GRAFT COPOLYMERIZATION OF CELLULOSE,CELLULOSE DERIVATIVES,AND LIGNOCELLULOSE

Abstract

The growth of polymer science has led to the development of new materials in direct competition with natural materials, many of which have been in use since earliest times. This has caused researchers to look more critically at both natural and synthetic macromolecules in order to learn more about their underlying structures and their relation to the properties exhibited by the macromolecules. In this regard, chemical modifications have been devised to impart certain desirable properties of both natural and synthetic macromolecules, and their applications have become an integral part of such chemical modifications. Various chemical modifications (e.g., change of functionality, oxidative degradation, inter- and intramolecular gelation, graft copolymerization), have been practiced to add improved properties to the base polymers. However, among all these methods, modification of polymers via graft copolymerization has been the subject of much interest and has made paramount contribution toward improved industrial and biomedical applications.     

Cooperative conformational transitions of linear biopolymers

Conformational transitions in proteins, nucleic acids, and other biopolymers evidently play a decisive role in many biological processes, particularly in control processes. They often proceed cooperatively, i.e. the elementary process of the transition of an individual segment of these macromolecules in influenced by the state of other segments via intramolecular interactions. In general, the segments favor the same state as their neighbours. The resulting equilibrium properties of cooperative systems, e.g. the sharpness of the transitions and their dependence on the chain length, can be quantitatively explained for linear systems by the linear Ising model. The molecular causes of the cooperativity can be explained for simple model polymers.     

Structure and properties of single complex macromolecules and of related bulk systems

Structure and dynamics of complex macromolecules in computer simulated systems is analyzed. The algorithm based on cooperative molecular rearrangements is applied to various macromolecular structures represented in a simplified form on the lattice. Various macromolecular architectures such as linear chains, stars, dendrimers, bottle‐brush polymers as well as cyclic chains and catenane are considered both as single molecules and as dense systems corresponding to polymer melts. A broad range of structural parameters characteristic for each system is taken into account. In some cases, the simulation results are compared with the behavior of real systems in which the structure and dynamics has been studied by X‐ray scattering and mechanical spectroscopy, respectively.     

Seeking high-sensitivity flow injection analysis

The use of flow-injection systems for biotechnology assays is attrctive but the reduced sensitivity of such systems over their manual descrete-sample counterparts has limited their use. Model systems are studied to develop the concepts needed for the design of high-sensitivity flow-injection systems for the determination of macromolecules. Both open- and packed-tube systems were examined. Initial hydrodynamic studies were done with dye; then selected designs were tested for protein determinations based on a bromocresol green assay. The packed-bed systems provided better mixing, but dispersion was about the same as that of the open-tube systems and back-pressures were much higher. This work indicates that combinations of narrow (i.d. ? 0.5 mm) and short (? 10 cm) open tubes, small-volume flow cells (8 μl) and slow flow rates (? 0.05 ml min^-1) give better sensitivity.     

Interactions of quinine with polyacrylic and poly-L-glutamic acids in aqueous solutions

Drug-loaded polymers provide an attractive form for controlled drug delivery systems. A proper knowledge of polymer-drug interactions can aid in the designing of polymers for various drug-delivery applications. In this paper we have investigated the interaction of a drug such as quinine, with synthetic macromolecules such as poly(acrylic acid), PAA, and poly(L-glutamic acid), PGA, at pH 7 and 37 °C by fluorescence spectroscopy and viscometry. The analysis of the binding isotherms revealed that the association process is positive cooperative up to a threshold concentration and then it is negative. In addition, the thermodynamic parameters vary along the isotherm. Results also suggest that there is an optimum polymer to quinine ratio. Based on the viscometry results a mechanism of the interaction in which the polymer conformation plays a determinant role is proposed. Since the conformation depends on the molecular size, the architecture of the macromolecule, the effective charge and ergo the ionic strength, all these variables have been taken into account and their effect on the binding discussed.     

Conformation and rigidity of ladder polymer molecules

Two new samples of cyclo-linear polyphenyl-siloxane (CLPhS) and a sample of cyclo-linear poly-3-methyl-butene-1 silsesquioxane (CLMBS) have been investigated by viscometry, diffusion, sedimentation and flow birefringence methods. The size of the Kuhn statistical segment (A), characterizing the rigidity of macromolecules, was determined from hydrodynamic models using the theory of a persistent model. The values of A greatly exceed the corresponding values for flexible (coil-shaped macromolecules) and for linear siloxanes. This confirms the ladder structure of the double main chain of the polymers under investigation. The values of segmental anisotropy, anisotropy of the monomer unit and the unit length of the macromolecules in the CLPhS samples were determined from dynamooptical properties. A comparison of the rigidity for the three CLPhS samples investigated (one of them studied previously) shows that it is different for different samples. This fact suggests that the flexibility mechanism of polymers of this type is affected by the defectiveness of structure, i.e. by the occurrence of single bonds in the main chain. It is shown that the study of hydrodynamic and optical properties of the molecules of such polymers may serve as a sensitive method for detection and quantitative investigation of defectiveness of structure.     

