High-temperature polymerization of ϵ-caprolactam by using as catalyst the Li,Na, or K salts derived from MAlEt4 or MOAlEt2·AlEt3 and monomer

High-temperature polymerization of ?-caprolactam by using the salts derived from MAlEt₄ (where M is Li, Na, and K) and monomer as catalyst was carried out. Polymerization occurs at 140–170°C, a temperature at which alkali metal caprolactamate has almost no catalytic activity for initiation. m-Cresol-insoluble polymer was obtained at temperatures lower than 231°C. Formation of a m-cresol-insoluble polymer depends on the polymerization temperature and time, and was observed under conditions where Al(Lac)₃ has no catalytic activity. All the polymers obtained by NaAl(Lac)_4–n(NHBu)_n (n = 1 or 2) at 202°C were soluble in m-cresol. These trends observed in the case of MAl(Lac)₄ are considered to be due to initiation by Al(Lac)₃, which is a component of the catalyst used.     

Contribution to the study of self-avoiding random walks (SARW) confined to strips and capillaries

A flexible chain that can assume all possible positions on a lattice without intersection of segments (self-avoiding random walk, SARW) has been used for a long time as a model of polymers in highly dilute solution, taking into account the excluded volume. In this article, we extend to a SARW subject to spatial constraints an analytical accurate method we have established for a SARW on an unbounded lattice. We now consider a square or cubic lattice extending without limit in the x direction but confined to D layers in the other directions. This is a model for the study of constrained macromolecules the behavior of which is important for instance in connection with the properties of thin polymeric films or fibers, or with the solubility of biopolymers in lipid bilayer membranes. We give recurrence relationships for calculating C_n, the total number of configurations, and x _n, the mean x projection of the end-to-end separation, for a chain length n. Our method, being analytical, allows a considerable economy of computational time with respect to other methods such as Monte Carlo calculations. It enables us to investigate the asymptotic behavior of x _n and to write the partition function of the system.     

The formation of solid solutions in the tetrahydrofuran-tetra(n-propyl)ammonium fluoride-water system

The phase diagram of the tetrahydrofuran (THF)-tetra(n-propyl)ammonium fluoride (Prp₄ NF)-water system has been studied by differential thermal analysis (DTA). Solid solutions have been detected of the general formula THF·x Prp₄NF·(17–2x) H₂O, wherex changes from 0.06 to 0.5. The formation of solid solutions is due to the variable degree of the filling of the fragment consisting of four D-cavities in CS-II clathrate hydrates by the tetra(n-propyl)ammonium cation. The solid solution obtained is peculiar in that its vacancies are occupied by the blocks of four D-cavities each. Besides, this kind of displacement of two water molecules by an ionic pair Prp₄N⁺+F^–, where only the charges of the substituting and substituted groups are equal, takes place here. It appears that this type of solid solution has been discovered for the first time.     

Effects of polystyrene-b-poly(aminomethyl styrene)s as stabilizers on dispersion polymerization of styrene in alcoholic media

The effects of polystyrene-b-poly(aminomethyl styrene) (PS_n-b-PAMS_m) stabilizers on the particle size (D_n) and size distribution (PSD) in dispersion polymerization of styrene were investigated. The block copolymers, PS_n-b-PAMS_m, were prepared as follows: (i) atom transfer radical polymerization (ATRP) of styrene (PS-Br), (ii) ATRP of vinylbenzylphthalimide with the PS-Br (PS-b-PVBP), and (iii) treatment of the PS-b-PVBP with hydrazine. When the dispersion polymerization of styrene proceeded at 60 °C in ethanol with PS₁₉-b-PAMS₁₃₀ stabilizer, spherical polystyrene particles with D_n=0.91 μm (PSD = 1.01) were obtained. The particle size was strongly affected by the copolymer composition. With an increase in PAMS block length from m=54 to 100 in PS₁₇-b-PAMS_m, particle diameter became smaller from 1.55 to 0.91 μm. On the other hand, an increase in the length from m=20 to 82 in PS₃₄-b-PAMS_ms caused an increase in particle size from 0.35 to 0.70 μm. Titration of the particles suggests that 14–81% of stabilizers used in the polymerization system were attached on the polystyrene particle surfaces, depending on the composition of the block copolymers. Thus, for the dispersion polymerization of styrene, PS_n-b-PAMS_m block copolymers have both functions as a stabilizer during polymerization and surface-modification sites of polystyrene particles.     

