Orientational Measurements in Polymers Using Vibrational Spectroscopy

The mechanical properties of polymers are strongly influenced not only by the structure of the material but by the magnitude of the molecular orientation. Thus a great deal of interest exists in information about the molecular orientation in samples introduced by drawing or other forming processes. Several techniques of evaluation of this orientation exist such as birefringence, x-ray diffraction, sonic modulus, and fluorescence measurements [l, 2]. Vibrational analysis of oriented polymers provides a method of determining independently the molecular orientation both in the crystalline and amorphous phases of polymers. By using vibrational techniques, a number of macromolecules have been studied in the solid state for a variety of different processes. It is the purpose of this review to summarize the recent theoretical and experimental results which have occurred since the review of Zbinden [3]. Infrared and Raman measurements will be reported since they are complementary to each other in their applications and results.     

Current analytical methods for plant auxin quantification – A review

Plant hormones, and especially auxins, are low molecular weight compounds highly involved in the control of plant growth and development. Auxins are also broadly used in horticulture, as part of vegetative plant propagation protocols, allowing the cloning of genotypes of interest. Over the years, large efforts have been put in the development of more sensitive and precise methods of analysis and quantification of plant hormone levels in plant tissues. Although analytical techniques have evolved, and new methods have been implemented, sample preparation is still the limiting step of auxin analysis. In this review, the current methods of auxin analysis are discussed. Sample preparation procedures, including extraction, purification and derivatization, are reviewed and compared. The different analytical techniques, ranging from chromatographic and mass spectrometry methods to immunoassays and electrokinetic methods, as well as other types of detection are also discussed. Considering that auxin analysis mirrors the evolution in analytical chemistry, the number of publications describing new and/or improved methods is always increasing and we considered appropriate to update the available information. For that reason, this article aims to review the current advances in auxin analysis, and thus only reports from the past 15 years will be covered.     

Characterization of supramolecular polymers

Supramolecular polymers are made of monomers that are held together by noncovalent interactions. This is the reason for the wide range of novel properties, such as reversibility and responses to stimuli, exhibited by supramolecular polymers. A range of supramolecular polymerization methods have been developed leading to a number of novel supramolecular materials. However, standard techniques for the characterization of supramolecular polymers have yet to be established. The dynamic nature of supramolecular polymers makes them difficult to be fully characterized using conventional polymer techniques. This tutorial review summarizes various methods for characterizing supramolecular polymers, including theoretical estimation, size exclusion chromatography, viscometry, light scattering, vapor pressure osmometry, mass spectrometry, NMR spectroscopy, scanning probe microscopy, electron microscopy, and atomic force microscopy-based single molecule force spectroscopy. Each of these methods has its own particular advantages and disadvantages. Most of the methods are used to characterize the supramolecular polymer chain itself. However, some of the methods can be used to study the self-assembled state formed by supramolecular polymers. The characterization of a supramolecular polymer cannot be realized with a single method; a convincing conclusion relies on the combination of several different techniques.     

LC-MS-based procedures for monitoring of toxic organophosphorus compounds and verification of pesticide and nerve agent poisoning

Organophosphorus compounds (OPCs) are used worldwide as, e.g., flame retardants, plasticizers, and pesticides and remaining stockpiles of OPC nerve agents are present in military arsenals. These OPCs exhibit acute and potential chronic toxicity to man, the environment, and biota thus emphasizing the need for efficient analytical procedures to monitor potential risk to health. Therefore, this review discusses LC-MS-based procedures for OPC detection, addressing sample preparation, separation, ionization, and detection in comprehensive detail. For sample preparation conventional liquid-liquid extraction (LLE) and diverse solid-phase extraction (SPE) procedures are still used most frequently. Nevertheless, during the last three years a number of sophisticated novel methods have been introduced. Solid-phase microextraction (SPME), stir-bar-sorptive extraction (SBSE), membrane-assisted solvent extraction (MASE), and specifically designed molecularly imprinted polymers (MIP) exhibit high potential for frequent use in the future. Additional emphasis in this review is dedicated to the quite young history and current progress in ionization and MS detection of OPCs. The number of relevant published LC-MS reports has tripled in the last five years. This is especially due to the proliferating use of electrospray ionization (ESI), nowadays an indispensable and reliable tool for LC-MS coupling. LC-MS is becoming an appropriate complementary or replacement method for the more traditional GC-MS methods, and not only for non-volatile, hydrophilic, and ionic OPCs. The last section of this review covers recent approaches for verification of OPC poisoning. LC-MS-MS detection of phosphylated peptides generated from inhibited circulating serum butyrylcholinesterase (BChE) by valuable proteomics techniques enables proof of intoxication on the molecular level. Therefore, this review gives a comprehensive overview on the status quo of LC-MS-based OPC analysis in respect of both technical progress and relevant applications.      

