Oligomeric Side Chains Research Articles

Structural characterization of corn fiber hemicelluloses extracted by organic solvent and screening of degradation enzymes

An integrated treatment coupling peracetic acid delignification, dimethyl sulfoxide extraction, and ethanol precipitation were performed to isolate hemicellulose from de-starched corn fiber. Based on chemical composition, molecular weight distribution, methylation, and nuclear magnetic resonance spectroscopy, it is proposed that hemicelluloses in corn fiber were composed of two polysaccharides, glucuronoarabinoxylan (about 80 %) and xyloglucan (about 20 %). Xylose (about 46 %) and arabinose (about 32 %) were the main components in glucuronoarabinoxylan. More than half of the xylose units in the glucuronoarabinoxylan backbone chain were substituted at O-2 and/or O-3 by various monomers or oligomeric side chains. Based on structure analysis, five hemicellulases were selected and added to Penicillium oxalicum MCAX enzymes for enzymatic hydrolysis of corn fiber. The results showed that the addition of hemicellulases increased the sugar yield of corn fiber. These results demonstrate the effectiveness of enzyme consortium constructed by elucidating the chemical structure of hemicellulose in corn fiber for the degradation of corn fiber and also provide a general solution for the rational construction of targeted and efficient enzyme systems for the degradation of lignocellulosic biomass.

Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties: The Case of Oligoxazoline-Based Graft Polymers.

Many synthetic polymers used to form polymer-brush films feature a main backbone with functional, oligomeric side chains. While the structure of such graft polymers mimics biomacromolecules to an extent, it lacks the monodispersity and structural purity present in nature. Here we demonstrate that side-chain heterogeneity within graft polymers significantly influences hydration and the occurrence of hydrophobic interactions in the subsequently formed brushes and consequently impacts fundamental interfacial properties. This is demonstrated for the case of poly(methacrylate)s (PMAs) presenting oligomeric side chains of different length (n) and dispersity. A precise tuning of brush structure was achieved by first synthesizing oligo(2-ethyl-2-oxazoline) methacrylates (OEOXMAs) by cationic ring-opening polymerization (CROP), subsequently purifying them into discrete macromonomers with distinct values of n by column chromatography, and finally obtaining poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs) by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Assembly of POEOXMA on Au surfaces yielded graft polymer brushes with different side-chain dispersities and lengths, whose properties were thoroughly investigated by a combination of variable angle spectroscopic ellipsometry (VASE), quartz crystal microbalance with dissipation (QCMD), and atomic force microscopy (AFM) methods. Side-chain dispersity, or dispersity within brushes, leads to assemblies that are more hydrated, less adhesive, and more lubricious and biopassive compared to analogous films obtained from graft polymers characterized by a homogeneous structure.

Reversible aggregation of particles with short oligomeric sidechains at the surface studied with Langevin dynamics

We investigate nanoscopic aggregation of asphaltene nanoaggregates by means of Brownian dynamics simulations. Nanoaggregates that represent clusters of 6–10 asphaltene molecules are modelled as spherical particles with an attractive core consisting of polyaromatic hydrocarbons rings and short aliphatic tails that protrude from the surface, as in a spherical brush. As two such nanoaggregates approach each other, the steric repulsion that arises from interactions between the tails, is modelled using Alexander-de Gennes theory and Derjaguin approximation, while the attraction upon contact between polyaromatic cores, caused by van der Waals and other interactions is modelled as a Morse potential. The aggregation occurs when the steric barrier is overcome and the cores come into contact. Our simulations show that, with shallow interaction potentials, that is, with weak attractions and low barriers, the nanoaggregates form small agglomerates with ramified structure that are in metastable equilibrium with uniform solutions. These agglomerates can be described with a fractal dimensions below 1.5, which may represent soluble asphaltenes. The increase in attraction strength promotes aggregation and destabilizes the systems as in the case of dilution with a flocculant, for which several aggregation regimes are observed. Increasing the well-depth and/or barrier for nanoaggregate interaction leads to classical diffusion limited and reaction limited regimes. We find that with high barrier the clusters formed are less close-packed, and may represent the weak gel state typical for bitumen gel.

Synthesis and self-assembly of fluorene-vinylene alternating copolymers in “Hairy-Rod” architecture: side chain – mediated tuning of conformation, microstructure and photophysical properties

In the present work, we demonstrate that the side chain choice, as a tunable parameter, is an effective strategy to drive molecular ordering, packing motifs and overall microstructure of a conjugated polymer. By applying Wittig polycondensation novel ‘rod-coil’ structures, in ‘hairy-rod’ architecture, based on fluorenylene vinylene copolymers with well-defined oligomeric side chains were synthesized using ‘T’-shaped or ‘Cross’-shaped p-terphenyl macromonomers. The overall character of the copolymers was systematically varied by attaching of hydrophilic PEG 2000, hydrophobic polar oligo-ε-caprolactone or hydrophobic and non-polar oligostyrene side chains. Self-assembling of the copolymers by simple direct dissolution method was achieved in various solvents by modifying their selectivity in relation to the side chain or main chain. The morphology investigations demonstrated that unique nanofeatures obtained in each case (helical foldamers, vesicles, disks, or helical turns) depend on the nature, number, and position of the side chains which influence the photophysical properties. The ‘hairy-rod’ topology is also responsible for the self-assembly of the materials in molten state, as thermal analysis revealed, and the propensity of the new synthesized conjugated main chain for helical folding was evidenced, as well.

