Summary: A computer simulation model is proposed to study film growth and surface roughness in aqueous (A) solution of hydrophobic (H) and hydrophilic (P) groups on a simple three dimensional lattice of size with an adsorbing substrate. Each group is represented by a particle with appropriate characteristics occupying a unit cube (i.e., eight sites). The Metropolis algorithm is used to move each particle stochastically. The aqueous constituents are allowed to evaporate while the concentration of H and P is constant. Reactions proceed from the substrate and bonded particles can hop within a fluctuating bond length. The film thickness ( ) and its interface width ( ) are examined for hardcore and interacting particles for a range of temperature ( ). Simulation data show a rapid increase in and followed by its non‐monotonic growth and decay before reaching steady‐state and near equilibrium ( ) in asymptotic time step limit. The growth can be described by power laws, e.g., with a typical value of in initial time regime followed by at . For hardcore system, the equilibrium film thickness ( ) and surface roughness ( ) seem to scale linearly with the temperature, i.e., at low and at higher . For interacting functional groups in contrast, the long time (unsaturated) film thickness and surface roughness, and decay rapidly followed by a slow increase on raising the temperature.
Growth of the average film thickness at a temperature . 相似文献
A novel helical poly(macromonomer) [poly(M‐PS): absolute = 82 800–252 000, determined by GPC/RALLS] with a polyacetylene main chain and polystyrene (PS) side chains was synthesized by the polymerization of acetylene‐terminated M‐PS [ = 2 000, / = 1.20, = 18] with an Rh catalyst. M‐PS was prepared by ATRP of styrene using the acetylene‐containing initiator 2‐bromo‐2‐methylpropionic acid (S)‐1‐methylpropargyl ester ( l ). In solutions, poly(M‐PS) exhibited an intense CD signal at 345–355 nm, indicating that it possessed a predominantly one‐handed helical conformation. Poly(M‐PS) had a stable helical conformation irrespective of solvents and temperature.
The dilution of tert‐butylamine (tBA) with water and subsequent cooling leads to a large series of different crystalline hydrates by an in situ IR laser melting‐zone procedure. The crystal structures were determined for tBA?n H2O, with n=0, , 1, 7 , 7 , 9 , 11, and 17. For the two lower hydrates (n= , 1), one‐ and two‐dimensional hydrogen‐bonded networks are formed, respectively. The higher hydrates (n>1) exhibit a clathrate‐like three‐dimensional water framework with the tBA molecules as part of, or sitting inside, the cages. In all cases, tBA is hydrogen‐bonded to the H2O framework. In the intermediate range (1相似文献
We describe the controlled fabrication of ultrathin multilayer films consisting of tri‐vanadium‐ substituted heteropolytungstate anions (denoted as P2W15V3) and a cationic polymer of quaternized poly (4‐vinylpyridine) partially complexed with osmium bis(2,2′‐bipyridine) (denoted as QPVP‐Os) on the 4‐aminobenzoic acid (4‐ABA) modified glassy carbon electrode (GCE) surface based on layer‐by‐layer assembly. Cyclic voltammetry and UV‐vis absorption spectrometry have been used to easily monitor the thickness and uniformity of thus‐formed multilayer films. The V‐centered redox reaction of P2W15V3 in the multilayer films can effectively catalyze the reduction of BrO and NO . The resulting P2W15V3/QPVP‐Os multilayer film modified electrode behaves as a much promising electrochemical sensor because of the low overpotential for the catalytic reduction of BrO and NO , and the catalytic oxidation of ascorbic acid. 相似文献