A rheological,optical, and x-ray study of the relaxation of orientation of nematic PBZT

The ultimate properties of liquid crystalline polymers depend upon the achievement of high orientation, usually by means of flow fields. The properties are limited by disorientation which can occur before the product is solidified. Such cooperative orientation and disorientation phenomena also underlie the complex fluid rheology and product microstructure of these materials. The orientation and subsequent disorientation can be followed dynamically by optical and x-ray techniques. Normally, monitoring of orientation is possible only by “fast” techniqes, such as birefringence, these are not applicable to opaque and strongly scattering liquid-crystalline systems. To enable examination of the full dynamic response of concentrated nematic solutions of poly(1,4-phenylene-2,6 benzobisthiazole) (PBZT) the Daresbury Synchrotron Radiation Source was used. PBZT is among the most rigid macromolecules and serves as a good model for other materials of its class. The orientation process determined optically and from x-rays is correlated with fluid rheology and availabel theoretical approaches. During relaxation from near perfect mesogen alignment three principal stages of the disorientation process were identified corresponding to solvent disorientation (first stage of stress relaxation), banding (slow stress relaxation and mesogen disorientation), and finally a very slow banding to polydomain transition. © 1993 John Wiley & Sons, Inc.     

Polymers in living systems: from biological lubrication to tissue engineering and biomedical devices

The roles of macromolecules in living systems as information storage systems (as DNA) and in biochemical synthesis have been much studied and are relatively well understood. Far less is known about their physical behavior at biological surfaces and interfaces. This review considers in particular the roles of polymers in biological lubrication and its relation both to diseases such as osteoarthritis and to remedies such as tissue engineering. The lubricating behavior of common bio‐interfacial macromolecules including mucins, hyaluronan, lubricin, and aggrecan are described, and insights into the mechanism of biolubrication are examined in the light of the recently revealed role of hydration lubrication in water‐based (including living) systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Polymer complexes stabilized through hydrogen bonds: A semiquantitative theoretical model

Many studies have been devoted to the formation and behavior of polymer complexes. Unfortunately, the complexity of such systems do not allow a rigorous theoretical approach presently. In this paper we develop a semiquantitative theoretical model for cooperative association between macromolecules. The model is especially adapted for reversible polymer complexes stabilized through weak interactions, e.g., through hydrogen bonds. Theoretical predictions are compared with potentiometric and viscometric experimental results of poly(acrylic acid)/polybase system and a good agreement is established. The influence of parameters such as degree of neutralization of the polyacid, concentration, and molecular weight of polymers is also conveniently predicted.     

Dendrons and dendritic catalysts immobilized on solid support: Synthesis and dendritic effects in catalysis

Dendrimers, the aesthetically beautiful macromolecules displaying a variety of potentially useful architecture‐induced properties, are traditionally assembled in solution. However, since 1988, a number of dendritic structures have been assembled on insoluble organic and inorganic polymers, and thus dendronized supports have been formed. One of the major applications of these new materials is in the field of heterogeneous catalysis. Supported dendritic catalytic systems, bearing the catalytic units on the dendron periphery, have been examined in the last 5 years in such reactions as hydroformylation, Heck and other Pd‐catalyzed C? C bond formations, oxidation, and enantioselective addition to aldehydes. In the majority of these studies, substantial dendritic effects on the reactivity, selectivity, or recyclability of the catalysts were observed. Although a number of factors have been suggested as sources of the effects, it is most likely that the phenomenon has a multicomponent origin. Additional research, including a full determination of the effects and their causes, is likely to lead to markedly better heterogeneous catalytic systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 235–262, 2005     

基于冠醚衍生物的超分子聚合物

自组装现象是生命科学最本质的内容之一,生物体系可以精确地利用非共价键相互作用形成高度有序的功能组装体.受到大自然的启发,近年来利用分子自组装构筑包括超分子聚合物在内的有序聚集体是超分子科学的研究热点.此类组装体不仅在拓扑学上具有重要的意义,而且可以用来制备动态的超分子功能材料.冠醚作为第一代超分子主体化合物,由于其结构...     