Influence of intrachain interactions on the kinetics of styrene polymerization and copolymerization

In the free-radical polymerization of styrene, it has been observed that the onset of an acceleration of the polymerization due to increased solution viscosity can be quantitatively measured as occurring at a critical point. The product of the degree of polymerization of the polymer in solution at the critical point times its volume fraction can be represented by a temperature-dependent constant (P?_n, V_c, = K ). The value of the constant passes through a maximum between 60 and 90°C. The value of the constant is somewhat lower than that for the phenomenon called chain entanglement. It is postulated that the temperature-dependent behavior of K is due to a previously reported solution phase transition which is believed to be caused by interaction between phenylgroups on the polystyrene chain. Observations on the ultraviolet absorbance of styrene copolymers and calculations on the absolute rate of copolymerization of styrene with methyl methacrylate are presented to support the postulated intrachain interactions.     

Multiwalled Carbon Nanotubes Encased in Ruthenium Oxide Film as a Hybrid Material for Neurotransmitters Sensor

A hybrid film (MWCNTs‐RuO_x?nH₂O) which contains multiwalled carbon nanotubes (MWCNTs) along with the incorporation of ruthenium oxide (RuO_x?nH₂O) has been synthesized on glassy carbon electrode (GCE), gold (Au), indium tin oxide (ITO) and screen printed carbon electrode (SPCE) by potentiostatic methods. The presence of MWCNTs in the hybrid film enhances surface coverage concentration (Γ) of RuO_x?nH₂O to ≈2100%. The surface morphology of the hybrid film deposited on ITO has been studied using scanning electron microscopy and atomic force microscopy. These two techniques reveal that the RuO_x?nH₂O incorporated on MWCNTs. Electrochemical quartz crystal microbalance study too reveals the incorporation of MWCNTs and RuO_x?nH₂O. The MWCNTs‐RuO_x?nH₂O hybrid film exhibits promising enhanced electrocatalytic activity towards the biochemical compounds such as epinephrine and norepinephrine. The electrocatalytic responses of these analytes at RuO_x?nH₂O, MWCNTs and MWCNTs‐RuO_x?nH₂O hybrid films have been measured using cyclic voltammetry. The obtained sensitivity values from electrocatalysis studies of analytes for MWCNTs‐RuO_x?nH₂O hybrid film are higher than the RuO_x?nH₂O and MWCNTs films. Finally, the flow injection analysis has been used for the amperometric studies of analytes at MWCNTs‐RuO_x?nH₂O hybrid film modified SPCEs.     

Polymerization Kinetics of Water-Soluble N-Vinyl Monomers in Aqueous and Organic Solution

Summary: Free-radical batch polymerization (FRP) of N-vinyl pyrrolidone (NVP) and N-vinyl formamide (NVF) monomers in aqueous solution as well as NVP polymerization in organic (n-butanol) solution has been studied. The differences found in rate of monomer conversion with monomer and solvent choice correlates well with the differences in values of the propagation rate coefficients (k_p) and their variation with monomer concentration measured in independent pulsed-laser polymerization studies, a result demonstrating that a generalized understanding of water-soluble vinyl monomers can be obtained once their k_p differences have been accounted for. A reasonable representation of polymer molecular mass averages and the complete molecular mass distributions for the three systems was obtained by assuming that the rate coefficient for transfer to monomer, polymer, and organic solvent also vary as a function of monomer concentration.     

