Graft Copolymerization of Vinyl Monomers onto Cellulose and Cellulosic Materials

Abstract

Graft copolymerization is a novel method which has wide application in synthesizing new forms of polymeric materials and also in modifying the properties of natural polymers [1,2]. Much research has been done on grafting polymeric molecules on to cellulose to produce materials of new properties intermediate between those of cellulose and those of synthetics. A variety of property changes can be imparted to cellulose through grafting without destroying the crystallinity or crystallization potential of the substrate or reducing its melting point. Some of the most dramatic changes in properties which have been brought about by grafting to cellulose are viscoelasticity, stereoregularity, hygroscopicity, water repellency, improved adhesion to a variety of substances, settability, soil resistance, bacteriocidal properties, and thermal stability.     

MOLECULAR TRANSPORT OF ORGANIC LIQUIDS THROUGH POLYMER FILMS

Abstract

The molecular transport of small molecules through polymer films has been the subject of active research over almost three decades [1–8]. The main thrust in this area is either to accumulate a large body of experimental data to assess the stability of polymer films for extreme serviceability or to develop new theories which describe the phenomenology of transport processes, the latter often being studied in terms of three important parameters: permeation, diffusion, and solubility, in adition to the swelling phenomenon.     

Biological applications of amide and amino acid containing synthetic macrocycles

ABSTRACT

Amino acid derived macrocycles with elaborate well-defined stereochemistry are a unique class of compounds that have been isolated from natural sources. Macrocycles like cyclosporine, octreotide, and valinomycin have been used in multiple applications, like drugs or ion sensors. Chemists have long been fascinated by the unique molecular recognition capabilities of these macrocycles and tried to design synthetic analogs with similar functions. This article is focused on reviewing current research on amide and amino acid containing macrocycles that have been developed in research laboratories for biological recognition, specifically for anion sensing, ion transport, carbohydrate sensing, and peptide sensing.     

Nonlinear Neural Mapping Analysis of the Adverse Effects of Drugs

Abstract

Numerous drugs have been identified as presenting adverse effects towards the driving of vehicles. A large set of these drugs was compiled and classified into ten categories. Nonlinear neural mapping (N2M) was used to derive a typology of these molecules and also to link their adverse effects to therapeutic categories and structural information.     

Thickness dependent penetrant gas transport properties and separation performance within ultrathin polysulfone membrane: Insights from atomistic molecular simulation

Simulation technique has been employed to elucidate the effect of thickness upon confinement to gas transport properties in pure and binary mixtures within ultrathin polysulfone membranes. It is found that the gas diffusivity, solubility, and permeability are improved with increment in membrane thickness, which can be rationalized through bigger free volume in thicker polymeric membranes attributed to diminishing chains relaxation. The effect is found to be exceptionally perceptible in thinner polymeric films beneath 400 Å. Accuracy of the simulation methodology has been validated by demonstrating good accordance with actual gas permeability data. As for binary condition, the gas transport properties are demonstrated to be comparatively lower than its pure counterpart due to competitive sorption and barrier for diffusion in the presence of secondary gas molecules. In addition, quantitative re‐evaluation of published correlations and establishment of new empirical models have been conducted to associate membrane thickness effect to gas transport characteristics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 131–158     

Applications of High Performance Size Exclusion Chromatography To The Analysis of Oligomers and Small Molecules

Abstract

Size exclusion chromatography of small molecules has been investigated with high efficiency columns of crosslinked polystyrene. Performance evaluations and calibrations have been determined in toluene and in tetrahydrofuran, and the effect of the solvents on solute retention is discussed. Oligomer separations of samples obtained in the thermal degradation of several polymeric materials are reported, and the utility of the technique for polymer degradation studies is clearly evidentiated.     

超分子化学药物研究

超分子药物化学是超分子化学在药学领域的新发展．该领域研究活跃,发展迅速,是一个充满活力的新兴交叉学科领域,并正在逐渐变成一个相对独立的研究领域．迄今已有许多两个或两个以上分子通过非共价键力形成的超分子化学药物应用于临床．超分子化学药物可具有良好的安全性、低毒性、不良反应少、高生物利用度、药物靶向性强、多药耐药性小、生物相容性好、高疗效以及其开发成本低、周期短、成功可能性大等诸多优点而备受关注,显示出超分子化学药物具有很大的发展潜力．本文首次给出了超分子药物的定义．结合自己的工作,参考国内外文献综述了超分子化学药物在抗肿瘤、抗炎镇痛、抗疟、抗菌、抗真菌、抗结核、抗病毒、抗癫痫、作为心血管和磁共振成像药物等医药领域的研究与开发状况,并展望其发展趋势与应用前景．     

