Chemical Modification Research Articles

Influence of chemical modifications of the crystallophore on protein nucleating properties and supramolecular interactions network.

Crystallophores are lanthanide complexes that have demonstrated outstanding induction of crystallization for various proteins. This article explores the effect of tailored modifications of the crystallophore first generation and their impact on the nucleating properties, and protein crystal structures. Through high-throughput crystallization experiments and dataset analysis, we evaluated the effectiveness of these variants, in comparison to the first crystallophore generation G1. In particular, the V1variant, featuring a propanol pendant arm, demonstrated the ability to produce new crystallization conditions for the proteins tested (hen-egg white lysozyme, proteinase K and thaumatin). Structural analysis performed in the case of hen egg-white lysozyme along with Molecular Dynamics simulations, highlights V1's unique behavior, taking advantage of the flexibility of its propanol arm to explore different protein surfaces and form versatile supramolecular interactions.

Tailoring Cyano Substitutions on Quinoxaline‐based Small‐Molecule Acceptors Enabling Enhanced Molecular Packing for High‐Performance Organic Solar Cells

AbstractCyanation is a common chemical modification strategy to fine‐tune the energy levels and molecular packing of organic semiconductors, especially materials used in organic solar cells (OSCs). Generally, cyanation is used to modify the end groups of high‐performance small‐molecule acceptors (SMAs). However, the cyanation strategy has not been investigated on the central backbone of SMAs, which could introduce stronger intermolecular interaction and enhance the π–π stacking for rapid charge transport. This paper, for the first time, reports a new cyanation strategy on the central benzo‐quinoxaline core and synthesizes two novel A‐DA'D‐A type SMAs, named BQx‐CN and BQx‐2CN, with mono‐ and di‐cyanide groups, respectively. Through tailoring the number of CN groups, the BQx‐CN‐based OSC exhibits the best device performance of 18.8%, which is significantly higher than the non‐cyano BQx‐based one. The reason for the superior performance of BQx‐CN‐based devices can be attributed to the fine‐tuned energy level, stronger packing, and ideal phase segregation, which lead to superior exciton dissociation, faster charge transport, and suppressed recombination, therefore the highest fill factor (FF) and power conversion efficiencies (PCE). The research demonstrates the effectiveness of the cyanation strategy on the central core of SMAs for enhanced molecular packing and better performance of OSCs.

Investigation of Phase Transformations and Ordering Mechanisms in a Pd–Cu–Ag–Ru Alloy

An in‐depth analysis of phase transformations in a Pd–Cu–Ag alloy, crucial for applications in hydrogen membranes and electrical components, is presented. The investigation emphasizes the influence of the deformation rate and addition of Ag on the formation of the ordered CuPd phase. This study focuses on a specific alloy composition, 49.1% Cu–41.3% Pd–8.3% Ag–1.3% Ru, investigating its behavior under various conditions. Through comprehensive analysis, including the influence of the initial state, deformation variations, and chemical composition modifications, high‐energy X‐ray diffraction to unveil detailed phase evolution dynamics is used. Surprisingly, experimental findings deviate from the anticipated phase diagram, uncovering a previously unrecognized three‐phase region with the formation of AgPd. Notably, the study reveals the pivotal role of the alloy's Ag content in the development of ordered CuPd and AgPd phases. The addition of Ru exhibits no involvement in the observed phase transformations, contributing to the understanding of the alloy's composition‐dependent behavior. This research provides valuable insights into the intricate interplay of factors influencing phase transformations, offering a nuanced perspective beyond theoretical predictions. The newfound understanding of Ag's role and Ru's inertness refines material design considerations, enhancing the grasp of the alloy's thermodynamic stability under varying conditions.

Advances in the Chemistry and Biology of Specialised Pro-Resolving Mediators (SPMs)

This review article assembles key recent advances in the synthetic chemistry and biology of specialised pro-resolving mediators (SPMs). The major medicinal chemistry developments in the design, synthesis and biological evaluation of synthetic SPM analogues of lipoxins and resolvins have been discussed. These include variations in the top and bottom chains, as well as changes to the triene core, of lipoxins, all changes intended to enhance the metabolic stability whilst retaining or improving biological activity. Similar chemical modifications of resolvins are also discussed. The biological evaluation of these synthetic SPMs is also described in some detail. Original investigations into the biological activity of endogenous SPMs led to the pairing of these ligands with the FPR2/LX receptor, and these results have been challenged in more recent work, leading to conflicting results and views, which are again discussed.