Measurement of nanoparticles by light-scattering techniques

Nanoparticles (NPs), due to their unique physical and chemical properties, especially their minute particle size (?100 nm), find applications in numerous industrial, commercial and consumer products. After their end-user applications, these NPs find their way into the environment and food products. The NPs so discharged need to be quantified accurately to determine their toxicity and exposure levels.At this time, there is a need to develop a unified method for their determination. There are plenty of techniques available in the market that were initially used for colloidal particles (e.g., microscopy, spectroscopy and the recent addition of magnetic resonance), but each of these techniques has a certain degree of uncertainty.Further, sample homogeneity, sample preparation, instrument-operating procedures, and statistical practices are likely to add to the complexity of the problem. In this context, this review attempts to understand the widely-used light-scattering techniques, including their theory, practice and real-world use in determination of NPs in environmental and food applications.     

Verification of the microdomain model of crystallinity in polyvinyl chloride by electron microscopy

A study of the fine scale microstructure of PVC was carried out using a combination of high resolution transmission electron microscopy and digital image analysis techniques. The images obtained contained a degree of order of the approximate size and distribution as predicted by the microdomain model of crystallinity in PVC. The microdomain model for crystallinity in PVC has been built up from previous studies using various analytical techniques including wide- and small-angle x-ray diffraction and differential scanning calorimetry. Earlier studies using transmission electron microscopy did not find any direct evidence supporting this model. Significant advances in both electron microscope and image processing technology had taken place since the earlier microscopic studies. The TEM imaging and image analysis procedures that have been utilized in this research may be applicable to the imaging of very fine scale ordering in other polymers. © 1996 John Wiley & Sons, Inc.     

Cyclic polymers: Advances in their synthesis,properties, and biomedical applications

Since the time first synthetic macrocycles were observed as academic curiosities, great advances have been made. Thanks to the development of controlled polymerization processes, new catalytic systems and characterization techniques during the last decades, well-defined cyclic polymers are now readily accessible. This further permits the determination of their unique set of properties, mainly due to their lack of chain ends, and their use for industrial applications can now be foreshadowed. This review aims to give an overview on the recent progresses in the field of ring polymers to this day. The current state of the art of the preparation of cyclic polymers, the challenges related to it such as the purification of the samples and the scalability of the synthetic processes, the properties arising from the cyclic topology and the potential use of cyclo-based polymers for biomedical applications are as many topics covered in this review.     

Poly(lactic acid)‐based nanocomposites

Classic plastics accumulate in nature causing environmental pollution, yet as a counterbalance they benefit society in many ways. They are versatile, cost‐effective, and can be tailored to have desired properties. The global environment has led to the fabrication of commodity plastics from environmentally degradable polymers. Poly(lactic acid) (PLA) is the most promising among the environmentally friendly polymers available. PLA‐based plastics have mechanical, thermal, and transparency similar to traditional plastics, and they can be molded and fabricated using the same equipment and procedures. Their material properties are enhanced through nanocomposites, compatibilizers, plasticizers, and other fillers (flame retardant, ultraviolet filter, etc.). This review summarizes mass production techniques and property reinforcements (focusing on nanocomposites and plasticizers) for PLA‐based plastics for commodity use. Copyright © 2016 John Wiley & Sons, Ltd.     

Conductive polymer-based microextraction methods: A review

Conductive polymers (CPs) are classified as materials which exhibit highly reversible redox behavior and the unusual combined properties of metal and plastics. CPs, due to their multifunctionality, ease of synthesis and their stability, have attracted more attentions in different fields of research, including sample preparation. CPs along with several commercial hydrophilic sorbents, are alternative to the commercially available hydrophobic sorbents which despite their high specific surface areas, have poor interactions and retentions in the extraction of polar compounds. This review covers a general overview regarding the recent progress and new applications of CPs toward their synthesis and use in novel extraction and microextraction techniques including solid phase microextraction (SPME), electrochemically controlled solid-phase microextraction (EC-SPME) and other relevant techniques. Furthermore the contribution of nano-structured CPs in these methodologies is also reviewed.     