Performance of solvent-resistant membranes for non-aqueous systems: solvent permeation results and modeling

Membrane processes like reverse osmosis (RO) and nanofiltration (NF) can be low energy consuming operations as compared to the traditional chemical engineering unit operations and have been widely used for aqueous systems. Since such membrane processes are low energy consuming operations, their use in non-aqueous systems would offer considerable energy savings. Thus, the study is directed towards development and experimental verification of membrane materials and transport models to explain permeation properties of non-aqueous solvent systems. The understanding of polymer–solvent interactions is critical towards the development of suitable materials and also the prediction of the transport mechanisms.Pure solvent permeation studies were conducted to understand the mechanism of solvent transport through polymeric membranes. Different membrane materials (hydrophilic and hydrophobic) as well as different solvents (polar and non-polar) were used for the study. Pure solvent fluxes for hydrophilic membranes used showed that polar solvents (methanol, ethanol, iso-propanol) had a significantly higher flux (8–10 times) than that of the non-polar solvents (pentane, hexane, octane). On the contrary, the non-polar solvent flux was two to four times that of the polar solvents for hydrophobic membranes. For example, hexane flux at ∼13 bar through a hydrophobic silicone based NF membrane was ∼0.6×10⁻⁴ cm³/cm² s. And that through a hydrophilic aromatic polyamide based NF membrane was ∼6×10⁻⁴ cm³/cm² s. A simple model based on a solution-diffusion approach is proposed for predicting the pure solvent permeation through hydrophobic polymeric membranes. The model uses molar volume and viscosity of the solvent as parameters for predicting the pure solvent permeability. The model reasonably predicts the pure solvent permeation (R²=0.89, S.E.∼4%) for hydrophobic membranes. The model has also been experimentally verified using high solution temperatures and also literature experimental data. To extend the predictions to different membranes (hydrophilic and hydrophobic), surface energy and sorption values have been used as a parameter along with the solvent physical properties.     

Polymeric Nanocomposites—Polyhedral Oligomeric Silsesquioxanes (POSS) as Hybrid Nanofiller

Abstract

Polyhedral oligomeric silsesquioxane (POSS), a hybrid nanostructured macromer has been used in the last decade for preparation of polymeric nanocomposites. Its versatile chemistry, which lends it for almost infinite chemical modification, sets it apart from other nanostructured fillers like nanoclays, carbon nanotubes, and carbon nanofibers. Depending on its functionality, 3‐D network, bead or pendant type‐POSS based polymeric nanocomposites can be synthesized. These have the potential to be designed for products with specific nanostructures for specific end‐use applications. This article discusses the trends in current research involving use of POSS macromers for modification of mainly thermal and viscoelastic properties of various polymers.     

Study of Thin Polymeric Film Deposited by the PECVD Process for use at 193 nm

A plasma enhanced chemical vapor deposition (PECVD) reactor was used to deposit thin polymeric films with high absorption at 193 nm. The reactor is suitable to deposit uniform and pinhole free thin polymeric films with conformality over 95%. Conformal films with thickness as low as 200 Å have been deposited on silicon, glass, and quartz substrates, as well as silicon oxide, silicon nitrate, and aluminum films. Deposited films had variations in thickness of 3 to 5% over an area of 8 inches in diameter. Thin films deposited on silicon substrates under varying levels of RF power were scanned using the AFM technique. The measurements show increasing surface roughness of the scanned samples as the RF power increases.     

Influence of the presence of small gas molecules in the structure of comblike polyacrylates: a Monte Carlo study

A theoretical strategy has been developed to study the motion of small molecules through ordered polymeric systems. The strategy, which has been incorporated into a computer program denoted MCDP/2, is especially useful to study comblike polymers organized in biphasic arrangements. This is because it is based on a configurational bias Monte Carlo algorithm, which is more efficient than conventional methods to study dense systems. The MCDP/2 program has been used to investigate the influence of CH(4) and CO(2) gas molecules in the structure of isotactic poly(octadecyl acrylate), a typical comblike polymer. For this purpose, the pure polymer and different molecular systems constituted by several gas molecules dissolved in the polymer matrix have been simulated. Results indicated that the structural relaxation of the polymer is not coupled to the motion of gas molecules. The importance of these results in the field of molecular modeling of transport properties in comblike polymers is discussed.     