Optimization of bimetallic Cu–Au and Ag–Au clusters by using a modified adaptive immune optimization algorithm

A modified adaptive immune optimization algorithm (AIOA) is designed for optimization of Cu–Au and Ag–Au bimetallic clusters with Gupta potential. Compared with homoatom clusters, there are homotopic isomers in bimetallic cluster, so atom exchange operation is presented in the modified AIOA. The efficiency of the algorithm is tested by optimization of Cu_nAu_38‐n (0 ≤ n ≤ 38). Results show that all the structures with the putative global minimal energies are successfully located. In the optimization of Ag_nAu_55‐n (0 ≤ n ≤ 55) bimetallic clusters, all the structures with the reported minimal energies are obtained, and 36 structures with even lower potential energies are found. On the other hand, with the optimized structures of Cu_nAu_55‐n, it is shown that all 55‐atom Cu–Au bimetallic clusters are Mackay icosahedra except for Au₅₅, which is a face‐centered cubic (fcc)‐like structure; Cu₅₅, Cu₁₂Au₄₃, and Cu₁Au₅₄ have two‐shell Mackay icosahedral geometries with I_h point group symmetry. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009     

Multi‐Objective Optimization of Semi‐Batch Copolymerization Reactors Using Adaptations of Genetic Algorithm

Summary: The polymerization of styrene‐acrylonitrile (SAN) random copolymers in semi‐batch reactors is optimized using multiple objective functions that are often conflicting and non‐commensurate in nature. These include the average composition of the copolymer product, its number‐average molecular weight, its polydispersity index, and the conversion of monomers attained in the reactor. Two decision/control variables are used, namely, the rate of continuous addition of a monomer‐solvent‐initiator mixture (having a specified and fixed composition) and the history of the temperature in the reactor. The elitist non‐dominated sorting genetic algorithm, NSGA‐II, is adapted and used for decision variables that are functions of time (trajectory optimization). This robust, AI (artificial intelligence)‐based technique, enables the solution of far more complex optimization problems than those reported in the literature. A set of several non‐dominating (equally good) Pareto optimal solutions was obtained. These provide insights into the conflicting nature of the objective functions. An engineer (decision maker) can then use his judgment (often intuitive) to choose the preferred solution from among these possibilities.

Pareto set of optimal solutions and some corresponding state variables for a Reference Problem.     

New algorithm for the numerical solution of the integro-differential equation with an integral boundary condition

In this paper, a sequence of approximate solution converging uniformly to the exact solution for a class of integro-differential equation with an integral boundary condition arising in chemical engineering, underground water flow and population dynamics and other field of physics and mathematical chemistry is obtained by using an iterative method. Its exact solution is represented in the form of series in the reproducing kernel space. The n-term approximation u _n (x) is proved to converge to the exact solution u(x). Moreover, the first derivative of u _n (x) is also convergent to the first derivative of u(x).     

Construction and utilisation of planar graphs of two series of IPR fullerenes through the use of threefold rotational symmetry

Threefold rotational symmetry has been used to develop an algorithm for the construction of planar graphs of IPR fullerenes and to factorize their characteristic polynomials. Two series of fullerenes of the formula C_60+12n and C_60+18n have thus been obtained. The algorithm has been shown to be useful for predicting the nature of variation of the point groups of the fullerenes with increased n, for counting the number of ¹³C nuclear magnetic resonance (NMR) signals (along with their relative intensities), and also for obtaining a large part of their eigenspectra. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

An NMR, DSC, and IR spectroscopy study of the composite formed during low-temperature postradiation polymerization of C2F4 in the presence of a 3D graphene material

By solid-state magic angle-spinning nuclear magnetic resonance spectroscopy (NMR), differential scanning calorimetry (DSC), and IR spectroscopy, polytetrafluoroethylene (PTFE) samples obtained by low-temperature (T = ?196°C) postradiation polymerization of tetrafluoroethylene (C₂F₄) and C₂F₄ mixtures with a 3D graphene material formed by the microwave exfoliation of graphite oxide films (MEGO) have been investigated. It has been shown that the melting point of PTFE in the PTFE-MEGO composite is 332.5°C, which is 8.8°C above the melting point of pure PTFE obtained under the same conditions. According to the measured values of specific enthalpy of melting ΔH _m (51.5 and 45.4 J/g), the degrees crystallinity (x _c) of 0.63 and 0.55 have been calculated for the pure polymer and the composite, respectively. It has been also found that none of the PTFE-containing samples examined has terminal CF₃ groups typical of PTFE prepared by conventional suspension polymerization.     

