Template-Free Self-Assembly of Two-Dimensional Polymers into Nano/Microstructured Materials

In the past few decades, enormous efforts have been made to synthesize covalent polymer nano/microstructured materials with specific morphologies, due to the relationship between their structures and functions. Up to now, the formation of most of these structures often requires either templates or preorganization in order to construct a specific structure before, and then the subsequent removal of previous templates to form a desired structure, on account of the lack of “self-error-correcting” properties of reversible interactions in polymers. The above processes are time-consuming and tedious. A template-free, self-assembled strategy as a “bottom-up” route to fabricate well-defined nano/microstructures remains a challenge. Herein, we introduce the recent progress in template-free, self-assembled nano/microstructures formed by covalent two-dimensional (2D) polymers, such as polymer capsules, polymer films, polymer tubes and polymer rings.     

An Update on Molecularly Imprinted Polymer Design through a Computational Approach to Produce Molecular Recognition Material with Enhanced Analytical Performance

Molecularly imprinted polymer (MIP) computational design is expected to become a routine technique prior to synthesis to produce polymers with high affinity and selectivity towards target molecules. Furthermore, using these simulations reduces the cost of optimizing polymerization composition. There are several computational methods used in MIP fabrication and each requires a comprehensive study in order to select a process with results that are most similar to properties exhibited by polymers synthesized through laboratory experiments. Until now, no review has linked computational strategies with experimental results, which are needed to determine the method that is most appropriate for use in designing MIP with high molecular recognition. This review will present an update of the computational approaches started from 2016 until now on quantum mechanics, molecular mechanics and molecular dynamics that have been widely used. It will also discuss the linear correlation between computational results and the polymer performance tests through laboratory experiments to examine to what extent these methods can be relied upon to obtain polymers with high molecular recognition. Based on the literature search, density functional theory (DFT) with various hybrid functions and basis sets is most often used as a theoretical method to provide a shorter MIP manufacturing process as well as good analytical performance as recognition material.     

Epigenetic Modifications Induced by Olive Oil and Its Phenolic Compounds: A Systematic Review

Many studies demonstrated that olive oil (especially extra virgin olive oil: EVOO) phenolic compounds are bioactive molecules with anti-cancer, anti-inflammatory, anti-aging and neuroprotective activities. These effects have been recently attributed to the ability of these compounds to induce epigenetics modifications such as miRNAs expression, DNA methylation and histone modifications. In this study, we systematically review and discuss, following the PRISMA statements, the epigenetic modifications induced by EVOO and its phenols in different experimental systems. At the end of literature search through “PubMed”, “Web of Science” and “Scopus”, 43 studies were selected.Among them, 22 studies reported data on miRNAs, 15 on DNA methylation and 13 on histone modification. Most of the “epigenomic” changes observed in response to olive oil phenols’ exposure were mechanistically associated with the cancer preventive and anti-inflammatory effects. In many cases, the epigenetics effects regarding the DNA methylation were demonstrated for olive oil but without any indication regarding the presence or not of phenols. Overall, the findings of the present systematic review may have important implications for understanding the epigenetic mechanisms behind the health effects of olive oil. However, generally no direct evidence was provided for the causal relationships between epigenetics modification and EVOO health related effects. Further studies are necessary to demonstrate the real physiological consequences of the epigenetics modification induced by EVOO and its phenolic compounds.     

The Development of Maillard Reaction,and Advanced Glycation End Product (AGE)-Receptor for AGE (RAGE) Signaling Inhibitors as Novel Therapeutic Strategies for Patients with AGE-Related Diseases

Advanced glycation end products (AGEs) are generated by nonenzymatic modifications of macromolecules (proteins, lipids, and nucleic acids) by saccharides (glucose, fructose, and pentose) via Maillard reaction. The formed AGE molecules can be catabolized and cleared by glyoxalase I and II in renal proximal tubular cells. AGE-related diseases include physiological aging, neurodegenerative/neuroinflammatory diseases, diabetes mellitus (DM) and its complications, autoimmune/rheumatic inflammatory diseases, bone-degenerative diseases, and chronic renal diseases. AGEs, by binding to receptors for AGE (RAGEs), alter innate and adaptive immune responses to induce inflammation and immunosuppression via the generation of proinflammatory cytokines, reactive oxygen species (ROS), and reactive nitrogen intermediates (RNI). These pathological molecules cause vascular endothelial/smooth muscular/connective tissue-cell and renal mesangial/endothelial/podocytic-cell damage in AGE-related diseases. In the present review, we first focus on the cellular and molecular bases of AGE–RAGE axis signaling pathways in AGE-related diseases. Then, we discuss in detail the modes of action of newly discovered novel biomolecules and phytochemical compounds, such as Maillard reaction and AGE–RAGE signaling inhibitors. These molecules are expected to become the new therapeutic strategies for patients with AGE-related diseases in addition to the traditional hypoglycemic and anti-hypertensive agents. We particularly emphasize the importance of “metabolic memory”, the “French paradox”, and the pharmacokinetics and therapeutic dosing of the effective natural compounds associated with pharmacogenetics in the treatment of AGE-related diseases. Lastly, we propose prospective investigations for solving the enigmas in AGE-mediated pathological effects.     