Crystal Structures of Aripiprazole, a New Anti-psychotic Drug, and of its Inclusion Compounds with Methanol, Ethanol and Water

Aripiprazole, 7-[4-[4-(2,3-dichlorophenyl)-1-piperazinyl]butoxy]-3,4-dihydrocarbostyril, is an important new neuroleptic drug used in the treatment of schizophrenia and related psychoses. This study elucidates its detailed molecular structure and two preferred conformational forms, and relates to the solvates of this compound when crystallized from different environments. The latter is associated with the hydrogen-bonding capacity of aripiprazole through the piperazinyl and dihydrocarbostyril functions. Four unique crystal forms of this compound have been characterized using X-ray single crystal determinations, including an anhydrous structure (1), methanol (2) and hemi-ethanol (3) solvates and a hydrate (4). They were found to consist of hydrogen bonded dimers of the aripiprazole moieties that involve the cyclic (–NH–CO–)₂ di-amide interaction synthon in 1–3 (with the solvent molecules attached to them in 2 and 3), or of hydrogen bonded polymeric aggregates sustained by extended multiple bonding through water bridges in 4. These modes of supramolecular association involve two different conformers with similar energy of the drug moiety.     

QUANTITATIVE ASPECTS OF POLYMER DEGRADATION IN THE LIVING BODY

Abstract

Over the last several decades extensive clinical research has been devoted to the medical application of polymeric implants. Scientists in the last few years have paid special attention to the chemical physics of the processes that accompany the reaction of polymers with living tissue. Two main questions must first be answered in this type of study.     

Interaction of solid and polymeric lithium electrolytes with composites based on carbon fibers and silicon nanoclusters: Quantum-chemical modeling

In the framework of the search for promising electrodes and membranes for lithium-ion batteries, quantum-chemical modeling of the contact area of the solid (Li₁₀GeP₂S₁₂) and polymeric LiNafion · nDMSO-based electrolytes with an anode as carbon fibers coated with silicon nanoclusters (Si _n C _m ) has been performed by the density functional theory method with inclusion of gradient correction and periodic conditions (PBE/PAW). It has been found that the polymeric electrolytes form a better contact with the electrode surface than the solid electrolytes. The barriers to lithium transport in the polymeric LiNafion · nDMSO-based electrolyte have been estimated at 0.3 eV, and those to Li migration from the electrolyte into the electrode have been estimated at 0.4 eV.     

Polymeric particulates to improve oral bioavailability of peptide drugs

Oral administration remains the most convenient way of delivering drugs. Recent advances in biotechnology have produced highly potent new molecules such as peptides, proteins and nucleic acids. Due to their sensitivity to chemical and enzymatic hydrolysis as well as a poor cellular uptake, their oral bioavailability remains very low. Despite sophisticated new delivery systems, the development of a satisfactory oral formulation remains a challenge. Among the possible strategies to improve the absorption of drugs, micro- and nanoparticles represent an exciting approach to enhance the uptake and transport of orally administered molecules. Increasing attention has been paid to their potential use as carriers for peptide drugs for oral administration. This article reviews the most common manufacturing methods for polymeric particles and the physiology of particle absorption from the gastrointestinal (GI) tract. In a second part, the use of polymeric particulate systems to improve the oral absorption of insulin is discussed.     

Hydrogen-bonded Networks in Crown Ether Complexes of Hydrated Metal Ions

Abstract

The hydrated metal nitrates (M(NO₃)₃.6H₂O, M[dbnd]Co, Ni, Cu, Zn and Cd) have been crystallised from water in the presence of 18-crown-6 and their structures determined by X-ray crystallography. In the case of copper, a pseudo four-coordinate square planar complex resides in an extended six-coordinate octahedral array which is further bound in a single-stranded one-dimensional hydrogen bonded polymeric mode. For M[dbnd]Co,Ni,Zn and Cd isomorphous complexes are isolated where the octahedral [M(H₂O)₅(NO₃)⁺ cation resides in a two-dimensional polymeric network through hydrogen bonds between the water ligands and either the crown ether oxygens or unbound nitrate ions or water molecules.     