Multi‐Objective Optimization of a Batch Copoly(ethylene‐polyoxyethylene terephthalate) Reactor Using Different Adaptations of Nondominated Sorting Genetic Algorithm

Summary: A multi‐objective optimization is carried out for a copoly(ethylene‐polyoxyethylene terephthalate) (CEPT) batch reactor using different adaptations of the elitist nondominated sorting genetic algorithm (NSGA‐II). Several two objective function problems are formulated and solved. One objective is to minimize the total copolymerization time and other objective is to minimize the formation of total undesirable side products, namely, acid end group, vinyl ester end group, diethylene glycol ester end group of polyethylene terephthalate, and diethylene glycol. End‐point constraint is incorporated to obtain the specified number‐average degree of copolymerization. The operating temperature history of batch CEPT reactor is the only important decision variable for first optimization problem, whereas operating temperature history and molar ratio of feed to the reactor are taken as decision variables for the second optimization problem. Optimal Pareto frontiers are obtained for both the problems studied. In order to operate the polymerization reactor optimally, it is found that higher isothermal temperature history is needed for short copolymerization time, whereas lower nonisothermal temperature history is required for higher copolymerization time. The results of NSGA‐II technique are analyzed and compared with the jumping gene (JG) and adapted jumping gene (aJG) operator in NSGA‐II separately. It is found that NSGA‐II‐JG is superior to NSGA‐II and NSGA‐II‐aJG.

Optimization of a batch copoly(ethylene‐polyoxyethylene terephthalate) reactor.     

Electronic structure of poly(pyrrole–thiophene) copolymers: Design of polymeric quasi-one-dimensional superlattices

Ab initio band structure results of polypyrrole (PPY) and polythiophene (PTP) obtained with a double-zeta basis set are reported. The electronic density of states (DOS ) of the various quasione-dimensional copolymers (superlattices) of the type (A_mB_n)_x (A = pyrrole; B = thiophene) have been calculated numerically within the ab initio SCF tight-binding approximation. These copolymers on the basis of the band positions of PPY and PTP are found to belong to the class of type II (staggered) superlattices. The trends in their electronic properties as a function of (i) composition (m/n), (ii) block sizes m and n, and (iii) arrangement of blocks in the copolymer chain are discussed.     

Transformation of macromonomers into ring‐opening polymerization macroinitiators: A detailed initiation efficiency study

In the present study, n‐butyl acrylate macromonomer (BAMM) (M_n = 1900 g mol^?1; PDI = 1.96) has been synthesized via a high‐temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO₄ as an oxidizing agent. The OH‐terminated macroinitiator pBA(OH)₂ has subsequently been employed for the ring‐opening polymerization (ROP) of ε‐caprolactone via various catalytic systems, that is, organo‐(1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene), metal (tin(II) 2‐ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA‐b‐pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization–mass spectrometry (ESI‐MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε‐caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and—while they cannot be suppressed—they can be minimized. The species generated during the eROP process include the desired block copolymer pBA‐b‐pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH)₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Atomically Precise Alloy Nanoclusters