Amorphous Polymers’ Foaming and Blends with Organic Foaming-Aid Structured Additives in Supercritical CO2, a Way to Fabricate Porous Polymers from Macro to Nano Porosities in Batch or Continuous Processes

Organic polymers can be made porous via continuous or discontinuous expansion processes in scCO₂. The resulting foams properties are controlled by the interplay of three groups of parameters: (i) Chemical, (ii) physico-chemical, and (iii) technological/process that are explained in this paper. The advantages and drawbacks of continuous (extrusion, injection foaming) or discontinuous (batch foaming) foaming processes in scCO₂, will be discussed in this article; especially for micro or nano cellular polymers. Indeed, a challenge is to reduce both specific mass (e.g., ρ < 100 kg·m⁻³) and cell size (e.g., average pore diameter ϕ_average^pores < 100 nm). Then a particular system where small “objects” (coreshells CS, block copolymer MAM) are perfectly dispersed at a micrometric to nanometric scale in poly(methyl methacrylate) (PMMA) will be presented. Such “additives”, considered as foaming aids, are aimed at “regulating” the foaming and lowering the pore size and/or density of PMMA based foams. Differences between these additives will be shown. Finally, in a PMMA/20 wt% MAM blend, via a quasi one-step batch foaming, a “porous to nonporous” transition is observed in thick samples. A lower limit of pore size (around 50 nm) seems to arise.     

Polymerization of supramonomers: A new way for fabricating supramolecular polymers and materials

Supramolecular polymers and materials are attracting more and more attention nowadays due to their dynamic properties such as reversibility, stimuli-responsiveness and self-healing. Conventionally, bifunctional or multi-functional monomers are first covalently synthesized, followed by the supramolecular complexation to form supramolecular polymers and materials. Recently, we have proposed the supramonomer concept to construct supramolecular polymers and materials in a different way. Supramonomers are bifunctional or multi-functional monomers fabricated by noncovalent synthesis, but can undergo traditional covalent polymerization. In this highlight article, we will summarize and discuss the fabrication of supramonomer and covalent polymerization methods of supramonomers; fabrication of multi-responsive supramolecular polymers from supramonomers; and fabrication of supramolecular materials from supramonomers. It is highly anticipated that the supramonomer concept will enrich the methodology towards supramolecular polymers and materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 604–609     

Improving the Cellular Selectivity of a Membrane-Disrupting Antimicrobial Agent by Monomer Control and by Taming

Antimicrobial resistance represents a significant world-wide health threat that is looming. To meet this challenge, new classes of antimicrobial agents and the redesign of existing ones will be required. This review summarizes some of the studies that have been carried out in my own laboratories involving membrane-disrupting agents. A major discovery that we made, using a Triton X-100 as a prototypical membrane-disrupting molecule and cholesterol-rich liposomes as model systems, was that membrane disruption can occur by two distinct processes, depending on the state of aggregation of the attacking agent. Specifically, we found that monomers induced leakage, while attack by aggregates resulted in a catastrophic rupture of the membrane. This discovery led us to design of a series of derivatives of the clinically important antifungal agent, Amphotericin B, where we demonstrated the feasibility of separating antifungal from hemolytic activity by decreasing the molecule’s tendency to aggregate, i.e., by controlling its monomer concentration. Using an entirely different approach (i.e., a “taming” strategy), we found that by covalently attaching one or more facial amphiphiles (“floats”) to Amphotericin B, its aggregate forms were much less active in lysing red blood cells while maintaining high antifungal activity. The possibility of applying such “monomer control” and “taming” strategies to other membrane-disrupting antimicrobial agents is briefly discussed.     