LABORATORY SYNTHESIS OF POLYETHYLENE GLYCOL DERIVATIVES

Abstract

In recent years, derivatives of polyethylene glycol (PEG) have proven valuable in a variety of diverse chemical and biological endeavors. Such applications include peptide synthesis, phase transfer catalysis, pharmaceutical modification, protein and cell purifications, polymer-bound reagents, and binding assays. Because of the great deal of interest surrounding this subject, this review will describe generally applicable laboratory methods for preparing PEG derivatives from the parent PEG. We have largely restricted discussion to this starting material because most research laboratories interested in applications are not equipped to handle complex ethylene oxide polymerizations used in large-scale industrial preparations and because PEG and some of its ethers and esters are the only commonly available polymeric starting materials. For the purpose of this review, PEG is defined as those polyoxyethylenes having hydroxyl endgroups and a molecular weight of 20,000 daltons or less.     

Synthesis and characterization of a dipeptide–copper(II)– 2-aminomethylbenzimidazole ternary complex

A new ternary complex [Cu(glygly)(AMBZ)(H₂O)]Cl·H₂O (1) (glygly?=?glycylglycine anion, AMBZ?= 2-aminomethylbenzimidazole) has been prepared and characterized by single-crystal X-ray diffractometry and ESR, electronic and IR spectroscopy. The copper(II) ion has a slightly distorted square-pyramidal coordination, being equatorially coordinated by the bidentate 2-aminomethylbenzimidazole and the bidentate glycylglycine anion and axially by a water molecule. The individual complex molecules are hydrogen bonded to their neighbors, forming a polymeric hydrogen-bonded lattice. Spectroscopic data are in accordance with the crystal structure.     

Predicted Influence of N-Acetyl Group Content on the Conformational Extension of Chitin and Chitosan Chains

ABSTRACT

Conformational analysis of chitosan molecules has been performed using the MM3(92) force field to investigate the role played by the acetamido groups on the stiffness of these chains. A high dielectric constant value was needed to model an aqueous environment and to reproduce the distribution of the N-acetyl glucosamine group orientation that is observed by NMR. Disaccharidic fragments, differently substituted at C2, were selected as models for chitin and chitosan chains. Their conformational space has been explored by means of adiabatic mapping of the glycosidic Φ,Ψ torsion angles. Although the overall features of all the potential energy surfaces created appear similar, the accessible conformational space of a glycosidic bond is affected by the nature of the substituent at C2 on the non-reducing residue of the disaccharide unit. This is illustrated by the differences in the calculated partition functions together with the predicted average homonuclear and heteronuclear coupling constants. Computed maps were used to predict polymeric unperturbed dimensions, characteristic ratio and persistence length of idealized chitin and chitosan chains, by Monte Carlo methods. Pure chitosan is predicted to be more coiled than pure chitin chains. At low N-acetyl group contents, chain extension appears to be dependent on the degree of substitution. Average chain dimensions increase monotonically for increases in content up to 60% of N-acetyl groups, but show no significant variation at higher contents. For molecules consisting of 50% amino and 50% N-acetylated residues, random, alternate and block patterns of substitution have been investigated. It has also been shown that the spatial extension of the polymer chains is dependent on the primary structure. Comparison with the literature experimental data is difficult because of the extreme diversity of the reported conformationally dependent values. However, such study provides a unique insight into the dependence of these two factors (degree of acetylation and distribution of acetyl groups) on the stiffness and flexibility of different chitin and chitosan chains.     

Polymeric seven-coordinated organotin(IV) complexes derived from 5-amino-2-chlorobenzoic acid and in vitro anti-cancer studies

Cancer cases are alarmingly increasing worldwide, and newer chemotherapeutic agents are needed. Recent analogs of cisplatin (carboplatin, lobaplatin, nedaplatin and oxaliplatin) and their marketing as advanced chemotherapeutic drugs have furthered the interest in metal-based anti-cancer drugs. In the current study, two new polymeric organotin(IV) carboxylate complexes (1 and 2) have been synthesized and characterized. Spectroscopic studies showed that coordination took place via carboxylates. Furthermore, X-ray crystallographic study on 1 indicated that it possesses a monomeric structure and exists in polymeric formation due to additional Sn–N coordination, assigning seven coordinations to each metal ion. Both the complexes were tested against three cancerous (human colon cancer, HCT 116; breast cancer, MCF-7; and leukemia, K562) and one non-cancerous (3T3-L1) cell lines. Complex 1 showed exceptional cytotoxicity against cancerous cell lines (IC₅₀ = 1.0 μM for HCT 116; 258.7 nM for MCF-7; and 46.7 nM K562) and remained comparatively non-toxic against normal cells (IC₅₀ = 37.0?μM). This shows that both complexes have selective cytotoxicity against cancer cells.