ng. The number of Rubipy molecules bound to heparin, determined in relationship to the number of disaccharide units (DU), showed that two to six heparin disaccharide units are bound by each fluorochrome molecule. Scatchard plot analysis showed one Rubipy-binding site (Kd = (8.56 +/- 2.97) x 10(-5) M). Heparinase activity was determined by densitometric analysis of the fluorescence intensity of the heparin-containing band of the gel. While heparinase I (EC 4.2.2.7.) degraded heparin and, to a lower degree, partially N-desulfated N-acetylated heparin (N-des N-Ac), heparinase II (no EC number) could efficiently degrade heparan sulfate (HS) and partially N-des N-Ac heparin. Finally, heparinase III (EC 4.2.2.8.) degraded HS almost exclusively. Only heparin and N-des N-Ac heparin were substrates for M3 tumor cell heparinases. We describe a qualitative, sensitive and simple method to detect heparinase activity and determine its substrate specificity using Rubipy fluorescence with heparin and heparan sulfate in multiple biological samples tested in parallel.     

Redox troponization as a novel method for the synthesis of stereoisomeric Eschenmoser's oximes and related non-benzenoid aromatic systems

A novel method for the synthesis of the oxime of 4-methyl-2,4,6-cycloheptatrien-1-one (Eschenmoser's oxime) is proposed. The method involves redox enlargement of the ring of 4-dibromomethyl-4-methyl-2,5-cyclohexadien-1-one oxime through the action of Ni(PPh₃)₄ in DMF (in the presence of Zn). The product is formed as a mixture ofsyn- andanti-forms readily interconverting in solutions. A similar reaction of 4-methyl-4-trichloromethyl-2,5-cyclohexadien-1-one oxime afforded the dimer of agem--centered semiquinoid carbene (1,2-bis-(1-methyl-4-oxyimino-2,5-cyclohexadienyl)-1,2-dichloroethylene), together withsyn- andanti-isomers of 4-chloro-5-methyl-2,4,6-cycloheptatrien-1-one oxime, which are readily separable but also quickly interconverting in solutions. For the latter compounds, the complete¹H NMR assignment of the stereoisomeric structures has been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 519–523, March, 1995.The authors are grateful to the International Science Foundation (Grant MHW000) as well as the Russian Foundation for Basic Research (Project No. 94-03-08873) for the financial support of the work.     

A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes

The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.