Catalytic Polymers Research Articles

Temporal Self-Regulation of Mechanical Properties via Catalytic Amyloid Polymers of a Short Peptide.

We report a short peptide that accessed dynamic catalytic polymers to demonstrate four-stage (sol-gel-weak gel-strong gel) temporal self-regulation of its mechanical properties. The peptide exploited its intrinsic catalytic capabilities of manipulating C-C bonds (retro-aldolase-like) that resulted in a nonlinear variation in the catalytic rate. The seven-residue sequence exploited two lysines for binding and cleaving the thermodynamically activated substrate that subsequently led to the self-regulation of the mechanical strengths of the polymerized states as a function of time and reaction progress. Interestingly, the polymerization events were modulated by the different catalytic potentials of the two terminal lysines to cleave the substrate, covalently trap the electrophilic products, and subsequently control the mechanical properties of the system.

Pyrrolidine-based catalytic microporous polymers in sustainable C[dbnd]N and C[dbnd]C bond formation via iminium and enamine activation

A new set of catalytic materials having a pyrrolidine moiety confined in microporous organic polymer networks (POPs) has been attained. These catalytic polymers have been prepared by a straightforward synthesis starting from microporous polymer networks made from isatin (or a mixture of isatin and trifluoroacetophenone) and 1,3,5-triphenylbenzene. The polymers efficiently catalyzed the formation of nitrones under very mild and sustainable conditions using green solvents through an iminium ion activation mechanism. The reactions are scalable, and polymers are easily recycled. Special attention has been paid to understanding all the factors that could affect the efficiency of the confined catalysts. The electronic and conformational characteristics of the pyrrolidine moiety attached to the porous polymers, as well as other features that could affect the transport through the network, such as molecular volume and shape of reactants and products, and even hydrophilic or hydrophobic properties, have been systematically evaluated. In addition, the heterogeneous polymers are also useful in CC bond formation through both iminium ion and enamine activation.

Polysulfide Catalytic Materials for Fast-Kinetic Metal-Sulfur Batteries: Principles and Active Centers.

Benefiting from the merits of low cost, ultrahigh‐energy densities, and environmentally friendliness, metal–sulfur batteries (M–S batteries) have drawn massive attention recently. However, their practical utilization is impeded by the shuttle effect and slow redox process of polysulfide. To solve these problems, enormous creative approaches have been employed to engineer new electrocatalytic materials to relieve the shuttle effect and promote the catalytic kinetics of polysulfides. In this review, recent advances on designing principles and active centers for polysulfide catalytic materials are systematically summarized. At first, the currently reported chemistries and mechanisms for the catalytic conversion of polysulfides are presented in detail. Subsequently, the rational design of polysulfide catalytic materials from catalytic polymers and frameworks to active sites loaded carbons for polysulfide catalysis to accelerate the reaction kinetics is comprehensively discussed. Current breakthroughs are highlighted and directions to guide future primary challenges, perspectives, and innovations are identified. Computational methods serve an ever‐increasing part in pushing forward the active center design. In summary, a cutting‐edge understanding to engineer different polysulfide catalysts is provided, and both experimental and theoretical guidance for optimizing future M–S batteries and many related battery systems are offered.

Regiospecific vs. non regiospecific click azide-alkyne polymerization: In vitro study of water-soluble antibacterial poly(amide aminotriazole)s