Biorecognizable polymers: Structure-properties relationship

The biocompatibility of polymers depends on their chemical composition, as well as physical and physico-chemical structure. However, biocompatibility is not an intrinsic polymer property since it relates to a particular localization of the polymer in the living organism. Any foreign macromolecule may be recognized by the living organism as “non-self”. The degree of recognition can be altered by modification of the structure of macromolecules or biomaterial surfaces. Modification of biomacromolecules (e.g., enzymes¹) or biomaterial surfaces with hydrophilic polymers, e.g., poly(ethylene oxide²) or other semitelechelic hydrophilic macromolecules³ has been shown to minimize biorecognition. On the other hand, to achieve specific recognition by cell receptors and/or antigens, complementary structures have to be incorporated as a part of the polymer structure^{4, 5}. The biorecognition of fluorescently labeled N-(2-hydroxypropyl)-methacrylamide copolymers containing side-chains terminated in acylated galactosamine by Hep G2 cells on the cellular and subcellular levels can be visualized by confocal fluorescence microscopy. The recognition of modified water soluble macromolecules strongly depends on their solution properties⁶. Incorporation of stimuli sensitive moieties into copolymer side-chains permits to control recognition by external stimuli, e.g., irradiation^{7, 8}, resulting in the change of the copolymer conformation. On the other hand, the biorecognition of unsoluble (crosslinked) copolymers depends mainly on their surface structure. The rationale for the structure modification of synthetic copolymers to regulate biorecognition will be reviewed. The principles will be described for the interaction of synthetic polymers with enzymes⁹, cell surface receptors and/or antigens^{10, 11}, lectins of the gastrointestinal tract^{12, 13}, and immobilized lectins¹⁴.     

The relationship between intramolecular hydrogen bonds and certain physical properties of regioselectively substituted cellulose derivatives

This article tries to provide some direct evidence about the relationship between the intramolecular hydrogen bonds in cellulose and their corresponding effect on physical properties. The formation of intramolecular hydrogen bonds has been proved to contribute directly to certain physical properties of cellulose, such as its solubility in solvents having different polarities, the relative reactivities of the hydroxyls in a repeating unit and its crystallinity, using a 6-O-methylcellulose (6MC) film that was known¹ to have intramolecular hydrogen bonds. The excellent solubility of 6MC when compared with other cellulose derivatives indicated a lack of interchain hydrogen bonds. A comparison of the relative reactivities between the C-2 and C-3 position hydroxyls in 6MC also indicates that intramolecular hydrogen bonds once formed in 6MC films are possibly maintained even after dissolution in solvents. In addition, the poor crystallinity exhibited by 6MC supports the idea that crystallization in cellulosics may be dependent more upon preferencial interchain hydrogen bonding at the C-6 position hydroxyls than upon a uniform structure such as that found in 6MC, where every structural unit is completely and regioselectively substituted, distinguishing it from other synthetic polymers such as polyolefins and polyesters. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 717–723, 1997     

Maxwell and Kerr effects in solutions of linear dendritic macromolecules

The linear dendritic polymers of the first and second generations have been investigated by the methods of flow birefringence and equilibrium and nonequilibrium electric birefringence. The side dendrons are attached to the polymer backbone through benzamide groups and contain long terminal hexyloxycarbonyl fragments. Optical, dynamic, dipolar, and conformational characteristics of the macromolecules in question have been analyzed in detail. It has been found that the macromolecules of dendritic polymers with dendrons based on L-aspartic acid possess permanent dipole moments and reorient in external electric and hydrodynamic fields according to the large-scale rotation mechanism. The introduction of rigid benzamide fragments substantially increases the equilibrium rigidity, optical anisotropy, and dipole moment of monomer units of dendritic macromolecules. The role of macro-and microform effects in the formation of optical features of the molecules under study is considered in detail.     

Thermosensitive Water–Polymer Systems Studied by Luminescent Spectroscopy. Copolymers of N-vinylcaprolactam and N-vinylpyrrolidone

Thermosensitive aqueous solutions of N-vinylcaprolactam/N-vinylpyrrolidone (co)polymers were investigated by luminescent spectroscopy. Investigation of the luminescent intensity and the bound fraction of luminescence indicators interacting to the (co)polymers in water showed that the chemical structure of the water-soluble poly-N-vinylamides defines their functional and structural characteristics such as conformation, intramolecular mobility, compactization and complexation. It was established that the complexing ability of VCL-VP copolymers exceeds that of PVP even at a low content of VCL units. At 85 mol% of VCL the complexation and compactization of the macromolecules were found to be higher than that of pure PVCL. A hinge-like action of VP units incorporated in PVCL structure is suggested to be a reason of the extreme behavior observed for 85:15 VCL:VP composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

Conformational characteristics of stereoregular PMMA and of the stereocomplex: new insights from FTIR measurements

Isotactic (i) and syndiotactic (s) PMMA polymers differ markedly in the physical properties. The fact that these physically unlike macromolecules strongly attract each other with the resultant formation of stereocomplexes is indeed remarkable. Although stereoregular PMMAs and the stereocomplex have been studied over decades, their conformational characteristics are yet a matter of controversy. We performed variable-temperature FTIR measurements on i-PMMA and s-PMMA, followed by a detailed analysis of the temperature dependence of integrated band intensities for C-O stretching modes in the region 1050-1300 cm⁻¹ and achieved, for the first time, the unambiguous conformational assignment for the C-O bands. This enabled reliable IR spectroscopic determination of conformational energies for the backbone and for the ester group. Besides, a comparative analysis of the C-O band intensities in the FTIR spectra of single-component and stereocomplex PMMA films, based on the established band assignments, revealed new features in the structure of the stereocomplex.     