Organocatalytic Upgrading of Biomass Derived Building Blocks

The depletion of finite primary fossil fuels we are facing makes necessary a deep metamorphosis in fundamental parts of the chemical industry. A progressive transition from petro-based starting materials toward renewable biomass-derived sources will have to take place in the synthesis of added-value chemicals, important for our everyday life, such as pharmaceuticals, polymers, agrochemicals etc. Moreover, greener processes, carried out under friendlier reaction conditions, must be designed to address current concerns about the climate change and the resulting pressing need to reduce the environmental footprint of chemical processes. To this end, organocatalysis could offer a valuable opportunity for upgrading biomass-derived platform molecules in line with the principles of Green Chemistry. This review presents some of recent and remarkable advancements in this emerging area. Organocatalysis has proven to be an efficient tool to transform low value bio-based renewable platform building blocks into new high value bio-based chemicals, with potential applications as synthetic intermediates, innovative materials and pharmaceutically active compounds.     

聚合物热激活延迟荧光材料的分子设计与器件性能

聚合物热激活延迟荧光(TADF)材料应用于有机发光二极管(OLEDs)中以来,取得了飞速发展,迄今为止已经报道了多种不同分子结构及性能优异的聚合物TADF发光材料.它们具有不含重金属的化学结构、100%的理论内量子效率和易于通过溶液加工进行大面积制造的优势.本文从分子结构和发光颜色2个角度总结了不同结构TADF聚合物的研究进展,重点介绍了我们课题组在长链型TADF聚合物设计与OLEDs器件性能方面的研究工作,探究TADF聚合物颜色调控与效率提升的途径,论述了TADF聚合物存在的问题与未来发展.     

Mesoporous carbons from self-assembled polymers

Polymer self-assembly provides a robust and cost-efficient nanomanufacturing platform for enabling a broad range of applications, such as microelectronics, drug delivery, and separation membranes. This review focuses on discussing the progress and opportunities of self-assembled polymer in the synthesis of mesoporous carbons (MCs), which have aroused significant research interests over the past decades. Specifically, we will discuss the two most established approaches for converting nanostructured polymers to MCs, including templating-based and direct pyrolysis-based methods. We will also review the fundamental ordering mechanisms and kinetics of these polymeric systems and discuss the recent development of engineering methods for providing on-demand control over the pore size and morphology of MCs. Additionally, this review article also includes a section focusing on the strategies to further functionalize these materials from self-assembled polymers to enhance their performance, such as chemical activation, heteroatom doping, introduction of nanoparticles into the carbon matrix, and enhancing graphitization degree of carbon walls. Finally, a brief perspective is provided about the emerging research opportunity in this exciting field.     

“Click handle”-modified 2′-deoxy-2′-fluoroarabino nucleic acid as a synthetic genetic polymer capable of post-polymerization functionalization

The functions of natural nucleic acids such as DNA and RNA have transcended genetic information carriers and now encompass affinity reagents, molecular catalysts, nanostructures, data storage, and many others. However, the vulnerability of natural nucleic acids to nuclease degradation and the lack of chemical functionality have imposed a significant constraint on their ever-expanding applications. Herein, we report the synthesis and polymerase recognition of a 5-(octa-1,7-diynyl)uracil 2′-deoxy-2′-fluoroarabinonucleic acid (FANA) triphosphate. The DNA-templated, polymerase-mediated primer extension using this “click handle”-modified FANA (cmFANA) triphosphate and other FANA nucleotide triphosphates consisting of canonical nucleobases efficiently generated full-length products. The resulting cmFANA polymers exhibited excellent nuclease resistance and the ability to undergo efficient click conjugation with azide-functionalized molecules, thereby becoming a promising platform for serving as a programmable and evolvable synthetic genetic polymer capable of post-polymerization functionalization.

Polymerase-mediated incorporation of a “click handle”-modified fluoroarabinonucleic acid (cmFANA) triphosphate produces a new class of nuclease-resistant, evolvable genetic polymers that can be functionalized with azide-containing molecules.     