Novel linear cationic poly(amide aminotriazole)s (PATnD) with secondary amine groups in the backbone were obtained by using azide-alkyne 1,3-dipolar cycloaddition reactions: metal- and solvent-free (thermal conditions, PATTnD) or copper(I)-catalyzed (Sharpless conditions, PATCnD). PATnD were investigated in vitro against strains of E. coli, P. aeruginosa, S. aureus, and S. epidermidis. Hemolytic activity was tested using human red blood cells (hRBC), and very low or no hemolytic activity was observed. The cytotoxicity of PATnD polymers against Human Gingival Fibroblasts (HGnF) cells was concentration-dependent, and significant differences between PATT1D and PATC1D were observed. The ability of these polymers to induce resistance against both Gram-positive and Gram-negative bacteria was also assessed. Studied bacterial strains acquired resistance to catalytic polymers (PATCnD) in initial passages meanwhile resistance to thermal polymers (PATTnD) appears in later passages, being the increase of the minimum inhibitory concentration lower than in catalytic polymers. This result, together with the higher biocidal capacity of thermal polymers compared to catalytic ones, seems to suggest an influence of the regiospecificity of the polymers on their antibacterial characteristics. This study also demonstrates that PAT1D polymers, which do not appear to have strong hydrophobic residues, can exert significant antimicrobial activity against Gram-positive bacteria such as S. epidermidis. This pair of polymers, PATC1D and PATT1D, displays the greatest antimicrobial activity while not causing significant hemolysis along with the lowest susceptibility for resistance development of the polymers evaluated.

Electro-Polymerization of Hydrogen-Bonding Conductive Polymers As Metal-Free Electrocatalysts for Energy Conversion

Electrocatalytic hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2RR) are the key reactions for conversion of renewable electricity into storable chemical energies. It is crucially important to develop active and stable electrocatalysts without relying on rare metal elements for sustainable energy systems. Recently, some metal-free conductive organic polymers such as polydopamine (PDA) and poly guanine (PGA) synthesized by oxidative chemical vapor deposition (oCVD) have been found to exhibit high catalytic activity and durability for HER and CO2RR1,2. In addition to their conductivity of the π-conjugated system of the main chain, these polymers contain heteroatoms such as N and O at high densities, which are believed to act as hydrogen bonding sites for stabilization of reaction intermediates. However, their exact structures and relationship to the catalytic activities are not fully grasped.In this study, we employ electro-polymerization as the mean to obtain catalytic polymers. Taking polyaniline (PANI) as the host, hydrogen bonding monomers such as dopamine (DA), guanine (GA) and neutral red (NR) are to be introduced to obtain co-polymers with controlled structure and density of the hydrogen bonding sites. Comparison of their electrocatalytic activity to those of the respective homo-polymers should reveal the effective catalytic sites and its product selectivity, which should result in optimal design of the catalyst.Electro-polymerization of PANI and PNR was carried out at an ITO glass substrate in an aqueous solution containing 50 mM ANI or NR and 0.1 M H2SO4 during 50 times potential cycling between -0.5 and +0.6 V vs. Ag/AgCl under the N2. Copolymers were obtained by mixing the monomers at appropriate ratios. The films were characterized by FT-IR spectra.PANI, PNR and their copolymer appeared dark green, dark red and black, respectively. While CVs during electropolymerization of PANI continue to increase the redox peaks of PANI as typically expected, those for PNR show decrease of anodic current suggesting inactiveness of PNR for its redox (Figs. 1 a, b). When they are mixed together, a new redox peak in between those from PANI and another irreversible anodic peak close to +0.9 V appear, which indicate loading of NR in redox active form into PANI (Fig. 1c). The FTIR spectrum of the copolymer showed significant difference from the homo-polymers of PANI and PNR with intense absorption peaks between 800 and 1600 cm-1 (Fig. 1d). These peaks arise from infrared-activated vibrations (IRAV) due to the presence of polaron in the main chain, thus are indicative of its conductive nature. These results suggest improvement of conductivity by heterogeneity in copolymers. Its relevance to the catalytic property and optimal density of hydrogen bonding sites are to be further investigated.

PKa Modulation of Pyrrolidine-Based Catalytic Polymers Used for the Preparation of Glycosyl Hydrazides at Physiological pH and Temperature.

