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Polymers Nov 2018Polyhydroxyalkanoates (PHAs) are polyesters synthesized by bacteria as a carbon and energy storage material. PHAs are characterized by thermoplasticity,... (Review)
Review
Polyhydroxyalkanoates (PHAs) are polyesters synthesized by bacteria as a carbon and energy storage material. PHAs are characterized by thermoplasticity, biodegradability, and biocompatibility, and thus have attracted considerable attention for use in medical, agricultural, and marine applications. The properties of PHAs depend on the monomer composition and many types of PHA monomers have been reported. This review focuses on biosynthesized PHAs bearing aromatic groups as side chains. Aromatic PHAs show characteristics different from those of aliphatic PHAs. This review summarizes the types of aromatic PHAs and their characteristics, including their thermal and mechanical properties and degradation behavior. Furthermore, the effect of the introduction of an aromatic monomer on the glass transition temperature () of PHAs is discussed. The introduction of aromatic monomers into PHA chains is a promising method for improving the properties of PHAs, as the characteristics of aromatic PHAs differ from those of aliphatic PHAs.
PubMed: 30961192
DOI: 10.3390/polym10111267 -
Polymers Aug 2022A molecularly imprinted polymer (MIP) is a synthetic polymer that has characteristics such as natural receptors which are able to interact and bind to a specific... (Review)
Review
A molecularly imprinted polymer (MIP) is a synthetic polymer that has characteristics such as natural receptors which are able to interact and bind to a specific molecule that is used as a template in the MIP polymerization process. MIPs have been widely developed because of the need for more selective, effective, and efficient methods for sample preparation, identification, isolation, and separation. The MIP compositions consist of a template, monomer, crosslinker, initiator, and porogenic solvent. Generally, MIPs are only synthesized using one type of monomer (mono-functional monomer); however, along with the development of MIPs, MIPs began to be synthesized using two types of monomers to improve the performance of MIPs. MIPs used for identification, separation, and molecular analysis have the most applications in solid-phase extraction (SPE) and as biochemical sensors. Until now, no review article has discussed the various studies carried out in recent years in relation to the synthesis of dual-functional monomer MIPs. This review is necessary, as an improvement in the performance of MIPs still needs to be explored, and a dual-functional monomer strategy is one way of overcoming the current performance limitations. In this review article, we discuss the techniques commonly used in the synthesis of dual-functional monomer MIPs, and the use of dual-functional monomer MIPs as sorbents in the MI-SPE method and as detection elements in biochemical sensors. The application of dual-functional monomer MIPs showed better selectivity and adsorption capacity in these areas when compared to mono-functional monomer MIPs. However, the combination of functional monomers must be selected properly, in order to achieve an effective synergistic effect and produce the ideal MIP characteristics. Therefore, studies regarding the synergistic effect of the MIP combination still need to be carried out to obtain MIPs with superior characteristics.
PubMed: 36080573
DOI: 10.3390/polym14173498 -
Cell Chemical Biology Jul 2022A critical step in repurposing the cellular translation machinery for the synthesis of polymeric products is the acylation of transfer RNA (tRNA) with unnatural... (Review)
Review
A critical step in repurposing the cellular translation machinery for the synthesis of polymeric products is the acylation of transfer RNA (tRNA) with unnatural monomers. Toward this goal, flexizymes, ribozymes capable of aminoacylation, have emerged as a uniquely adept tool for charging tRNA with ever increasingly diverse substrates. In this review, we present a library of monomer substrates that have been tested for tRNA acylation with the flexizyme system. From this mile-high view, we provide insights for understanding the chemical factors that influence flexizyme-mediated tRNA acylation. We conclude that flexizymes are primitive esterification catalysts that display a modest binding affinity to the monomer's aromatic recognition element. Together, these robust, yet flexible, flexizyme systems provide researchers with unprecedented access for preparing unnatural acyl-tRNA and the opportunity to repurpose the translation machinery for the synthesis of novel biologically derived structures beyond native proteins and peptides.