Molecular Mechanisms behind Acetylene Adsorption and Selectivity in Functional Porous Materials

Since its first industrial production in 1890s, acetylene has played a vital role in manufacturing a wide spectrum of materials. Although current methods and infrastructures for various segments of acetylene industries are well-established, with emerging functional porous materials that enabled desired selectivity toward target molecules, it is of timely interest to develop new efficient technologies to promote safer acetylene processes with a higher energy efficiency and lower carbon footprint. In this Minireview, we, from the perspective of materials chemistry, review state-of-the-art examples of advanced porous materials, namely metal–organic frameworks and decorated zeolites, that have been applied to the purification and storage of acetylene. We also discuss the challenges on the roadmap of translational research in the development of new solid sorbent-based separation technologies and highlight areas which require future research efforts.     

Applications of Hybrid Polymers Generated from Living Anionic Ring Opening Polymerization

Increasingly precise control of polymer architectures generated by “Living” Anionic Ring-Opening Polymerization (Living AROP) is leading to a broad range of commercial advanced material applications, particularly in the area of siloxane macromers. While academic reports on such materials remain sparse, a significant portion of the global population interacts with them on a daily basis—in applications including medical devices, microelectronics, food packaging, synthetic leather, release coatings, and pigment dispersions. The primary driver of this increased utilization of siloxane macromers is their ability to incorporate the properties of silicones into organic structures in a balanced manner. Compared to organic polymers, the differentiating properties of silicones—low T_g, hydrophobicity, low surface energy, and high free molal space—logically lend themselves to applications in which low modulus, release, permeability to oxygen and moisture, and tactile interaction are desired. However, their mechanical, structural and processing properties have until recently precluded practical applications. This review presents applications of “Living” AROP derived polymers from the perspective of historical technology development. Applications in which products are produced on a commercial scale—defined as not only offered for sale, but sold on a recurrent basis—are emphasized. Hybrid polymers with intriguing nanoscale morphology and potential applications in photoresist, microcontact printing, biomimetic soft materials, and liquid crystals are also discussed. Previously unreported work by the authors is provided in the context of this review.     

Current Trends in Acetins Production: Green versus Non-Green Synthesis

To utilize excess glycerol produced from the biodiesel industry, researchers are developing innovative methods of transforming glycerol into value-added chemicals. One strategy adopted is the conversion of glycerol into acetins, which are esters of glycerol that have wide applications in cosmetics, pharmaceuticals, food and fuel additives, and plasticizers and serve as precursors for other chemical compounds. Acetins are synthesized either by traditional chemical methods or by biological processes. Although the chemical methods are efficient, productive, and commercialized, they are “non-green”, meaning that they are unsafe for the environment and consumers. On the other hand, the biological process is “green” in the sense that it protects both the environment and consumers. It is, however, less productive and requires further effort to achieve commercialization. Thus, both methodologies have benefits and drawbacks, and this study aims to present and discuss these. In addition, we briefly discuss general strategies for optimizing biological processes that could apply to acetins production on an industrial scale.     

Biomedical application of responsive ‘smart’ electrospun nanofibers in drug delivery system: A minireview

Electrospinning is a versatile method for producing continuous nanofibers. It has since become an easy and cost-effective technique in the manufacturing process and drawn keen interests in most biomedical field applications. Nanofibers have garnered great attention in nanomedicine due to their resemblance with the extracellular matrix (ECM). Like nanoparticles, its unique characteristics of higher surface-to-volume ratio and the tunability of the polymers utilizing nanofiber have increased the efficiency in encapsulation and drug-loading capabilities. Smart or “stimuli-responsive” polymers have shown particular fascination in controlled release, where their ability to react to minor changes in the environment, such as temperature, pH, electric field, light, or magnetic field, distinguishes them as intelligent. Polymers are a popular material for the design of drug delivery carriers; consequently, various types of drugs, including antiviral, proteins, antibiotics, DNA and RNA, are successfully encapsulated in the pH-dependent nanofibers with smart polymers which is a polymer that can respond to change such as pH change, temperature. In this minireview, we discuss applications of smart electrospun pH-responsive nanofibers in the emerging biomedical developments which includes cancer drug targeting, oral controlled release, wound healing and vaginal drug delivery.     