Inspired by the ability of enzymes to use the surrounding hydrophobic and/or polarizable groups to modulate the pKa of a given amino acid, we designed a series of soluble polymers able to decrease the basicity of pyrrolidine (from 11.2 to 8.6 pKa units), which clearly increases its aminocatalytic activity at physiological pH in C═N bond formation reactions via ion iminium activation. Other parameters such as charge density, hydrophobic/hydrophilic balance, and aggregation state have been studied as important factors in the catalytic activity of the polymers for a given substrate. To demonstrate the utility of our approach, an optimal pyrrolidine-based catalytic polymer has been used for the formation of C-N bonds between hydrazides and free sugars as the model system for the preparation of glycoconjugates.

Tyrosinase Electrochemical Biosensors Monitoring Medicinally Significant Substances.

Nowadays in biosensing, development of analytical techniques is focused on improvement for monitoring biologically active species in living organisms, especially in real-time analysis. This article provides an overview of applications of electrochemical tyrosinase biosensors in the analysis of medicinally significant substances, also known as biomarkers. At the beginning, special attention is paid to characterisation of the tyrosinase enzyme, explanation of reaction mechanisms of tyrosinase with various types of electrochemical transducers and techniques needed for stable immobilization of this biocatalyst on the transducer surface used. In this case, amperometric transducers represent the most frequently used type of electrochemical sensing because they usually provide sensitive current response to the presence of analyte in the sample. Many scientific works suggest that these very selective bioanalytical devices could find application in the clinical diagnosis of various serious diseases because they represent the effective analytical tools for diagnosis of neurodegenerative disorders, detection of microbial pathogens responsible for foodborne illness and diagnosis of cytopathology, especially melanoma cancer. Additionally, various kinds of electrochemical tyrosinase biosensors are presented which were developed to determine the catalytic activity of other enzymes significant for human metabolism, medicaments and their metabolic products, several hormones, amino acids and proteins. Despite all of their advantages, it is necessary to state that tyrosinase biosensors are still not used in the routine laboratory practice due to their relatively short service life which is not longer than one month unfortunately. Never-ending development of catalytic polymers imitating the tyrosinase active site could be one of ways to solve this serious drawback.

Combining advantages of homogeneous organocatalysis and heterogeneous catalysis with thermosensitive single-chain nanoparticles in a representative tetrahydropyranilation of alcohols

A significant scientific problem solved in this work is the development of effective polymer catalysts that allow carrying out organic reactions under homogeneous conditions with high rates and to remove catalyst from the system as a heterophase without the use of special treatment, thus combining the advantages of both homogeneous and heterogeneous catalysis. Kinetic experiments show high catalytic activity of the synthesized catalyst in homogeneous regime even at low dosage of the catalyst. Thus, it was demonstrated that tetrahydropyranilation of methanol was completed in nearly quantitative yield of the corresponding ether in 80 min at 60 °C with a dosage of the polymeric catalyst as low as 0.2 mol%. On the other hand anomalous decrease in the values of the effective rate constant was observed when the reaction was run at temperatures below the phase transition temperature. Kinetic data were used along with thermodynamic calculations to discuss the effect of the synthesized polymeric catalyst on the stabilization of the transition state. The high activity of the catalyst is complemented by its high sedimentation ability; thus, it usually takes a few minutes for the polymer to precipitate from the alcohol solution when cooled below the phase-transition temperature after the completion of the reaction. It was also revealed via dynamic light scattering that catalytic polymers adopt a thermodynamically stable conformation of the single-chain nanoparticles with average hydrodynamic radius in the range 2–2.5 nm.

Foldamer hypothesis for the growth and sequence differentiation of prebiotic polymers

It is not known how life originated. It is thought that prebiotic processes were able to synthesize short random polymers. However, then, how do short-chain molecules spontaneously grow longer? Also, how would random chains grow more informational and become autocatalytic (i.e., increasing their own concentrations)? We study the folding and binding of random sequences of hydrophobic ([Formula: see text]) and polar ([Formula: see text]) monomers in a computational model. We find that even short hydrophobic polar (HP) chains can collapse into relatively compact structures, exposing hydrophobic surfaces. In this way, they act as primitive versions of today's protein catalysts, elongating other such HP polymers as ribosomes would now do. Such foldamer catalysts are shown to form an autocatalytic set, through which short chains grow into longer chains that have particular sequences. An attractive feature of this model is that it does not overconverge to a single solution; it gives ensembles that could further evolve under selection. This mechanism describes how specific sequences and conformations could contribute to the chemistry-to-biology (CTB) transition.