The constitutive equations for liquid crystalline polymers recently proposed by one of us [1] are applied here to interpret the behaviour of the shear viscosity η and the first normal stress difference N1() measured for liquid crystalline (LC) solutions of hydroxypropylcellulose in acetic acid. N1( ) is observed to change from positive to negative and again to positive, as the shear rate increases, at lower concentrations, in the LC phase. The -values at which N1 changes sign depend on the molecular mass (degree of polymerization) and on the concentration. η shows a small Newtonian plateau at low shear rates and a strong shear-thinning at higher values of . The rate of decrease of η in this region shows an “hesitation” similar to one previously observed in LC solutions of poly-γ-benzyl-L-glutamate PBLG. All these observations can be rationalized within the frame-work of Martins' theory. The expressions for N1() and η derived from this theory fit very well (quantitatively) to the experimental data and some fundamental viscoelastic parameters of the system under study are thereby obtained for the first time. 相似文献
Unmodified β‐cyclodextrin has been directly used to initiate ring‐opening polymerization of ϵ‐caprolactone in the presence of yttrium trisphenolate. Well‐defined cyclodextrin (CD)‐centered star‐shaped poly(ϵ‐caprolactone)s have been successfully synthesized containing definite average numbers of arms (Narm = 4–6) and narrow polydispersity indexes (below 1.10). The number‐average molecular weight ( ) and average molecular weight per arm ( ) are controlled by the feeding molar ratio of monomer to initiator. The prepared star‐PCL with of 2.7 × 103 is in fully amorphous and that with of 13.3 × 103 is crystallized. In addition, the obtained poly(e‐caprolactone) (PCL) stars with various molecular weights have different solubilities in methanol and tetrahydrofuran, which can be applied for further modifications. 相似文献
The radical cation and the radical anion of ‘syn’-cyclobuta[1,2-c:3,4-c′]di-1,6-methano[10]annulene (‘syn’-4a,12a:6a, 10a-bishomobinaphthylene; 3 ) have been characterized by their hyperfine data. The highly resolved ESR spectrum of $ 3^{+ \atop \dot{}} $ is dominated by a triplet splitting from the outer pair of methano β-protons (Ho). In contrast, the ESR spectrum of $ 3^{- \atop \dot{}} $ is poorly resolved with the largest coupling constants arising from perimeter α-protons. The different hyperfine features of $ 3^{+ \atop \dot{}} $ and $ 3^{- \atop \dot{}} $ are rationalized by MO models. The SOMO of $ 3^{+ \atop \dot{}} $ ψSA(b1), has substantial LCAO coefficients of the same sign at the bridged atoms C(1), C(6), C(11), and C(16), whereas in the SOMO of $ 3^{- \atop \dot{}} $, ψSS(a1), the four atoms lie in the vertical nodal planes. The large width and the reluctance to saturation of the lines in the ESR spectrum of $ 3^{- \atop \dot{}} $ are attributed to the near-degeneracy of the lowest antibonding MO's. Due to their similar nodal properties, the SOMO's of $ 3^{- \atop \dot{}} $ and the radical anions of binaphthylene ( 4 ), 1,6-methano[10]annulene ( 1 ), and naphthalene ( 2 ) are interrelated. Moreover, because the cyclic π-systems in 3 and 1 deviate in the same way from planarity, the effect of such distortions on the coupling constants, aHμ, of the perimeter α-protons in $ 3^{- \atop \dot{}} $ and $ 1^{- \atop \dot{}} $ should be comparable. Indeed, on going from $ 4^{- \atop \dot{}} $ to $ 3^{- \atop \dot{}} $, the |aHμ| values are reduced exactaly by half as much as the corresponding values on passing from $ 2^{- \atop \dot{}} $ to $ 3^{- \atop \dot{}} $, of which the cyclic π-systems are twice contained in $ 4^{- \atop \dot{}} $ and $ 3^{- \atop \dot{}} $ respectively. 相似文献