Photochromic Spirooxazines Functionalized with Oligomers: Investigation of Core−Oligomer Interactions and Photomerocyanine Isomer Interconversion Using NMR Spectroscopy and DFT

Photochromic spirooxazines functionalized with poly(ethylene glycol) (PEG) and poly(dimethylsiloxane) (PDMS) oligomers were monitored using NMR spectroscopy at temperatures between 193 and 233 K before and after in situ exposure to UV irradiation. NOESY and ROESY experiments reveal the TTC (trans-s-trans-cis) isomer to be the dominant merocyanine isomer formed on photolysis, with some CTC (cis-s-trans-cis) isomer also present. Significant ROE cross peaks were observed between the "bulk" of the oligomeric units and protons across the entire photochromic core of the molecule, the intensity of these cross peaks suggesting that the interaction of the oligomer side chain and core of the molecule is significantly enhanced by the permanent attachment, especially with the PDMS side chain. The 2D NMR spectra indicate that there is exchange between the TTC and CTC isomers even at 193 K. This isomerization of the parent spirooxazine compounds, lacking the oligomeric side chains, was found to be acid-catalyzed, and DFT calculations support the strong possibility that it is the protonated merocyanine form that undergoes the facile isomerization process. Interconversion of the different merocyanine isomers is suggested to be fast on the NMR time scale under many experimental conditions, precluding the observation of different isomers using NMR spectroscopy at room temperature.

Towards Monodomains of Self-Organized Comb-Shaped Polymeric Supramolecules

AbstractWe have previously shown that hierarchical self-organization is achieved upon physically bonding amphiphilic molecules to diblock copolymers. Here we discuss the effect of imposed shear flow to achieve overall alignment of the locally self-organized structures. We will first present shear aligned polystyrene-block-poly(4-vinyl pyridine) diblock copolymers (PS-b-P4VP), where pentadecyl phenol (PDP) has been hydrogen bonded to the pyridines. Depending on the selected molecular weights, eg. hexagonal arrangement of PS cylinders in the lamellar matrix of P4VP(PDP) can be obtained with high overall order of both structures. This is a template to obtain discrete PS nanorods, which have P4VP corona once the PDP molecules have been cleaved off by a solvent treatment. Selecting a relatively high molecular weight PS block and a short P4VP block leads to mesoporous materials with emptied cylinders with P4VP brushes at the walls. The glassy state of the PS matrix prevents the pores from collapsing. The pyridine groups of PS-b-P4VP can be protonated using eg. toluene sulphonic acid and the resulting polymeric salt has been complexed using PDP. The weight fractions have been selected so that the polyelectrolyte/amphiphile complex self-organizes into cylindrical domains with hexagonal packing. Shear alignment leads to high overall order. SAXS in combination with structural models suggests that within the cylinders there are parallel self-organized layers. The conductivity is anisotropic. We will also discuss dielectric reflectors based on self-organized block polyelectrolytes consisting PS-b-P4VP where DBSA has been complexed to P4VP. In this case, plasticization due to the oligomeric side chains promotes a facile structure formation at long periodicities in comparison to concepts based on eg. blends of high molecular weight polymers and block copolymers. Finally, plasticized comb-shaped supramolecules based on rigid conjugated poly(p-pyridine) are discussed. Even gentle shearing leads to highly aligned lamellar structures, which show efficient polarized photoluminescence.

A new kind of ternary copolymer for ionic conduction

Two novel ternary copolymers, MNEC-TPC-LDABS and MMEC-TPC-LDABS, were synthesized by condensation copolymerization of mannitol-containing oligomeric side chains (MNEC) or melamine-containing oligomeric side chains (MMEC) with terephthaloyl chloride (TPC) and lithium 2,5-diaminobenzene sulfonate (LDABS), respectively, to become thermally stable and mechanically strong ionic conductors. Incorporating anionic groups (SO) into the structure of copolymers increases mobile cation concentration and introducing MNEC and MMEC enhances ionic conductivity via flexible chain motion assistance. The conductivity (ς) of MNEC-TPC-LDABS is 7.82 × 10−5 S/cm and of MMEC-TPC-LDABS is 9.17 × 10−5 S/cm, both measured at 25°C. The crystallinity and Tg of the copolymers were greatly decreased by the incorporation of dendritic macromolecule units of MNEC or MMEC. The temperature dependencies of the ionic conductivity for two polymers show curved Arrhenius plots, which suggest that ionic conduction is closely associated with segmental motion of the polymer hosts. The conductivity of the polymer electrolytes obeys the Williams–Landel–Ferry (WLF) and Vogel–Tammann–Fulcher (VTF) equation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 953–959, 1999