On the Emergence of a Proto-Metabolism and the Assembly of Early Protocells

Protocells are envisaged as encapsulated networks of catalytic polymers, e.g., RNAs, which are thought to have existed on the prebiotic Earth, as precursors to contemporary biological cells. Such protocells were not alive in the way this word would apply to a contemporary unicellular organism, but instead represented a necessary evolutionary step toward those first forms of cellular life. In this review, we explore how chemicals synthesized by minerals or delivered by meteorites could have contributed to the emergence of the first protocells and supported their evolution towards primitive cellular life.

Effect of Aminosilane Compounds as External Donors on Isospecific Polymerizations of 1-Butene with MgCl2/TiCl4/DIBP Catalyst

Four aminosilane compounds were synthesized and employed as external electron donors for 1-butene polymerization with MgCl2 supported Ziegler-Natta catalyst. The four aminosilane compounds are di(piperidinyl)dimethoxysilane (DPPDMS), di(piperidinyl)- diethoxysilane (DPPDES), di(pyrrolidinyl)dimethoxysilane (DPRDMS) and di(pyrrolidinyl)- diethoxysilane (DPRDES). A detailed study has been performed on the effects of the chemical structure of different external electron donors on the catalytic efficiency, isotacticity, melting temperature and molecular weight distribution of obtained poly(1-butene). Poly(1-butene) products have been characterized with gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) analysis. The results indicated that: first, aminosilane compounds with dimethoxy groups showed higher catalytic efficiency and polymers isospecificity than those of with diethoxy groups. Conversely, the aminosilane compounds with diethoxy groups were conductive to obtaining polymers with broader molecular weight distribution than those of with dimethoxy groups. Second, compared with single DPPDMS or TEOS (tetraethyl orthosilicate), DPPDMS/TEOS complex in a proper molar ratio would not only increase the catalytic efficiency and isotacticity of obtained polymers, but also broaden the molecular weight distribution of polymers. Third, the effects of other factors on catalytic efficiency and isotacticity of polymers product were also studied, including different amount of hydrogen, concentration of external donor and cocatalyst. Di(piperidinyl)dimethoxysilane (DPPDMS) was synthesized and employed as external electron donors for 1-butene polymerization with MgCl2 supported Ziegler-Natta catalyst. Compared with single DPPDMS or TEOS (tetraethyl orthosilicate), DPPDMS/TEOS complex in a proper molar ratio would not only increase the catalytic efficiency and isotacticity of obtained polymers, but also broaden the molecular weight distribution of polymers. The selection of molar ratio should depend on the requirements to the polymer.

Catalysts from synthetic genetic polymers.

The emergence of catalysis in early genetic polymers like RNA is considered a key transition in the origin of life1, predating the appearance of protein enzymes. DNA also demonstrates the capacity to fold into three-dimensional structures and form catalysts in vitro2. However, to what degree these natural biopolymers comprise functionally privileged chemical scaffolds3 for folding or the evolution of catalysis is not known. The ability of synthetic genetic polymers (XNAs) with alternative backbone chemistries not found in nature to fold into defined structures and bind ligands4 raises the possibility that these too might be capable of forming catalysts (XNAzymes). Here we report the discovery of such XNAzymes, elaborated in four different chemistries (ANA (arabino nucleic acids)5, FANA (2′-fluoroarabino nucleic acids)6, HNA (hexitol nucleic acids) and CeNA (cyclohexene nucleic acids)7 directly from random XNA oligomer pools, exhibiting in trans RNA endonuclease and ligase activities. We also describe an XNA-XNA ligase metalloenzyme in the FANA framework, establishing catalysis in an entirely synthetic system and enabling the synthesis of FANA oligomers and an active RNA endonuclease FANAzyme from its constituent parts. These results extend catalysis beyond biopolymers and establish technologies for the discovery of catalysts in a wide range of polymer scaffolds not found in nature8. Evolution of catalysis independent of any natural polymer has implications for the definition of chemical boundary conditions for the emergence of life on earth and elsewhere in the universe9.