New Chromatographic and Hyphenated Techniques for Hydrophilic Copolymers

Most synthetic polymers are distributed in more than one parameter of molecular heterogeneity. For hydrophobic copolymers there are different chromatographic techniques available to analyse these distributions. As a result of the increasing interest in hydrophilic polymers and copolymers new chromatographic techniques are developed for the characterization of these polymers as well. However, very frequently these polymers contain highly polar or charged functional groups making them soluble only in aqueous mobile phases. There are several problems related to the use of aqueous mobile phases in polymer chromatography. Even the SEC analysis of such copolymers is not straightforward. As for HPLC in aqueous mobile phases, there are only a few applications in the literature so far. In addition to the fact that only a very limited number of stationary phases is available for aqueous HPLC of polymers, the interactions of polyelectrolytes in such chromatographic systems are not well understood. The present paper addresses the problems related to the application of SEC and HPLC in aqueous mobile phases. For graft copolymers with a polyethylene oxide backbone, e.g. PEG-g-polymethacrylic acid and PEG-g-polyvinyl alcohol, it will be shown that methods can be developed that give accurate molar mass and chemical composition information. Two-dimensional chromatography where aqueous HPLC and SEC are coupled on-line will be shown to be the most powerful analysis tool for the analysis of such copolymers. The hyphenation of the chromatographic separation techniques with spectroscopic detection techniques provides further insight into the molecular complexity of these copolymers.     

Chiral recognition applications of molecularly imprinted polymers: a critical review

Molecular imprinting technology offers the unique opportunity to tailor chiral stationary phases with predefined chiral recognition properties by employing the enantiomers of interest as binding-site-forming templates. Added advantages, such as ease of preparation, chemical robustness, low-cost production, and the possibility of shaping molecularly imprinted polymers (MIPs) in various self-supporting formats, render them attractive materials for a broad range of chiral recognition applications. In this review a critical overview on recent developments in the field of MIP-based chiral recognition applications is given, focusing on separation techniques and molecular sensing. Inherent limitations associated with the use of enantioselective MIP materials in high-performance separation techniques are outlined, including binding site heterogeneity and slow mass transfer characteristics. The prospects of MIP materials as versatile recognition elements for the design of enantioselective sensor systems are highlighted.     

Morphology of organosilicon ladder polymers

The morphology of organosilicon ladder polymers was studied by various methods, including x-ray techniques, diffraction of monochromatic polarized light, and electron microscopy. The morphology is discussed as a function of the chemical composition, the molecular weight, and the method of preparation.     

Thermal modification of layer-by-layer assembled gold nanoparticle films

Gold nanoparticle films are assembled on glass and quartz substrates by a simple and highly efficient layer-by-layer deposition procedure that uses only commercially available cationic polymers. The film samples are then modified by heat curing in the temperature range of 25–1100 °C. The changes in the film conductance and colour with the curing temperature are related to the respective changes in micro-morphology of films on quartz as observed by scanning electron microscopy. In addition, we have demonstrated that the heat curing can embed the gold nanoparticle layer in the glass substrates. Because of the preparation simplicity and peculiar properties of these films, they could be used in various practical applications.     

Mass spectrometry in the structural analysis of flavonoids

Flavonoids are very common and widespread secondary plant metabolites. They have a wide range of biological and physiological activities and serve as chemotaxonomic marker compounds. Therefore, they have been extensively investigated both in the past and during recent years. The interest in them is still increasing. In the search for new compounds, and also in quality control, there is a need to have reliable methodology for the analysis of flavonoids. Mass spectrometry can make an invaluable contribution because of its high sensitivity, possibilities of coupling with liquid chromatography and the availability of powerful tandem mass spectrometric techniques. A review of currently available mass spectrometric methodology used in the structure elucidation of flavonoids is presented. Sample preparation, liquid chromatographic/mass spectrometric analysis and tandem mass spectrometric procedures for the characterization of flavonoid aglycones, O-glycosides, C-glycosides and acylated glycosides are considered.     

