Interaction between the strong anionic character of strong anions and the hydrophobic association property of hydrophobic blocks in macromolecular chains of a water‐soluble copolymer

The copolymerization of acrylamide, sodium 2‐acrylamido‐2‐methyl propane sulfonate, and styrene was carried out in a microemulsion medium, and ternary copolymers based on polyacrylamide, which contained both strong anionic groups (? SO₃Na) and hydrophobic blocks (polystyrene), were synthesized. The structures and compositions of the copolymer were characterized by various means (Fourier transform infrared, ultraviolet, and elemental analysis). The aqueous solution properties were investigated with a florescence probe technique and apparent viscosity measurements, and the interactions between the strong anionic character of the anionic groups and the hydrophobic association behavior of the hydrophobic blocks was intensively examined. After the simultaneous addition of the strong anionic groups and hydrophobic association blocks to the main chains of polyacrylamide, the synergism of the electroviscosity effect of the strong anionic groups and the hydrophobic association effect of the hydrophobic blocks obviously enhanced the apparent viscosity of aqueous copolymer solutions, and the synergism of greater salt tolerance of the strong anionic groups and the strengthened hydrophobic association of the hydrophobic blocks in brine solutions resulted in increased salt resistance for the copolymer. However, the presence of strong anionic groups (? SO) in the macromolecules weakened the intermolecular hydrophobic association effect of the copolymer in aqueous solutions to a certain degree; that is, the strong anionic groups produced a certain negative influence on the hydrophobic association effect of the hydrophobic blocks. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 714–722, 2005     

Chain helicity of a poly(phenylacetylene) with chiral centers between backbone and mesogenic groups on side chains

An optically active poly(phenylacetylene), poly{2-(R)-methyl-2-[4′-(tetradecyloxy)biphenyl-4-yloxy]propyl 4-ethynylbenzoate} (P1) is synthesized in a high yield with a high molecular weight (1.3 × 10⁶ g/mol) by [Rh(nbd)Cl]₂ catalyst. The chemical structure of the polymer is characterized by IR and NMR spectroscopies with satisfactory analysis data. The polymer is soluble in many common organic solvents. It shows circular dichroism (CD) band in the absorption region of the polyacetylene backbone, indicating that P1 is chiroptical owing to the formation of helical conformation with an excess screw sense. Combining the results of CD and light scattering experiments, we find that addition of poor solvent can induce the neighboring helical segments within a single polymer strand to become closer, resulting in exciton coupling prior to polymer precipitation. The exciton coupling can be kept in the solid state after solvent evaporation.     

Influence of various chemical treatments on the interactions between hemp fibres and a lime matrix

In this paper, results presented concern both the chemical and physical behaviours of hemp fibres in lime-based mineral matrix in order to better understand the role of chemical modifications of cellulosic fibres in the evolution of the macroscopic properties, essentially mechanical ones, of such composite materials. The role of fibres surface treatment has been also studied through various chemical treatments applied on hemp fibres. In a first step, the influence of such treatments on the fibre characteristics has been investigated by several means, such as scanning electron microscopy, thermal analysis, X-ray diffraction and FTIR spectroscopy, in order to evaluate their consequences on the fibre behaviour itself. Secondly, an attempt to characterise the influence of the various chemical treatments of fibres on the mechanical behaviour of hemp reinforced lime-based composites has been completed by a three points bending testing campaign. According to the results, it seems that the modifications induced by specific chemical treatments (EDTA, NaOH) on fibres play a major role in the strengthening of the lime/fibres interface but also in the improvement of the overall stiffness of the composite (with respect to the one reinforced by untreated fibres) most probably related to a specific stiffening process of the fibre itself.     

Enhanced dead-end elimination in the search for the global minimum energy conformation of a collection of protein side chains

Although the conformational states of protein side chains canbe described using a library of rotamers, the determinationof the global minimum energy conformation (GMEC) of a largecollection of side chains, given fixed backbone coordinates,represents a challenging combinatorial problem with importantapplications in the field of homology modelling. Recently, wehave developed a theoretical framework, called the dead-endelimination method, which allows us to identify efficientlyrotamers that cannot be members of the GMEC. Such dead-endingrotamers can be iteratively removed from the system under studythereby tracking down the size of the combinatorial problem.Here we present new developments to the dead-end eliminationmethod that allow us to handle larger proteins and more extensiverotamer libraries. These developments encompass (i) a procedureto determine weight factors in the generalized dead-end eliminationtheorem thereby enhancing the elimination of dead-ending rotamersand (ii) a novel strategy, mainly based on logical argumentsderived from the logic pairs theorem, to use dead-ending rotamerpairs in the efficient elimination of single rotamers. Thesedevelopments are illustrated for proteins of various sizes andthe flow of the current method is discussed in detail. The effectivenessof dead-end elimination is increased by two orders of magnitudeas compared with previous work. In addition, it now becomesfeasible to use extremely detailed libraries. We also providean appendix in which the validity of the generalized dead-endcriterion is shown. Finally, perspectives for further applicationswhich may now become within reach are discussed.     