Topics: Acylation; Catalysis; Peptides; RNA, Catalytic; RNA, Transfer; Transfer RNA Aminoacylation
PubMed: 35413283
DOI: 10.1016/j.chembiol.2022.03.012 -
Journal of Molecular Biology May 2013Cooperativity of ligand binding to allosteric receptors can be quantified using the Hill coefficient (nH) to measure the sigmoidal character of the binding curve.... (Review)
Review
Cooperativity of ligand binding to allosteric receptors can be quantified using the Hill coefficient (nH) to measure the sigmoidal character of the binding curve. However, for measurements of the transition between conformational states, nH values can be misleading due to ambiguity of the reference state. For cooperative ligand binding, the reference state is a hyperbolic curve for a monomer with a single binding site characterized by nH=1. Therefore, binding curves with nH>1 provide a direct measure of cooperativity. For the dependence of the conformational state on ligand concentration, curves with nH>1 are observed, but in virtually all cases, the equivalent allosteric monomer has a value of nH<1. The ratio of the two nH values defines the effective cooperativity and always corresponds to nH=N (the number of protomers in the oligomer) for concerted transitions as specified by the Monod-Wyman-Changeux model. Dose-response curves for homopentameric α7 nicotinic receptors illustrate this relationship for both wild-type and mutant forms. For functional allosteric monomers such as G-protein-coupled receptors, normalization stretches the dose-response curve along the y-axis, thereby masking the "allosteric range" and increasing the apparent cooperativity to a limit for monomers of nH =1. The concepts of equivalent monomer and allosteric range were originally proposed in 1965 by Crick and Wyman in a manuscript circulated among the proponents of allostery, but only now published for the first time in this special issue.
Topics: Allosteric Regulation; Allosteric Site; Animals; Humans; Kinetics; Ligands; Models, Biological; Models, Molecular; Receptors, Cell Surface
PubMed: 23523898
DOI: 10.1016/j.jmb.2013.03.011 -
Journal of Pharmacy & Bioallied Sciences May 2019Methyl methacrylate monomer of denture base resins was modified with several monomers to achieve better physico-mechanical properties without compromising the... (Review)
Review
BACKGROUND
Methyl methacrylate monomer of denture base resins was modified with several monomers to achieve better physico-mechanical properties without compromising the biocompatibility. However, there are no consensuses on the best strategy to achieve best modified monomer.
PURPOSE
To identify and evaluate the differences in the properties between conventional and modified monomers and to verify the influence of several variables on the properties of denture base acrylic resin.
MATERIALS AND METHODS
This study was executed by following the Preferred Reporting Items for Systematic Reviews and Meta-Analyses statement. In-vitro studies that investigated the properties of conventional and modified monomers were selected. Searches were carried out in the Ebscohost, PubMed, Semantic scholar and J-stage databases. The search commenced from the year 1995 and the last search was done till November 2018. A comparison was performed between modified and unmodified monomers. The analyses were carried out using fixed-effect models.
RESULTS
The meta-analysis results showed high heterogeneity in all aspects, and higher flexural strength for monomers modified with 20% methacrylic acid.
CONCLUSION
Although the articles included in this meta-analysis showed high heterogeneity and high risk of bias, the in-vitro literature seems to suggest that use of modified monomers could improve the properties of denture base resins. Other variants of monomer modifications and their tested parameters were discussed in this systematic review as well. Dimensional accuracy is an unexplored variable to be evaluated extensively in the future researches.
PubMed: 31198322
DOI: 10.4103/JPBS.JPBS_34_19 -
Biomaterial Investigations in Dentistry 2023Biological evaluation of resin-based dental composites has traditionally been based on in vitro endpoint tests with different methods to determine loss of cell... (Review)
Review
Biological evaluation of resin-based dental composites has traditionally been based on in vitro endpoint tests with different methods to determine loss of cell viability and cell morphology changes after exposure to the material or monomer constituents. The data reveals a potential for biological effects, but clinical relevance of such data is limited. Positive allergy tests and allergic clinical reactions to dental monomers are observed in dental personnel and patients. The aim of this review is to address newer research on molecular events caused by exposure to resin-based composites to have a better understanding of the potential for clinical adverse effects. A more accurate understanding of the biological aspects of dental composite materials has been found after studying parameters like glutathione depletion, oxidative stress, genotoxicity, and immunomodulatory key effects in various cell culture models. Using omics-based approaches allow for a broader and non-specified search of changes caused by methacrylate exposure. Defense mechanisms and adaption are observed in cells exposed to monomer concentrations relevant to clinical exposure. The above-mentioned methods are the foundations for modified testing strategies. The clinical relevance of most available in vitro endpoint tests is of limited relevance for the patient. Research focusing on molecular mechanisms has given new insight into methacrylate toxicity in exposed cells. Using this knowledge from mechanistic studies to develop standardized in vitro biocompatibility tests will likely improve their clinical relevance.
PubMed: 37347059
DOI: 10.1080/26415275.2023.2223223 -
Genome Research Jun 2022Recent advances in long-read sequencing opened a possibility to address the long-standing questions about the architecture and evolution of human centromeres. They also...