Fluorine-rich planetary environments as possible habitats for life.

In polar aprotic organic solvents, fluorine might be an element of choice for life that uses selected fluorinated building blocks as monomers of choice for self-assembling of its catalytic polymers. Organofluorine compounds are extremely rare in the chemistry of life as we know it. Biomolecules, when fluorinated such as peptides or proteins, exhibit a “fluorous effect”, i.e., they are fluorophilic (neither hydrophilic nor lipophilic). Such polymers, capable of creating self-sorting assemblies, resist denaturation by organic solvents by exclusion of fluorocarbon side chains from the organic phase. Fluorous cores consist of a compact interior, which is shielded from the surrounding solvent. Thus, we can anticipate that fluorine-containing “teflon”-like or “non-sticking” building blocks might be monomers of choice for the synthesis of organized polymeric structures in fluorine-rich planetary environments. Although no fluorine-rich planetary environment is known, theoretical considerations might help us to define chemistries that might support life in such environments. For example, one scenario is that all molecular oxygen may be used up by oxidation reactions on a planetary surface and fluorine gas could be released from F-rich magma later in the history of a planetary body to result in a fluorine-rich planetary environment.

“Key-vs.-Lock”-Like Polymer Reactor Made of Molecularly Imprinted Polymer Containing Metal Nanoparticles

This study aimed at the present dilemma in selective catalysis, about how to furnish metal-nanoparticle catalysts with predictable selectivity. This issue was addressed by developing a “key-vs.-lock”-like polymer reactor made of an elaborate molecularly imprinted polymer containing metal nanoparticles, which was capable of predictably and selectively catalyzing its specified substrate. Unlike reported polymer reactors and enzyme-like imprinted polymer catalysts, which lack either predictable selectivity or reactive metal nanoparticles, this polymer reactor has incorporated both of the molecular recognition ability of the polymer carrier and the catalytic sites of metal nanoparticles into one entire entity and thereby dictated selective catalysis. This study highlighted how this polymer reactor works in a selective way in contrast to reported catalytic polymers or polymer reactors, which thus opens opportunities of tailoring selective catalysts for controlled chemical processes.

Preface for the special issue of the 3rd KACST-Oxford Petrochemical Forum

The 3rd KACST-Oxford Petrochemical Research Forum (KOPRC Forum) was held in August 2013, some of the presentations in the forum have been submitted to the special issue of Applied Petrochemical Research. This paper collection covers most of topics of petrochemical technologies including catalyst and catalytic process, polymers, feedstocks and process improvements.

Artificial enzyme with magnetic properties and peroxidase activity on indoleamine metabolite tumor marker

Stable and easily-handled synthetic materials mimicking natural enzymes activity would find important biotechnological applications. This article describes the synthesis and characterization of magnetic molecularly imprinted catalytic polymers that exhibit peroxidase-like activity towards 5-hydroxyindole-3-acetic acid (5-HIAA) oxidation. This multifunctional material is obtained from highly crystalline magnetite nuclei coated with a silica layer to protect the iron nucleus from oxidation and to provide anchoring for hydroxyl surface groups. After acrylic functionalization via sol–gel process, a molecularly imprinted polymer with hemin as catalytic center and 5-HIAA as template has been successfully attached to the structure. The resulting hybrid composite is magnetically separable and possesses excellent catalytic ability for the selective oxidation of the indoleamine metabolite tumor marker, showing Michaelis–Menten kinetics with this molecule but not towards other structural analogs. Therefore, it can be considered an artificial peroxidase enzyme.

