Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

On worst-case aggregation analysis for network location problems

Network location problems occur when new facilities must be located on a network, and the network distances between new and existing facilities are important. In urban, regional, or geographic contexts, there may be hundreds of thousands (or more) of existing facilities, in which case it is common to aggregate existing facilities, e.g. represent all the existing facility locations in a zip code area by a centroid. This aggregation makes the size of the problem more manageable for data collection and data processing purposes, as well as for purposes of analysis; at the same time, it introduces errors, and results in an approximating location problem being solved. There seems to be relatively little theory for doing aggregation, or evaluating the results of aggregation; most approaches are based on experimentation or computational studies. We propose a theory that has the potential to improve the means available for doing aggregation.This research was supported in part by the National Science Foundation, Grant No. DDM-9023392.     

Synthesis and characterization of novel thermoresponsive‐co‐biodegradable hydrogels composed of N‐isopropylacrylamide,poly(L‐lactic acid), and dextran

A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004     

Preparation, characterization and thermolysis of metal nitrate complexes with 4,4’-bipyridine

Two bis(bipyridine) polymeric metal nitrate complexes with 4,4’-bipyridine of simple formula like [M(bipy)₂](NO₃)2⋅xH₂O (where M=Co, Ni and Cu; x=4, 2 and 0, respectively) have been prepared and characterized. Their thermal decomposition has been undertaken using simultaneous TG-DTG-DTA and DSC in nitrogen atmosphere and non-isothermal TG in air atmosphere. Isothermal TG has been performed at decomposition temperature range of the complexes to evaluate the kinetics of decomposition by applying model-fitting as well as isoconversional method. Possible mechanistic pathways have also been proposed for the thermolysis. Ignition delay measurements have been carried out to investigate the response of these complexes under the condition of rapid heating.     

The acoustic spectrophonometer: a novel bioanalytical technique based on multifrequency acoustic devices

A measurement technique similar to optical absorption spectroscopy but based on evanescent acoustic waves is described in this paper. This format employs a planar spiral coil to vibrate a single crystal of quartz from 6 to 400 MHz, in order to measure multifrequency acoustic spectra. Consistency with the defined Sauerbrey and Kanazawa terms K1 and K2 when applied to multiple frequencies was found for these specific operating conditions in terms of a significant fit between the measured and calculated values: For an IgG surface density of 13.5 ng mm(-2) the measured value of K1 is 22.5 x 10(-6) and the calculated value is 20.4 x 10(-6), whilst for glycerol viscous loadings of 5.131 cP the measured value of K2 is 0.47 and the calculated value is 0.54. Thus for these specific surface loadings the multifrequency data fits to the predictions of the Sauerbrey model to within 10% and to Kanazawa model within 13%. However collective frequency shifts for 5.131 cP solutions of sucrose, dextran and glucose were found to exhibit an unanticipated additional variability (R2 < 0.4) with frequency, but retained a square root of frequency dependency within a factor 2 of the interpolated K2 values. The response to the 5.131 cP dextran solution was found to be significantly below the other isoviscous solutions, with a substantially reduced frequency shift and K2 value than would be expected from its bulk viscosity. In comparison with these viscous solutions, IgG protein films consistently produced linear frequency shifts with little scatter (R2 > 0.96) that were proportional to the operating frequency, and fully consistent with the Sauerbrey model under these specific conditions. A t-test value of 14.52 was calculated from the variance and mean of the two groups, and demonstrates that the acoustic spectrophonometer can be used to distinguish between the acoustic impedance characteristics of two chemical systems that are not clearly differentiable at a single operating frequency.     

Sorption of triethyleneglycol and tetraethyleneglycol by silicalite at fixed water activities

The sorption of tetraethyleneglycol by silicalite-1 and triethyleneglycol by silicalite-1 and a silicalite-1/silicalite-2 intergrowth has been studied at 25°C and at fixed water activities in the range 0.111<a _w<0.902 by an isopiestic method. All of the glycol uptakes are between 0.95 and 1.2 molecules per unit cell and in all cases they are essentially independent of water activity. The water content of the silicalite-1 was more sensitive to water activity and glycol content than was that of the silicalite-1/2 intergrowth.     

Hypersonic evanescent waves generated with a planar spiral coil

A planar spiral coil has been used to induce hypersonic evanescent waves in a quartz substrate with the unique ability to focus the acoustic wave down onto the chemical recognition layer. These special sensing conditions were achieved by investigating the application of a radio frequency current to a coaxial waveguide and spiral coil, so that wideband repeating electrical resonance conditions could be established over the MHz to GHz frequency range. At a selected operating frequency of 1.09 GHz, the evanescent wave depth of a quartz crystal hypersonic resonance is reduced to 17 nm, minimising unwanted coupling to the bulk fluid. Verification of the validity of the hypersonic resonance was carried out by characterising the system electrically and acoustically: Impedance calculations of the combined coil and coaxial waveguide demonstrated an excellent fit to the measured data, although above 400 MHz a transition zone was identified where unwanted impedance is parasitic of the coil influence efficiency, so the signal-to-noise ratio is reduced from 3000 to 300. Acoustic quartz crystal resonances at intervals of precisely 13.2138 MHz spacing, from the 6.6 MHz ultrasonic range and onto the desired hypersonic range above 1 GHz, were incrementally detected. Q factor measurements demonstrated that reductions in energy lost from the resonator to the fluid interface were consistent with the anticipated shrinkage of the evanescent wave with increasing operating frequency. Amplitude and frequency reduction in contact with a glucose solution was demonstrated at 1.09 GHz. The complex physical conditions arising at the solid-liquid interface under hypersonic entrainment are discussed with respect to acceleration induced slippage, rupture, longitudinal and shear radiation and multiphase relaxation affects.     

MgF(3)(-) as a transition state analog of phosphoryl transfer

The formation of complexes between small G proteins and certain of their effectors can be facilitated by aluminum fluorides. Solution studies suggest that magnesium may be able to replace aluminum in such complexes. We have determined the crystal structure of RhoA.GDP bound to RhoGAP in the presence of Mg(2+) and F(-) but without Al(3+). The metallofluoride adopts a trigonal planar arrangement instead of the square planar structure of AlF(4)(-). We have confirmed that these crystals contain magnesium and not aluminum by proton-induced X-ray emission spectroscopy. The structure adopted by GDP.MgF(-) possesses the stereochemistry and approximate charge expected for the transition state. We suggest that MgF3(-) may be the reagent of choice for studying phosphoryl transfer reactions.     

Synthesis of novel rigid triazine-based calix[6]arenes

In this report, the stepwise synthesis of a novel rigid and functionalised macrocycle 2 based on triazine and phenylenediamine linkers, is presented. Poor recognition of the macrocycle 2 for its substrates is observed, which shows experimentally that for the meltriazine based-calix[6]arene system, the binding ability of the melamine moiety gets more benefit from the ring flexibility derived from a xylenediamine linker 1 than from a phenylenediamine linker 2.