Water sorption by poly(tetrahydrofurfuril methacrylate)'s

Polymers consisting of poly(heterocyclic methacrylate)s are considered as potential materials for clinical applications such as drug delivery and cartilage repair. Much of the success of these systems has been attributed to the complex nature of their water sorption properties. Dielectric permittivity is very sensitive to water sorption. Dielectric relaxation spectroscopy studies have been carried out on two heterocyclic poly(methacrylate)s: poly(tetrahydrofurfuryl methacrylate) (PTHFMA) and poly(3‐methyl tetrahydrofurfuryl methacrylate) (P3MTHFMA). The isochrones representing the dielectric losses show in both cases high conductivity at low frequencies and high temperatures. In PTHFMA two conductive processes are observed, which can be associated to the existence of two types of water sorption. These effects have been analyzed and were removed from the dielectric spectra by using classical empirical equations. Both polymers show ostensible α‐relaxation centered in the vicinity of 350 K at 10⁰ Hz. This relaxation was analyzed by means of the empirical Havriliak‐Negami equation. Reminiscent β‐relaxation could also exist. Both polymers present well defined γ and δ subglass absorptions at approximately 120 K, 160 K for PTHFMA and 125 K, 163 K for P3MTHFMA, at 10⁰ Hz, associated to local intramolecular relaxations in side groups. These relaxations were analyzed using semiempirical symmetric model. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 109–120, 2008     

Synthesis and properties of polycondensation polymers from compounds with asymmetric functional groups

The effect of conditions of polycondensation on the structure of polymers formed from monomers with symmetric and asymmetric functional groups by nonequilibrium polycondensation has been studied for the system with acceptor-catalytic polyesterification of β-hydroxyethyl ethers of bisphenols and terephthalic acid chloride in the presence of triethylamine. Polymers with statistical or regular arrangement of diol residues in the chain can be produced in such systems, depending on the way in which starting compounds are introduced in the reactor. A difference in the reactivity of functional groups in an asymmetric monomer is not sufficient to produce polycondensation polymers with a regular structure. Gradual introduction of the symmetric monomer is essential to yield polymers with predominant “head-to-head” (“tail-to-tail”) configurations. Some properties of the resulting polymers have been studied. Polymers with ordered residues of the asymmetric monomers in the macromolecules have higher softening temperatures and an increased tendency for crystallization than the statistic polymers.     

Gradient polymers and copolymers

Gradient polymers are two component polymeric systems in which the concentration of one component varies in a continuous way from one side to the other in systems with plane-parallel geometry. Such systems can be obtained from an amorphous polymeric matrix by diffusing into another monomer creating a gradient of concentration, which is fixed by, for example, photo-polymerization. Properties of such systems with plane-parallel geometry are discussed. Paricular attention is given to the systems with cylindrical geometry in which the gradient of the second polymer varies from the center to outside. This class of gradient polymers has a great practical application as gradient optical polymeric fibers and multifocal lenses. An interesting and new class of gradient polymers are systems systems consisting of semicrystalline polymeric matrices in which a gradient of structure is created by appropriate thermal treatment and an amorphous polymer gradient is formed by diffusion of a monomer and its subsequent polymerization. The structural, thermal and mechanical properties are discussed mainly for a model system consisting of polyethylene and polystyrene. The polymeric gradient systems, consisting of an oriented semicrystalline polymer and amorphous gradient polymer, are discussed showing that the structurally gradient matrices and amorphous polymer offer a great variety of factors which can influence the properties of multicomponent gradient polymers. Recently obtained gradient copolymers in which the chemical composition varies from one end to the other a macromolecule are presented. It is shown how such macromolecules can be obtained with different type of changes of the composition. The unusual properties of gradient copolymers are discussed considering their mechanical and thermal properties as well their specific behaviour as compatibilizers. © 1998 John Wiley & Sons, Ltd.     

Interpolymer complexes of poly(N-vinylpyrrolidone) with copolyimide-grafted side chains of poly(methacrylic acid)

The process of formation and structural organization of interpolymer complexes formed by macromolecules of poly(N-vinylpyrrolidone) and poly(methacrylic acid) chains grafted onto polyimide in solution is investigated via the method of polarized luminescence. A luminescent label of anthracene structure is covalently bound to both polymers. Relaxation times characterizing intramolecular mobility of each of the components in their interpolymer complex are measured in relation to the composition of the system.