Experimental consideration of the effects of calcium lignosulfonate and tannic acid on the flammability and thermal properties of polylactide composites

The purpose of this study was to determine the quantitative and qualitative effects of the form of natural phenolic compounds (NPCs) on the decomposition of polylactide (PLA) under different measurement conditions. For this purpose, thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), and pyrolysis-combustion flow calorimetry (PCFC) analyses were carried out not only on individual raw materials like calcium lignosulfonate (BX), tannic acid (TA), BX chemically modified with TA (BMT), but also on PLA/BX, PLA/TA, and PLA/BMT composites with 3, 6, and 9 wt.% of filler. Moreover, the work checked whether to obtain satisfactory results it is necessary to carry out chemical modification lasting many hours, or whether simple physical mixing of ingredients (TABX) is enough, e.g. in proportions 1:2, 2:4, 3:6. The results of these analyses showed that TA is neither a good flame retardant nor a highly swelling material, but when combined with BX physically or chemically, it can produce an interesting synergistic effect. This work proves that chemically obtained BMT hybrid material allows to reduce flammability by 30 % compared to PLA which cannot be achieved by physically mixing these components in a polymer melt. On the other hand, the addition of TABX is sufficient to achieve a good thermal stabilization effect under processing conditions.

Screening Splice-Switching Antisense Oligonucleotides in Pancreas-Cancer Organoids.

Aberrant alternative splicing is emerging as a cancer hallmark and a potential therapeutic target. It is the result of dysregulated or mutated splicing factors, or genetic alterations in splicing-regulatory cis-elements. Targeting individual altered splicing events associated with cancer-cell dependencies is a potential therapeutic strategy, but several technical limitations need to be addressed. Patient-derived organoids are a promising platform to recapitulate key aspects of disease states, and to facilitate drug development for precision medicine. Here, we report an efficient antisense-oligonucleotide (ASO) lipofection method to systematically evaluate and screen individual splicing events as therapeutic targets in pancreatic ductal adenocarcinoma organoids. This optimized delivery method allows fast and efficient screening of ASOs, e.g., those that reverse oncogenic alternative splicing. In combination with advances in chemical modifications of oligonucleotides and ASO-delivery strategies, this method has the potential to accelerate the discovery of antitumor ASO drugs that target pathological alternative splicing.

Conformations of a highly expressed Z19 α-zein studied with AlphaFold2 and MD simulations.

α-zeins are amphiphilic maize seed storage proteins with material properties suitable for a multitude of applications e.g., in renewable plastics, foods, therapeutics and additive manufacturing (3D-printing). To exploit their full potential, molecular-level insights are essential. The difficulties in experimental atomic-resolution characterization of α-zeins have resulted in a diversity of published molecular models. However, deep-learning α-zein models are largely unexplored. Therefore, this work studies an AlphaFold2 (AF2) model of a highly expressed α-zein using molecular dynamics (MD) simulations. The sequence of the α-zein cZ19C2 gave a loosely packed AF2 model with 7 α-helical segments connected by turns/loops. Compact tertiary structure was limited to a C-terminal bundle of three α-helices, each showing notable agreement with a published consensus sequence. Aiming to chart possible α-zein conformations in practically relevant solvents, rather than the native solid-state, the AF2 model was subjected to MD simulations in water/ethanol mixtures with varying ethanol concentrations. Despite giving structurally diverse endpoints, the simulations showed several patterns: In water and low ethanol concentrations, the model rapidly formed compact globular structures, largely preserving the C-terminal bundle. At ≥ 50 mol% ethanol, extended conformations prevailed, consistent with previous SAXS studies. Tertiary structure was partially stabilized in water and low ethanol concentrations, but was disrupted in ≥ 50 mol% ethanol. Aggregated results indicated minor increases in helicity with ethanol concentration. β-sheet content was consistently low (∼1%) across all conditions. Beyond structural dynamics, the rapid formation of branched α-zein aggregates in aqueous environments was highlighted. Furthermore, aqueous simulations revealed favorable interactions between the protein and the crosslinking agent glycidyl methacrylate (GMA). The proximity of GMA epoxide carbons and side chain hydroxyl oxygens simultaneously suggested accessible reactive sites in compact α-zein conformations and pre-reaction geometries for methacrylation. The findings may assist in expanding the applications of these technologically significant proteins, e.g., by guiding chemical modifications.

