Characterization of poly(carboxylic acid)/poly(ethylene oxide) blends formed through hydrogen bonding by spectroscopic and calorimetric analyses

The solid state of the complex between poly(acrylic acid) (PAA) and poly(ethylene oxide) (PEO), and that between poly(methacrylic acid) (PMAA) and PEO formed via hydrogen-bonding was studied by differential-scanning calorimetric (DSC) and by Fourier-transform infrared (FT–IR) spectroscopic measurements. Melting temperature T_m and the degree of the crystallinity X_c of PEO in the systems PAA (or PMAA)/PEO blends obtained from aqueous or dimethyl sulfoxide (DMSO) medium were measured in various unit mol % of PEO ([PEO]100/{[PAA(or PMAA)] + [PEO]}) where [ ] is the unit mole concentration. It was found that 50 unit mol % of PEO is a critical composition, which gives new evidence for the 1 : 1 complex formation between PAA (or PMAA) and PEO. From the FT–IR spectroscopic analysis in conjunction with DSC measurements we also found that the effects of solvent and of hydrophobic interaction (due to the α-methyl group of PMAA) are the important factors controlling the complexation in the solution and solid systems. These factors also affect the crystallization behavior and the microstructure of the PAA (or PMAA)/PEO blend in solid state.     

Synthesis of 2,3-dihydrospiro[benzofuran-2,4′ -piperidines] and 2,3-dihydrospiro[benzofuran-2,3′-pyrrolidines]

The synthesis of 2,3-dihydrospiro[benzofuran-2,4′-piperidines] 3 and 2,3-dihydrospiro[benzofuran-2,3′]-pyrrolidine] 6 is described. The synthesis was achieved by a Grignard reaction of a 2-fluorobenzylhalide with an appropriate cycloazaalkyl ketone to yield the tertiary alcohols 1 and 4 . Subsequent intramolecular displacement of the aromatic fluoride by the derived alkoxides provided the novel system. Nitration of 1′-acetyl-2,3-dihydrospiro[benzofuran-2,4′-piperidine] 7 resulted in a 5-nitro derivative.     

Conformal transition of form II to form I in poly(L-proline) and the aggregation of form I. I. Acetic acid–propanol solvent system

The conformational transition of Form II → Form I of Poly-L-proline and the intermolecular aggregation of the product Form I during and after the transition in the HOAc-propanol mixture solvent were studied, the ratio of HOAc:propanol being changed as 1:9, 1:6, and 1:4 v/v. For the study, the viscosity, light scattering, and dynamic light scattering of the system were measured. The experimental results exhibit that the concentration of Form II promotes the end-to-end type aggregation during and after the transition Form II → I. The extent of the aggregation is reduced in the order of the ratios of HOAc/propanol 1:9, 1:6, and 1:4 v/v. The end-to-end type aggregation is also reduced at higher temperatures. It was also observed that the end-to-end type aggregation occurs abruptly and strongly after the transition of Form II → I occurred to some extent. The point of the abrupt occurrence depends on the solvents and temperature. The light scattering and translational diffusion-coefficient measurements showed also similar phenomena. It was also observed that the side-by-side type aggregation occurs when the initial concentration of Form II of poly-L-proline is relatively small, and the transition temperature is relatively high (35 and 45°C). All the above mentioned experimental results are explained by a simple principle described in the text.     

Optimal M/G/1 Server Location on a Network Having a Fixed Facility

This paper considers the problem of locating a single mobile service unit on a network G where the servicing of a demand includes travel time to a permanent facility which is located at a predetermined point on G. Demands for service, which occur solely on the nodes of the network, arrive in a homogeneous Poisson manner. The server, when free, can be immediately dispatched to a demand: the service unit travels to the demand, performs some on-scene service, continues to the permanent facility, where off-scene service is rendered, and then it returns to its ‘home’ location, where possibly additional off-scene service is given. Previous research has examined the same problem, however without the presence of a permanent facility. The paper discusses methods of solving two cases when the server is unable to be immediately dispatched to service a demand: (1) the zero-capacity queueing system; (2) the infinite-capacity queueing system. For the first case we prove that the optimal location is included in a small set of points in the network, and we show how to find this set. For the second case, we present an 0(n³) algorithm (n is the number of nodes) to obtain the optimal location.     

Molecular dimensions of polypeptides in helicogenic solvents

The dependence of the molecular dimension of polypeptides in helicogenic solvents on molecular weight was calculated by using the Zimm-Bragg-Nagai theory in collaboration with the broken-rod model, in which the excluded volume effect was taken into account by setting the equivalent chain to be a nonintersecting chain. Our calculated results for PBLG in helicogenic solvents were compared with experiment with good agreement. The flexibility of the helices of PCBL and PELG as broken rods corresponded to that of PBLG without excluded volume effect (i.e., the broken rod of a self-intersecting chain) in a comparison of their experimental data with our calculated results for PBLG of self-intersecting and nonintersecting chains. Over a wide range of molecular weights M our theory explains the dependence of the length per monomeric residue h on M, even for short chains in which h > 1.5 Å.     