The electrochemical oxidation of bromide in the presence of ammonium ion (NH ) was studied by cyclic voltammetry and UV‐vis spectroscopy. The experimental results suggested that the anodically generated bromine (Br2) would be hydrolyzed to hypobromous acid (HBrO) at the pH range of 5–7 and was further disproportionate to hypobromite anion (BrO?) when pH was larger than 7. Both HBrO and BrO? were confirmed to be participated in the following homogeneous chemical reaction with the coexisted ammonium ion. However, HBrO is electroactive whereas BrO‐ is electroinactive at carbon electrode. Based upon the reaction of HBrO with NH , an indirect electrochemical method was proposed for determination of NH with dual‐electrode configuration in phosphate buffer solution (pH 7), where HBrO was produced at a generator electrode and the excess HBrO was subsequently detected at a collector electrode after a reaction with NH in a batch solution or in a micro flow injection analytical (micro‐FIA) system by using an interdigitated array (IDA) Pt microelectrode and a carbon film ring‐disk electrode (CFRDE), respectively. The decreasing of reduction current at the collector electrode was proportional to the concentration NH in both systems, with the detection limit below 3.0 μM. This approach shows the advantage of highly selectivity even in presence of a large amount of coexisted cations, and was successfully applied for the determination of NH in environmental water samples. 相似文献
A well‐defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S‐co‐CMS), = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S‐co‐HWS), = 6200 Da, PDI = 1.13). The P(S‐co‐HWS) polymer is subsequently ligated with tetrakis(4‐azidophenyl)methane to give HW‐functional star‐shaped macromolecules (P(S‐co‐HWS))4, = 25 100 Da, PDI = 1.08). Supramolecular star‐shaped copolymers are then prepared via self‐assembly between the HW‐functionalized four‐arm star‐shaped macromolecules ( P(S‐co‐HW )) 4 and cyanuric acid (CA) end‐functionalized PS (PS–CA, = 3700 Da, PDI = 1.04), CA end‐functionalized poly(methyl methacrylate) (PMMA–CA, = 8500 Da, PDI = 1.13) and CA end‐functionalized polyethylene glycol (PEG–CA, = 1700 Da, PDI = 1.05). The self‐assembly is monitored by 1H NMR spectroscopy and light scattering analyses. 相似文献
Summary: The miscibility behavior and intermolecular interactions among Dextran (Dx) with different molecular weight and Polyvinylpyrrolidone (PVP) blends were studied as dilute aqueous solutions at 25 °C by viscosity method. The intrinsic viscosity and the interaction coefficient were experimentally measured for each polymer-water as well as for Dx-PVP-water systems. These results served for the prediction of miscibility of the Dx/PVP blends with various blend compositions by using , , , , and parameters. Except Dx4/PVP with its all compositions (Dx4 with nominal molecular weight of 110 000), other blend systems are found to be almost miscible. The density measurements of these polymer solutions and their blends were conducted in order to compare with the viscosity findings. Lastly, all Dx with different molecular weight, PVP and their blends were characterized by infrared spectroscopy (FT-IR), and differential scanning calorimetry (DSC). 相似文献
The radical cations and the radical anions of 1,6-dithiapyrene ( 1 ) and 3,10-dithiaperylene ( 2 ) as well as those of three further Weitz-type S-donors 3 , 4 , and 5 have been studied by ESR spectroscopy. The experimental findings for (widths and behaviour on saturation of hyperfine lines) suggest that the ground state of this radical anion is effectively degenerate. With the exception of , the ESR studies of all radical ions could be complemented by the use of the ENDOR and general TRIPLE resonance techniques. In addition to proton hyperfine data, 33S coupling constants have been determined for (0.53mT), (0.46mT), and (0.34mT); they are in agreement with the predicted substantial π-spin populations at the S-atoms. 相似文献