Metal nanoclusters (NCs) have a particle size of about one nanometer, which makes them the smallest unit that can give a function to a substance. In addition, metal NCs possess physical and chemical properties that are different from those of the corresponding bulk metals. Metal NCs with such characteristics are expected to be important for use in nanotechnology. Research on the precise synthesis of metal NCs and elucidation of their physical/chemical properties and functions is being actively conducted. When metal NCs are alloyed, it is possible to obtain further various electronic and geometrical structures and functions. Thus, research on alloy NCs has become a hot topic in the study of metal NCs and the number of publications on alloy NCs has increased explosively in recent years. Such publications have provided much insight into the effects of alloying on the electronic structure and function of metal NCs. However, the rapid increase in knowledge has made it difficult for researchers (especially those new to the field) to grasp all of it. Therefore, in this review, we summarize the reported chemical composition, geometrical structure, electronic structure, and physical and chemical properties of Au_n−xM_x(SR)_m, Ag_n−xM_x(SR)_m, Au_n−xM_x(PR₃)_l(SR)_m, and Ag_n−xM_x(PR₃)_l(SR)_m (Au=gold, Ag=silver, M=heteroatom, PR₃=phosphine, and SR=thiolate) NCs. This review is expected to help researchers understand the characteristics of alloy NCs and lead to clear design guidelines to develop new alloy NCs with intended functions.     

Controlled synthesis of rare-earth polyniobatotantalates

We report the results obtained during developing methods for a controlled synthesis of monometal and bimetallic low-hydrated hydroxides (LHHs) of composition Nb _n Ta_{1 − n} O _x (OH)_{5 − x} · mH₂O, which represent a new class of precursors, and use of their based intermediates in synthesis of rare-earth niobatotantalates to produce materials having high phase homogeneity.     

Direct Mass Spectrometric Study of the Ionic Species Content of a C<Subscript>2</Subscript>HCl<Subscript>3</Subscript>/He/O<Subscript>2</Subscript> Microwave Discharge Plasma

Direct on-line studies of a C₂HCl₃/He/O₂ microwave discharge plasma made possible the evolution and detection of many unfamiliar ionic species. Numerous ionic chlorocarbons, chlorohydrocarbons, oxygenated chlorohydrocarbons, oxygenated hydrocarbon radicals, and simple hydrocarbon species were identified mass spectrometrically as by-products: C _m Cl _n (m = 1–4, 6, 8; n = 1–8), C _m H _n Cl _x (m = 1–4, 6, 7, 10; n, x = 1–6), C _m H _n Cl _x O _y (m = 1–5, 12; n = 1–7; x = 1, 2, 4, 6; y = 1–3), C _n H_2n−1O (n = 2, 3), C _m H _n (m = 2, 4, 6, 8; n = 2, 4), and so on. The studies clearly showed the presence of various unfamiliar positive ionic O-containing species such as C₂ClO₂, CCl₃CO, C₂H₂Cl₄O₂, and C₄H₂Cl₆O₃. It is apparent that positive-ion reactions play a significant role in producing many ionic species in the chemistry of C₂HCl₃ plasmas.     

Solvent Effect in PLA-PEG Based Nanoparticles Synthesis through Surfactant Free Polymerization

Summary: In this work one-pot synthesis of PEGylated PLA-based nanoparticles (NPs) without using any surfactant has been performed. Adopting ring opening polymerization of L,L–Lactide and 2-hydroxyethyl methacrylate (HEMA), vinyl end functionalized poly(lactic acid) macromonomers (HEMA-LA_n) have been produced with tunable number of lactic acid units (larger than 5) and a low molecular weight distribution. Macromonomers have been further copolymerized with modified PEG chains (HEMA-PEG_m) through a monomer starved semi-batch emulsion polymerization performed without using any surfactant. In these conditions, small and monodispersed NPs of around 150 nm are obtained. Since macromonomers with n larger than 5 are highly viscous at room temperature, they have to be dissolved in a solvent before their injection in the reactor. In this work the effects in changing the solvent adopted in the starved process (water miscible or non-miscible) and its amount have been investigated. Moreover, the effect of both PEG chains concentration and MW on the final NPs properties has been elucidated. The colloidal stability of the NPs produced using different solvents has been verified in phosphate buffered saline (PBS) solution via dynamic light scattering measurements; in addition the critical coagulation concentration of these PEGylated NPs has been determined.