Unnatural proteins for the control of surface forces

We introduce a new method for the stabilization of colloidal particles via the synthesis and adsorption of unnatural proteins. Biosynthesis of protein-based polymers offers the advantages of preparation of complex sequences through control of the primary sequence, monodisperse polymers, ease of combinatorial search for anchor blocks, environmentally friendly synthesis, use of water as the solvent, and incorporation of a palette of known natural proteins. We have synthesized an unnatural protein with the sequence thioredoxin-Pro(39)Glu(10) for modification of the forces between alumina particles. The polyglutamate sequence, Glu(10), is anionic (pH > 3) and is designed to anchor the protein to positively charged solids, e.g. alumina in water (pH < 9). The polyproline sequence, Pro(39), is neutral. The thioredoxin is a recombinant form of the natural globular protein with a histidine patch (His-patch-thioredoxin) and is zwitterionic. The combined thioredoxin-Pro(39) sequence is hydrophilic with pI approximately 6.3. This block is designed to remain in solution, thereby providing a steric barrier to the approach of two particles in a range of salt and pH conditions. Ellipsometry experiments show that thioredoxin-Pro(39)Glu(10) does adsorb to alumina. Force measurements with the atomic force microscopy (AFM) colloid probe technique show that adsorption of thioredoxin-Pro(39)Glu(10) leads to repulsive forces that decay exponentially with the separation between the surfaces and are independent of salt concentration in the range 0.001-0.1 M KNO(3). This demonstrates that the repulsive forces are not electrostatic. We hypothesize that the repulsion is due to confinement and loss of solvent for the adsorbed polymer; the forces are similar to those expected for a polymer brush. Force measurements between thioredoxin-coated alumina surfaces also show a repulsive force, but the force has a decay length that is consistent with electrostatic double-layer forces: the thioredoxin has not neutralized the surface charge of the underlying alumina. Our results point to interesting future experiments where recombinant DNA technology could be used to synthesize fusion proteins containing useful natural proteins and an anchor. This may allow preparation, via single-step aqueous self-assembly, of anchored proteins that maintain their natural structure. Our technique is not limited to homopolymer blocks; more complex primary sequences can be used.     

Absence of discrete spectrum in highly negative ions

LetH _N be the Hamiltonian for the Coulomb system consisting ofN particles of like charge in the field of a fixed point chargeZ. We show that if the particles are bosons, thenH _N has no discrete spectrum whenNN ₀=cZ ² for some constantc. If the particles are fermions, thenH _N is bounded below uniformly inN. These results can be extended to molecules and to other power law potentials.Research supported by the National Science Foundation, MCS78 -20455 USAOn leave from Department of Mathematics, University of Lowell, Lowell, MA O1854 USA     

Synthesis and characterization of conducting poly(aniline‐co‐o‐aminophenethyl alcohol)s

Poly(o‐aminophenethyl alcohol) and its copolymers containing the aniline unit were synthesized in aqueous hydrochloric acid medium by chemical oxidative polymerization. The chemical composition of these novel polymers was determined spectroscopically, and their viscosities were measured. These polymers exhibit good solubility in organic solvents that is attributed mainly to the polar hydroxyethyl side groups. Their structures (chain conformation and morphological structure) and properties (conductivity, electrochemical characteristics, glass transition, and degradation behavior) were characterized and then interpreted on the basis of the chemical composition along with the electronic and steric hindrance effects associated with the hydroxyethyl side group. Overall, the side group has a significant effect on the polymerization and influences the structure, chain conformation, and properties of the resultant polymer. The poly(aniline‐co‐o‐aminophenethyl alcohol)s containing 20–40 mol % o‐aminophenethyl alcohol units are potential conducting materials for microelectronic and electromagnetic shielding applications because they are easier to process than polyaniline but retain its beneficial properties. These polymers can also be used as a functional conducting polymer intermediate owing to the reactivity of the side group. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 983–994, 2002     

Computational investigation of the vibrational and electronic states of S2N2

The structures and vibrational frequencies of the ground and excited states of S(2)N(2) have been calculated using density functional (DF) methods. Time-dependent DF theory (TDDFT) has been used to calculate the excitation energies of the lowest 20 singlet-singlet transitions using a variety of methods. All computational methods predict a small highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. There is some disagreement in the ordering of the b(2g) and b(3g) pi orbitals. This is reflected in the ordering of the B(2u) and B(3u) states from the TDDFT calculations. The excitation energies and oscillator strengths strongly suggest it is the transitions to these states that are responsible for the experimental electronic spectrum. The calculated geometries and vibrational frequencies for these two states show that both have C(2v) equilibrium structures. Modelling of the vibrational progressions and band shapes suggest that the ordering of the states is B(2u)相似文献   

TheGF(p)-dimension of the codes generated by the classical point-line geometries overGF(p)

In this note we develop a combinatorial-algebro-geometric approach to give a new self-contained analysis of the structure and dimension of theGF(p)-codes generated by the point-line geometriesAG ₁ (n, p) andPG ₁ (n, p) of dimensionn overGF(p) as coordinate field. The novelty of this paper is a beautiful representation of these codes as nil-ideals of the modular group algebra , which leads to an easy derivation of the dimension formula.Dedicated to Professor Konrad Jacobs, Erlangen, on the occasion of this 65th birthday.