Plant Secondary Metabolites Produced in Response to Abiotic Stresses Has Potential Application in Pharmaceutical Product Development

Plant secondary metabolites (PSMs) are vital for human health and constitute the skeletal framework of many pharmaceutical drugs. Indeed, more than 25% of the existing drugs belong to PSMs. One of the continuing challenges for drug discovery and pharmaceutical industries is gaining access to natural products, including medicinal plants. This bottleneck is heightened for endangered species prohibited for large sample collection, even if they show biological hits. While cultivating the pharmaceutically interesting plant species may be a solution, it is not always possible to grow the organism outside its natural habitat. Plants affected by abiotic stress present a potential alternative source for drug discovery. In order to overcome abiotic environmental stressors, plants may mount a defense response by producing a diversity of PSMs to avoid cells and tissue damage. Plants either synthesize new chemicals or increase the concentration (in most instances) of existing chemicals, including the prominent bioactive lead compounds morphine, camptothecin, catharanthine, epicatechin-3-gallate (EGCG), quercetin, resveratrol, and kaempferol. Most PSMs produced under various abiotic stress conditions are plant defense chemicals and are functionally anti-inflammatory and antioxidative. The major PSM groups are terpenoids, followed by alkaloids and phenolic compounds. We have searched the literature on plants affected by abiotic stress (primarily studied in the simulated growth conditions) and their PSMs (including pharmacological activities) from PubMed, Scopus, MEDLINE Ovid, Google Scholar, Databases, and journal websites. We used search keywords: “stress-affected plants,” “plant secondary metabolites, “abiotic stress,” “climatic influence,” “pharmacological activities,” “bioactive compounds,” “drug discovery,” and “medicinal plants” and retrieved published literature between 1973 to 2021. This review provides an overview of variation in bioactive phytochemical production in plants under various abiotic stress and their potential in the biodiscovery of therapeutic drugs. We excluded studies on the effects of biotic stress on PSMs.     

Gastrointestinal cancer organoids—applications in basic and translational cancer research

Cancer is a major health problem and a leading cause of death worldwide. Early cancer detection and continuous changes in treatment strategies have improved overall patient survival. The recent development of targeted drugs offers new opportunities for personalized cancer treatment. Nevertheless, individualized treatment is accompanied by the need for biomarkers predicting the response of a patient to a certain drug. One of the most promising breakthroughs in recent years that might help to overcome this problem is the organoid technology. Organoid cultures exhibit self-renewal capacity, self-organization, and long-term proliferation, while recapitulating many aspects of their primary tissue. Generated patient-derived organoid (PDO) libraries constitute “living” biobanks, allowing the in-depth analysis of tissue function, development, tumor initiation, and cancer pathobiology. Organoids can be derived from all gastrointestinal tissues, including esophageal, gastric, liver, pancreatic, small intestinal and colorectal tissues, and cancers of these tissues. PDOs are amenable to various techniques, including sequencing analyses, drug screening, targeted therapy testing, tumor microenvironment studies, and genetic engineering capabilities. In this review, we discuss the different applications of gastrointestinal organoids in basic cancer biology and clinical translation.Subject terms: Gastrointestinal cancer, Cancer models     

From Phenotypic Hit to Chemical Probe: Chemical Biology Approaches to Elucidate Small Molecule Action in Complex Biological Systems

Biologically active small molecules have a central role in drug development, and as chemical probes and tool compounds to perturb and elucidate biological processes. Small molecules can be rationally designed for a given target, or a library of molecules can be screened against a target or phenotype of interest. Especially in the case of phenotypic screening approaches, a major challenge is to translate the compound-induced phenotype into a well-defined cellular target and mode of action of the hit compound. There is no “one size fits all” approach, and recent years have seen an increase in available target deconvolution strategies, rooted in organic chemistry, proteomics, and genetics. This review provides an overview of advances in target identification and mechanism of action studies, describes the strengths and weaknesses of the different approaches, and illustrates the need for chemical biologists to integrate and expand the existing tools to increase the probability of evolving screen hits to robust chemical probes.     

Surface forces and friction tuned by thermo-responsive polymer films

Thermo-responsive polymer films have enabled the development of various functional surfaces with switchable interfacial properties. Assessing the surface forces and friction on such films is of paramount importance. On the one hand, it allows us to extract a great deal of information on the interfacial properties of the films, e.g., adhesiveness and lubricity, and how they could be tuned using different stimuli. On the other hand, surface force measurements complement other thin-film analysis methods, e.g., ellipsometry, to better perceive the correlation between the molecular properties of the polymer chains and the interfacial properties of the film. On this basis, we will, herein, provide a concise review of some recent studies on surface forces and friction tuned by thermo-responsive polymer films. This outline comprises a summary of several research works addressing the effects of temperature, solvent composition, and salts on surface forces and friction. In the end, we briefly discuss a few select studies in which the regulation of surface forces by thermo-responsive polymers is examined with an emphasis on the potential applications.