Effective dispersants for concentrated, nonaqueous suspensions

With the aim of identifying effective dispersants that would yield stable, high solids loading (≥60 vol.%) suspensions of oxides, carbides, or nitrides in nonaqueous carriers such as paraffinic oils, a number of dispersants were evaluated, using in most cases A16SG grade alumina from Alcoa as the filler. Among those evaluated were some common dispersants, such as menhaden fish oil and oleic acid, and commercial dispersants not commonly used in ceramic processing, such as polymeric fatty esters and petroleum sulfonates. More importantly, a few dispersants were synthesized and evaluated. The latter dispersants contained straight or cyclic (benzenic) side chains located far from the head group on 18 carbon main-chain fatty acid molecules. Among these, the dispersants with a 5–10 carbon side chain or with a benzenic side chain yielded very fluid suspensions (≥60 vol.%) compared to those with long polymeric or oligomeric side chains, or with no side chains, or the commercial dispersants; in some cases, for the same solid loading, the suspension viscosities were an order of magnitude lower with the synthesized side chain dispersants. These results indicate that molecules with an optimum side chain length located sufficiently far from the head group and an optimum backbone (main chain) constitute the most effective dispersants for concentrated suspensions. By combining the advantages provided by wider particle size distributions and by these effective dispersants, suspensions highly concentrated (up to 74 vol.%), and yet processable and “flowing” paste-like have been prepared.

The chiral smectic H liquid crystalline structure of a comb-shaped side-chain polymer

The polymer investigated is a comb-shaped polymer with long oligomeric side chains containing a chiral center. The chiral center contains the strongly dipolar nitrile group bound to the aliphatic spacer between aryl units in a stereo-ordered fashion. The chemical structure of the comb polymer is shown below:

The influence of the side-chain sequence on the structure-activity correlations of immunomodulatory branched polypeptides. Synthesis and conformational analysis of new model polypeptides.

New branched polypeptides were synthesized for a detailed study of the influence of the side-chain structure on the conformation and biological properties. The first subset of polypeptides were prepared by coupling of tetrapeptides to poly[L-Lys]. These polymers contain either DL-Ala3-X [poly[Lys-(X-DL-Ala3)n]] or X-DL-Ala3 [poly[Lys-(DL-Ala3-X)n] (n less than or equal to 1)] tetrapeptide side chains. Another group of branched polymers comprise a mixture of DL-Alam and of DL-Alam-X oligomeric branches in a random distribution [poly[Lys-(DL-Alam-Xi)] (i less than 1, m approximately 3)]. In each subset the X = Leu or Phe derivatives were prepared. The N-protected tetrapeptides were synthesized by conventional liquid phase methods and were coupled as active esters. The degree of racemization was found relatively high both for active esters and coupled derivatives, when optically active amino acids were in the C-terminal position of the tetrapeptides. In the case of the poly[Lys-(Leu-DL-Ala3)n] derivative, comparative experiments were carried out using various methodical alterations. The highest stereochemical homogeniety could be achieved when the tetrapeptide active ester was synthesized by the "backing off" method. CD spectra of poly[Lys-(Xi-DL-Alam)] (i less than 1, m approximately 3) and of poly[Lys-(X-DL-Ala3)n] were analyzed and compared to those of poly[Lys-(DL-Alam-Xi)] and of poly[Lys-(DL-Ala3-X)n]. All measurements were performed in water solutions of varying pH values and ionic strengths. The data obtained suggest that branched polypeptides containing a mixture of two different types of oligomeric side chains (DL-Alam and DL-Alam-Xi or Xi-DL-Alam) distributed randomly adopt an almost identical conformation to those that comprise only the respective tetrapeptide (DL-Ala3-X or X-DL-Ala3) branches. The results also indicate that the tendency to form an ordered structure is determined by the identity and the position of the chiral amino acid X (Phe or Leu) in the side chain.

Attachment of (1→6)-linked malto-oligosaccharide side-chains to amylose and cellulose via 1,2-orthoesters

Comb-like molecules having oligomeric side-chains were prepared by condensation of peracetylated 1,2-(ethyl orthoacetate) derivatives of maltose, maltotetraose, and maltohexaose with 2,3-di- O-phenylcarbamoyl derivatives of amylose and cellulose. The distance between the maltose, maltotetraose, and maltohexaose branch-points introduced into amylose was 3–4, 10, and ∼ 17 d-glucose residues, respectively, and only slightly greater for cellulose. Thus, the branch frequency is considerably higher than that obtained previously by using the Bredereck and Helferich reactions. After saponification of the modified polysaccharides, the side chains of d.p. 4 and 6 attached to position 6 in the d-glucose residues of amylose and cellulose were easily extended by enzymic synthesis with potato phosphorylase.