Recent advances in long-read sequencing opened a possibility to address the long-standing questions about the architecture and evolution of human centromeres. They also emphasized the need for centromere annotation (partitioning human centromeres into monomers and higher-order repeats [HORs]). Although there was a half-century-long series of semi-manual studies of centromere architecture, a rigorous centromere annotation algorithm is still lacking. Moreover, an automated centromere annotation is a prerequisite for studies of genetic diseases associated with centromeres and evolutionary studies of centromeres across multiple species. Although the monomer decomposition (transforming a centromere into a monocentromere written in the monomer alphabet) and the HOR decomposition (representing a monocentromere in the alphabet of HORs) are currently viewed as two separate problems, we show that they should be integrated into a single framework in such a way that HOR (monomer) inference affects monomer (HOR) inference. We thus developed the HORmon algorithm that integrates the monomer/HOR inference and automatically generates the human monomers/HORs that are largely consistent with the previous semi-manual inference.
Topics: Algorithms; Centromere; Humans
PubMed: 35545449
DOI: 10.1101/gr.276362.121 -
Cells Nov 2018Aquaporins (AQPs) function as tetrameric structures in which each monomer has its own permeable pathway. The combination of structural biology, molecular dynamics... (Review)
Review
Aquaporins (AQPs) function as tetrameric structures in which each monomer has its own permeable pathway. The combination of structural biology, molecular dynamics simulations, and experimental approaches has contributed to improve our knowledge of how protein conformational changes can challenge its transport capacity, rapidly altering the membrane permeability. This review is focused on evidence that highlights the functional relationship between the monomers and the tetramer. In this sense, we address AQP permeation capacity as well as regulatory mechanisms that affect the monomer, the tetramer, or tetramers combined in complex structures. We therefore explore: (i) water permeation and recent evidence on ion permeation, including the permeation pathway controversy-each monomer versus the central pore of the tetramer-and (ii) regulatory mechanisms that cannot be attributed to independent monomers. In particular, we discuss channel gating and AQPs that sense membrane tension. For the latter we propose a possible mechanism that includes the monomer (slight changes of pore shape, the number of possible H-bonds between water molecules and pore-lining residues) and the tetramer (interactions among monomers and a positive cooperative effect).
PubMed: 30423856
DOI: 10.3390/cells7110209 -
Biophysical Reviews Aug 2017Secondary nucleation of monomers on the surface of an already existing aggregate that is formed from the same kind of monomers may lead to autocatalytic amplification of... (Review)
Review
Secondary nucleation of monomers on the surface of an already existing aggregate that is formed from the same kind of monomers may lead to autocatalytic amplification of a self-assembly process. Such monomer-dependent secondary nucleation occurs during the crystallization of small molecules or proteins and self-assembled materials, as well as in protein self-assembly into fibrous structures. Indications of secondary nucleation may come from analyses of kinetic experiments starting from pure monomers or monomers supplemented with a low concentration of pre-formed aggregates (seeds). More firm evidence requires additional experiments, for example those employing isotope labels to distinguish new aggregates arising from the monomer from those resulting from fragmentation of the seed. In cases of amyloid formation, secondary nucleation leads to the formation of toxic oligomers, and inhibitors of secondary nucleation may serve as starting points for therapeutic developments. Secondary nucleation displays a high degree of structural specificity and may be enhanced by mutations or screening of electrostatic repulsion.
PubMed: 28812278
DOI: 10.1007/s12551-017-0289-z -
Polymers Mar 2021Commonly, volumetric shrinkage occurs during polymerizations due to the shortening of the equilibrium Van der Waals distance of two molecules to the length of a... (Review)
Review
Commonly, volumetric shrinkage occurs during polymerizations due to the shortening of the equilibrium Van der Waals distance of two molecules to the length of a (significantly shorter) covalent bond. This volumetric shrinkage can have severe influence on the materials' properties. One strategy to overcome this volumetric shrinkage is the use of expanding monomers that show volumetric expansion during polymerization reactions. Such monomers exhibit cyclic or even oligocyclic structural motifs with a correspondingly dense atomic packing. During the ring-opening reaction of such monomers, linear structures with atomic packing of lower density are formed, which results in volumetric expansion or at least reduced volumetric shrinkage. This review provides a concise overview of expanding monomers with a focus on the elucidation of structure-property relationships. Preceded by a brief introduction of measuring techniques for the quantification of volumetric changes, the most prominent classes of expanding monomers will be presented and discussed, namely cycloalkanes and cycloalkenes, oxacycles, benzoxazines, as well as thiocyclic compounds. Spiroorthoesters, spiroorthocarbonates, cyclic carbonates, and benzoxazines are particularly highlighted.
PubMed: 33800726
DOI: 10.3390/polym13050806