Hybrid Polyoxotungstates as Functional Comonomers in New Cross‐Linked Catalytic Polymers for Sustainable Oxidation with Hydrogen Peroxide

Anchoring terminal octenyl tails on molecular polyoxotungstates yield polymerizable organic-inorganic monomers with formula [{CH(2)=CH(CH(2))(6)Si}(x)O(y)SiW(w)O(z)](4-) [x = 2, w = 11, y = 1, z = 39 (1); x = 2, w = 10, y = 1, z = 36 (2); and x = 4, w = 9, y = 3, z = 34 (3)]. These molecular hybrids can use aqueous hydrogen peroxide to catalyze the selective oxidation of organic sulfides in CH(3)CN. Copolymerization of 1-3 with methyl methacrylate and ethylene glycol dimethacrylate leads to porous materials with a homogeneous distribution of the functional monomers, as indicated by converging evidence from FTIR spectroscopy and electronic microscopy. The catalytic polymers activate hydrogen peroxide for oxygen transfer, as demonstrated by the quantitative and selective oxidation of methyl p-tolyl sulfide, which was screened as model substrate. The hybrid material containing monomer 2 was also tested in n-octane to evaluate its potential for the oxidation and removal of dibenzothiophene, a well-known gasoline contaminant.

Molecularly imprinted catalytic polymers with biomimetic chloroperoxidase activity

A method for the rational design of molecularly imprinted polymers with catalytic activity (MICs) that mimic hemeproteins is described. Density Functional Theory calculations applied to the pre-polymerization adduct and to a possible reaction intermediate allow to choose the best functional monomer that builds up the active sites. This functional monomer should stabilize both relevant stages, the first one in an adequate porogenic solvent and the second one in the aqueous reaction medium. In this work, a MIC was synthesized to catalyze the oxidation of 2,4,6-trichlorophenol (TCP), the substrate and template molecule. A hemin molecule was used as the catalytic centre and four functional monomers and six solvents were tested. According to the theoretical predictions, methacrylamide and 4-vinylpyridine MIPs successfully mimic the recently discovered ability of Chloroperoxidase (CPO) to catalyze the oxidative dechlorination of TCP in batch analysis. They exhibit good catalytic properties and substrate selectivity.

SELECTION, INTERPRETATION, AND THE EMERGENCE OF LIVING SYSTEMS

Abstract.The autocell proposal for the emergence of life and natural selection through the interaction of two reciprocally coupled self‐organizing processes specifically provides a protein‐first model for the origin of life that can be explored by computer simulations and experiment. Beyond the specific proposal it can be considered more generally as a thought experiment in which the principles deduced for the autocell could apply to other possible detailed chemical scenarios of catalytic polymers and protometabolism, including living systems emerging within membranelike barriers. The autocell model allows for the analysis of the emergence of not only agency and purpose but also of interpretation and semiosis as true living systems arise.

Eutectic Phase in Water‐Ice: A Self‐Assembled Environment Conducive to Metal‐Catalyzed Non‐Enzymatic RNA Polymerization

Information and catalytic polymers play an essential role in contemporary cellular life, and their emergence must have been crucial during the complex processes that led to the assembly of the first living systems. Polymerization reactions producing these molecules would have had to occur in aqueous medium, which is known to disfavor such reactions. Thus, it was proposed early on that these polymerizations had to be supported by particular environments, such as mineral surfaces and eutectic phases in water-ice, which would have led to the concentration of the monomers out of the bulk aqueous medium and their condensation. This review presents the work conducted to understand how the eutectic phases in water-ice might have promoted RNA polymerization, thereby presumably contributing to the emergence of the ancient information and catalytic system envisioned by the 'RNA-World' hypothesis.