Particle systems on flows

We start with a stochastic flow of diffeomorphisms of the space. Particles enter the space at random times and places. Each particle is carried by the flow for some random amount of time. We examine the point process formed by the particles at a fixed time, on the evolution of that point process as time varies, and on the equilibrium law of the point process.     

Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase

Stimuli‐responsive poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes were synthesized by (1) the radical copolymerization of N‐isopropylacrylamide and maleic anhydride with α,α′‐azobisisobutyronitrile as an initiator in 1,4‐dioxane at 65 °C under a nitrogen atmosphere, (2) the polyesterification (grafting) of prepared poly(N‐isopropylacrylamide‐co‐maleic anhydride) containing less than 20 mol % anhydride units with α‐hydroxy‐ω‐methoxy‐poly(ethylene oxide)s having different number‐average molecular weights (M_n = 4000, 10,000, or 20,000), and (3) the incorporation of macrobranched copolymers with poly(ethylene imine) (M_n = 60,000). The composition and structure of the synthesized copolymer systems were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy, and chemical and elemental analyses. The important properties of the copolymer systems (e.g., the viscosity, thermal and pH sensitivities, and lower critical solution temperature behavior) changed with increases in the molecular weight, composition, and length of the macrobranched hydrophobic domains. These copolymers with reactive anhydride and carboxylic groups were used for the stabilization of penicillin G acylase (PGA). The conjugation of the enzyme with the copolymers significantly increased the thermal stability of PGA (three times at 45 °C and two times at 65 °C). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1580–1593, 2003     

Peripherally tetra-palladated phthalocyanines

Phthalocyanines (M = Co, Zn or 2H) with four ({4-[(Z or E)-phenylazo]-1-naphthyl}oxy) substituents on the periphery have been synthesized to enlarge the absorbing range of the dyestuffs. Cyclopalladation of the azobenzene groups lead to network-type oligomeric products by formation of binuclear palladium (II) complexes and they have been further converted into monomeric species by treatment with acetylacetonate. The electronic spectra clearly indicate the absorptions resulting from phenylazo and naphthyl groups along with the Q and B bands of the phthalocyanines. The consequence of the palladation is a relatively intense broad absorption due to LMCT with maxima around 520 nm.     

Direct determination of sulfite in food samples by a biosensor based on plant tissue homogenate

In the work described here, a biosensor was developed for the determination of sulfite in food. Malva vulgaris tissue homogenate containing sulfite oxidase enzyme was used as the biological material. M. vulgaris tissue homogenate was crosslinked with gelatin using glutaraldehyde and fixed on a pretreated Teflon membrane. Sulfite was enzymatically converted to sulfate in the presence of the dissolved oxygen, which was monitored amperometrically. Sulfite determination was carried out by standard curves, which were obtained by the measurement of consumed oxygen level related to sulfite concentration. Several operational parameters had been investigated: the amounts of plant tissue homogenate and gelatin, percentage of glutaraldehyde, optimum pH and temperature. Also, some characterization studies were done. There was linearity in the range between 0.2 and 1.8 mM at 35 °C and pH 7.5. The results of real sample analysis obtained with the biosensor agreed well with the enzymatic reference method using spectrophotometric detection.     

Effective PET and ICT switching of boradiazaindacene emission: a unimolecular, emission-mode, molecular half-subtractor with reconfigurable logic gates

[reaction, structure: see text] We report a unimolecular system functioning as a combinatorial logic circuit for half-subtractor. The emission characteristics can be modulated by chemical inputs, and when followed at two different wavelengths, two functionally integrated logic gates XOR and INHIBIT are obtained. Both logic gates function in the emission mode, and with very large differences in the signal intensity allowing unequivocal assignment of logic-0 and logic-1.     

Photoisomerization of 2H,6H-Thiin-3-ones to 2-(Alk-1-enyl)thietan-3-ones

Reaction of 3-bromo-3-methylbutan-2-one ( 1 ) with mercapto-esters 2 affords 5-oxo-3-thiahexanoates 3 which cyclize to thiane-3,5-diones 4 . Conversion of these dicarbonyl compounds to their ethyl enol ethers 5–7 followed by reduction with LiAlH₄ gives 2H,6H-thiin-3-ones 8–10 . On irradiation (350 nm) in either MeCN, benzene, or i-PrOH, these newly synthesized heterocycles isomerize efficiently to 2-(alk-l-enyl)thietan-3-ones 11–13 . The rearrangement seems to proceed from an excited singlet state, as it is not quenched by naphthalene, and also occurs with the same efficiency in the presence of added alkene. A (9-S-3) sulfuranyl-alkyl biradical formed by bonding of C(α) of the enone C?C bond on sulfur is discussed as possible intermediate.     

Anomalous NMR behavior of meso compounds with remote stereogenic centers on addition of chiral shift reagent or chiral solvating agent

A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA.     

Thermal computations of temperature distribution and bulb heat transfer in an automobile headlamp

In this study, experimental and numerical analysis was performed to define thermal deformation inside the head lamp because of usage plastic materials and thermal loads. Buoyancy, radiation and conjugate effects were considered. Velocity and temperature distributions were obtained and possible hot points and condense regions can be determined. Nusselt number distribution on cylindrical bulb were computed and compared with literature. Relatively important heat transfer increase in natural convection was found.     

The Mixed Spin-1/2 and Spin-1 Ising–Heisenberg Model in the Mean-Field Approximation: a New Approach

Thermodynamic properties of the mixed spin-1 and spin-1/2 Ising–Heisenberg model are studied on a honeycomb lattice using a new approach in the mean-field approximation to analyze the effects of longitudinal D_z and transverse D_x crystal fields. The phase diagrams are calculated in detail by studying the thermal variations of the order parameters, i.e., magnetizations and quadrupole moments, and compared with the literature to assess the reliability of the new approach. It is found that the model yields both second-and first-order phase transitions, and tricritical points. The compensation behavior of the model is also investigated for the sublattice magnetizations, and longitudinal and transverse quadrupolar moments. The latter type of compensation is observed in the literature but its possible importance is overlooked.     

On the Existence Of Consistent Price Systems

We formulate a sufficient condition for the existence of a consistent price system (CPS), which is weaker than the conditional full support condition (CFS). We use the new condition to show the existence of CPSs for certain processes that fail to have the CFS property. In particular this condition gives sufficient conditions, under which a continuous function of a process with CFS admits a CPS, while the CFS property might be lost.