4-OH-TEMPO radical grafted onto a novel polyaromatic ether sulfone containing carboxyl side chains as solid catalyst for alcohol oxidation

2,2,6,6-Tetramethylpiperidinium-nitroxide (TEMPO) is a mild and efficient catalyst, which is important in the industrial production of selective oxidation of alcohols to the corresponding aldehyde or ketone compounds. However, it is a challenge to recover the expensive TEMPO catalyst in homogeneous catalytic systems. In this study, a novel polymer-supported catalyst was prepared using 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (4-OH-TEMPO) and polyaromatic ether sulfone (PAES). The successful grafting of 4-OH-TEMPO in PAES-C was demonstrated by ¹H nuclear magnetic resonance (¹H NMR) and Fourier transform infrared (FT-IR), load capacity can be calculated by elemental analysis (EA). BET and scanning electron microscopy (SEM) to depict the structure-performance relationship. Herein, SEM images revealed the existence of porous structure. This structure can effectively adsorb NO molecules to form a PAES-TEMPO/NO_x catalytic system to selectively oxidize benzyl alcohol. The experimental results indicated the high activity, the subsequent benzyl alcohol oxidation cycle can reach more than 93% conversion without showing a large loss of selectivity. More importantly, the as-prepared catalyst exhibited the attractive recyclability (recovery rate is 98%). After 10 consecutive runs, no significant loss of conversion and selectivity was observed (the conversion rate of benzyl alcohol was more than 93% and the selectivity was more than 95%). This study might provide some recommendation on the development of highly efficient catalysts for alcohol oxidation.     

Substituted poly(silylenemethylene)s with short range interactions that induce a preference for the same local conformation in unperturbed atactic, isotactic, and syndiotactic chains

A rotational isomeric state model has been developed for the poly(silylenemethylenes) with repeating sequence [Si(CH₃)R-CH₂]_x, R=-O(CH₂)_NOC₆H₄C₆H₅. The model incorporates all first- and second-order interactions, as well as higher order interactions that are mandatory in some of the conformations. Chains with all possible stereochemical sequences prefer a local conformation that is a run of trans states at the C-Si bonds in the backbone. This preference arises from an attractive second-order interaction of the first methylene group in the side-chain bonded to chain atom i with the silicon atoms indexed i±2. Unperturbed chains have larger dimensions than the simpler chain in which R is merely a methyl group. The temperature coefficients of the unperturbed dimensions are large and negative. The preference of unperturbed atactic, isotactic, and syndiotactic chains for the same local conformation may contribute to the facile formation of smectic phases by the presumably atactic chain, as reported by Park et al. [Macromolecules 35 (2002) 2776].     

IR spectroscopy approach for the study of interactions between an oxidized aluminium surface and a poly(propylene-g-acrylic acid) film

In this paper, we report the study of the interactions between a poly(propylene-g-acrylic acid) and an oxidized aluminium surface by IR spectroscopy. A deposit of a pure poly(acrylic acid) on the same surface is used as a model. Under free acid form (COOH) we demonstrate the formation of hydrogen bondings between the acrylic carboxyl groups and OH functions located at the surface of alumina. This is characterized by an IR absorption [v_(c?o)] at 1733 or 1743 cm^?1 when we observe the metal surface either after peeling of a PPg(OH) film initially pressed on it or after a deposit of PAA(OH). Under the carboxylate form (COO^?), we observe two modes of interaction, the one purely ionic between COO^? and Al³⁺ with an absorption located near 1550 cm^?1 and the other of complex form between COO^? and Al³⁺ giving a band near 1610 cm^?1. The water molecules can play a major part, in particular in the first case (COOH) where they destroy hydrogen bondings in favor of the formation of ? COO^? groups, interacting with the metal surface according to ionic or complex modes as above. © 1993 John Wiley & Sons, Inc.     

Study of a nanocomposite starch–clay for slow‐release of herbicides: Evidence of synergistic effects between the biodegradable matrix and exfoliated clay on herbicide release control

In this article a nanocomposite based on starch gel, a renewable polymer, and montmorillonite clay (MMT) is proposed as a host system for the slow‐delivery of a hydrophobic herbicide loaded in very high contents (50% in total weight), where the nanocomposite structure controls the release by imposing diffusional barriers to the active compound. The herbicide release rate in water showed that nanocomposites presented higher retentions than the neat samples (herbicide‐loaded starch or MMT), revealing a cooperative or synergic effect between the constituents. Biodegradation essays also revealed this cooperative behavior, showing longer biodegradation periods for the nanocomposite than the pristine materials. Also, a two‐step release was noticed, where the first step was controlled by starch (short periods) and the second was played by MMT (longer times). The nanocomposite structural analysis gave evidence that the release behavior is governed by the interaction between the constituents, even at very high herbicide contents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41188.