ESR and ENDOR studies have been carried out on the radical cations obtained consecutively by reaction of trans-10b, 10c-dimethyl-10b, 10c-dihydropyrene ( 4 ) with AlCl3 in CH2C12. The primarily formed ${\bf 4}^{+ \atop \dot{}}$ rearranges at 253 K to the radical cation(s) of 1,6- ( 5a ) and/or 1,8-dimethylpyrene ( 5b ). At 323 K, the spectra of ${\bf 5a}^{+ \atop \dot{}}$/${\bf 5b}^{+ \atop \dot{}}$ are replaced by that of the highly persistent radical cation of 1,3,6,8-tetramethylpyrene ( 6 ). Surprisingly, ${\bf 6}^{+ \atop \dot{}}$ is also the only observable paramagnetic product resulting from a treatment of 4,5,7,8- ( 1 ), 4,7,13,16- ( 2 ), and 4,5,12,13-tetramethyl[2.2]paracyclophane ( 3 ) with AlCl3 in CH2Cl2 at 353 K. The structures of the intermediates in the rearrangement [${\bf 1}^{+ \atop \dot{}}$, ${\bf 2}^{+ \atop \dot{}}$, ${\bf 3}^{+ \atop \dot{}}$] → ${\bf 6}^{+ \atop \dot{}}$ are discussed. 相似文献
The PANI/Au0 nanocomposite films were successfully prepared on glassy carbon electrode (GCE) using a simple alternate adsorption of water soluble polyaniline (PANI) and . The growth of the films was monitored by UV? Vis spectroscopy and cyclic voltammetry. was in‐situ reduced in the film due to the redox interaction between PANI and , without extra reductant. The ultrafine Au nanoparticles with the size of 2–4 nm were observed by transmission electron spectroscopy. The existence of zero‐valence Au nanocrystals (Au0) was confirmed by X‐ray photoelectron spectroscopy, X‐ray Diffraction and FTIR. PANI in the nano‐structured PANI/Au0 composite films displayed a good redox activity in neutral pH solution. The as‐obtained PANI/Au0/GCE presents an excellent electrocatalytic activity to hydrazine oxidation, and the mechanism of hydrazine oxidation was studied. The calibration curve on (PANI/Au0)5/GCE was obtained in the concentration range of 0.01–6 mM with the detection limit of 1 µM (S/N>3). The modified electrode has a great potential for hydrazine sensor application due to its ease of fabrication, good reproducibility and high stability. 相似文献
Summary: A novel chitosan derivative with polysarcosine side chains, i.e., chitosan‐graft‐polysarcosine [chitosan‐graft‐poly(N‐methylglycine)], was synthesized by ring‐opening polymerization of sarcosine N‐carboxyanhydride (NCA) with chitosan as a macroinitiator in the presence of carboxylic acids in dimethyl sulfoxide at 27 °C. Degree of substitution ( ) for polysarcosine side chains introduced to chitosan was controlled successfully by the feed amount of the additive nicotinic acid ( = 0.21–0.71). Independent of control, degree of polymerization ( ) for polysarcosine side chains was controlled by adjusting feed ratios of NCA monomer to chitosan ( = 14–43). Kinetic analysis of the propagation of sarcosine NCA was conducted by measuring CO2 evolution. Apparent kp values decreased with increased feed amounts of nicotinic acid, supporting the theory that propagation of NCA in the presence of nicotinic acid proceeds via equilibrium between active amine and dormant ammonium species.
Propagation mechanism of carboxylic acid‐mediated polymerization of sarcosine N‐carboxyanhydride. 相似文献
A composite film modified electrode containing a Keggin‐type heteropolyanion, H3(PMo12O40)?H2O, was fabricated with 3‐aminopropyltrimethoxysilane (APMS) attached on an electrochemically activated glassy carbon (GC) electrode through the formation of C? O? Si bond. PMo12O was then complexed with APMS through the electrostatic interaction between the phosphate groups of PMo12O and amine groups of APMS (PMo12O ‐APMS). XPS and cyclic voltammetry were employed for characterization of the composite film. The PMo12O ‐APMS modified electrode showed three reversible redox pairs with smaller peak‐separation and was stable in the larger pH range compared with that in a solution phase. The catalytic properties of the modified electrode for the reduction of ClO , BrO , and IO were studied and the modified electrode exhibited good electrocatalytic activities for the three anions. The experimental parameters, such as pH, temperature, and the applied potential were optimized. The detection limits were determined to be 7.0±0.35 μM, 4.0±0.17 μM, and 0.1±0.04 μM for ClO , BrO , and IO , respectively. The modified electrode was applied to natural water samples for the detection of ClO , BrO , and IO . 相似文献