"Clicking" on/with polymers: a rapidly expanding field for the straightforward preparation of novel macromolecular architectures

The combination of controlled polymerization techniques and "click" reactions form an efficient platform for the preparation of polymers in various architectures. In this critical review, an update of our 2007 review in Chem. Soc. Rev., we focus on the "click" reactions that have been used widely in the last four years to create new polymer architectures. Not only block copolymers and star-shaped polymers but also cyclic and dendritic macromolecules could be synthesized using these robust "click" reactions (205 references).     

New Routes to High Resolution and Automated Polymer Morphology Microscopy via Scanning Electron Microscopy

Summary: Polymer morphologies are traditionally studied by transmission electron microscopy (TEM). With the use of appropriate contrast enhancing heavy metal stains, direct images of the morphology as well as of the lamellar structure of semi-crystalline polymers can be obtained. Despite its clear strengths, this approach faces several challenges and difficulties: the laborious nature of ultra-thin section preparation, high capital investment, and no obvious routes to high-throughput. We propose an alternative approach to cover the major morphology imaging needs based on a new generation of high resolution scanning electron microscopes (SEM) that have been developed in recent years, and that does not rely on the need for ultra-thin section preparation. The proposed approach is capable of not only determining the general phase morphology, but also to image details such as the lamellar structure with sufficient resolution. Our approach is based on the use of backscattered electron imaging at low accelerating voltages. The backscattered electron images show high contrast and information content that is comparable to TEM. The main advantage of our SEM based approach is the ability to examine a polished surface, which requires less demanding sample preparation than producing ultra-thin sections. This opens the door to automated workflows where automated imaging, substantial productivity increases and high speed characterization options can be successfully realized. The successful approach is demonstrated for various polyolefin and engineering plastics samples.     

Molecularly imprinted polymers for sample preparation: A review

In spite of the huge development of analytical instrumentation during last two decades, sample preparation is still nowadays considered the bottleneck of the whole analytical process. In this regard, efforts have been conducted towards the improvement of the selectivity during extraction and/or subsequent clean-up of sample extracts. Molecularly imprinted polymers (MIPs) are stable polymers with molecular recognition abilities, provided by the presence of a template during their synthesis and thus are excellent materials to provide selectivity to sample preparation. In the present review, the use of MIPs in solid-phase extraction and solid-phase microextraction as well as its recent incorporation to other extraction techniques such as matrix-solid phase dispersion and stir bar sorptive extraction, among others, is described. The advantages and drawbacks of each methodology as well as the future expected trends are discussed.     

The use of (metallo-)supramolecular initiators for living/controlled polymerization techniques

The introduction of supramolecular interactions in synthetic polymers seems to be a promising approach towards novel 'smart' materials that combine both the (reversible) supramolecular interactions and the properties of the polymers. In this tutorial review, the use of (metallo-)supramolecular initiators for the preparation of end-functionalized (metallo-)supramolecular polymers will be discussed in detail. The different polymerization techniques that have been applied as well as the different ligands and metal complexes that were used to initiate these polymerizations will be discussed together with the resulting polymer properties.     

Recent Progress,Challenges and Prospects in Monitoring Plastic-Derived Xenoestrogens Using Molecularly Imprinted Sorbents

Indoor and outdoor exposure to plastic-derived xenoestrogens, such as phthalates and phenolic compounds, can adversely affect endocrine and reproductive systems in humans and wildlife. To accomplish the extraction of plastic-derived xenoestrogens from environmental samples, molecularly imprinted polymers (MIPs) have been proved to be selective, efficient, and reliable sorbents. Despite some problems associated with the use of MIPs as sorbents, these have been found to be of considerable interest due to their advantages of selectivity, easy synthetic procedures, and better stability over commercially available solid sorbents. Modifications in their synthetic strategies are continuously in progress and new approaches are being made through graphene oxide substrates, nanostructured platforms, nanoferrites, cryogels, and co-electropolymerization to design better sorbents. Apart from this, efforts to create molecularly imprinted solid phase microextraction (SPME) fibers have also been successful in improving the efficiency of the methodology. In future, the use of MIPs developed from advanced synthetic strategies, or as sorbents for more robust techniques like SPME and microextraction on packed sorbents, will add new horizons to explore the potential of MIPs in the field of plastic-derived xenoestrogens. This review presents various challenges, as well as progress and prospects associated with the extraction of plastic-derived phthalates and phenolic compounds using molecularly imprinted sorbents.