Enhancing cellulose fiber properties from chromolaena odorata and anana comosus through novel pulping chemical mixtures

The production of cellulose with exceptional properties has led to the modification of chemical pulping methods and the development of newer chemical pulping methods. This study developed mixtures of sodium hydroxide, ethanol, and anthraquinone as new pulping chemicals to produce alpha-cellulose from pineapple leaves and Saim weed stems. The addition of anthraquinone was noticed to influence the pulp yield positively and the FTIR of all the cellulose has the characteristic cellulose bands. Calculated Total crystallinity index (TCI), (Lateral order index) LOI., and Hydrogen bond intensity (HBI) from the FTIR presented PLSHAEC (68.38 %) and SWSHQEC (67.74 %) having high crystallinity. From the XRD, the 2? by all the materials is attributed to cellulose I diffraction, and the crystallinity index aligned with FTIR determined crystallinity. The determined particle average diameter using ImageJ software showed that PLSHQEC 3.00 had the smallest value, followed by 5.17 for PLSHQC, 5.32 for SWSHQEC, and 6.03 for SWSHQEC. From the thermal analysis, the onset of the degradation of all the cellulose occurred at different temperatures: 247.10? (PLSHQC), 253.38? (PLSHQEC), 240.20? (SWSHQC) and 242.58? (SWSHQEC). The increase in yield, higher crystallinity index, and smaller fiber diameter of the cellulose demonstrated anthraquinone as a better additive to produce quality cellulose that would undergo easy chemical modification.

From Protein Structures to Functional Biomimetics

AbstractThe development of complex molecular scaffolds with defined folding properties represents a central challenge in chemical research. Proteins are natural scaffolds defined by a hierarchy of structural complexity and have evolved to manifest unique functional characteristics; for example, molecular recognition capabilities that facilitate the binding of target molecules with high affinity and selectivity. Utilizing these features, proteins have been used as a starting point for the design of synthetic foldamers and enhanced biocatalysts, as well as bioactive reagents in drug discovery. In this account, we describe the strategies used in our group to stabilize protein folds, ranging from the constraint of bioactive peptide conformations to chemical protein engineering. We discuss the evolution of peptides into peptidomimetics to inhibit protein–protein and protein–nucleic acid interactions, and the selective chemical modification of proteins to enhance their properties for biotechnological applications. The reported peptide- and proteomimetic structures cover a broad range of molecular sizes and they highlight the importance of structure stabilization for the design of functional biomimetics.1 Introduction2 Constraining the Conformation of Peptides3 Peptide-Based Covalent Protein Modifiers4 Chemical Protein Engineering5 Conclusions

Investigation of Polymer-Asphalt Compatibility Using Molecular Dynamics Simulation.

Polymer modification is a promising approach to enhancing the performance of asphalt binders. However, a major issue plaguing polymer mixing with asphalt is the phase separation of these two components post-mixing. In the field of polymer science, the Flory-Huggins theory has been long established as the way to describe the conditions under which a mixture is stable or unstable. This Flory-Huggins interaction parameter χ and the molecular weights of the components are required under this theory. This work uses molecular dynamics simulations to calculate χ between various polymers found in waste plastics and asphalt. The compatibility of these polymers with the asphalt binder is discussed as a function of binder composition, molecular weight, and temperature. Four common polymers (polyethylene, polystyrene, polypropylene, and polybutadiene) were tested. While none of the polymers showed good compatibility with asphalt, PE was the most compatible. Stable compatibilization of plastics with asphalt will require additives or chemical modification of the plastic.

Improved interfacial adhesion of carbon fiber‐reinforced polydicyclopentadiene layered composite material by modification of norbornene derivatives

AbstractSurface chemical grafting modifications of carbon fibers (CFs) using 5‐(triethoxysilyl)norbornene (TOS), norbornene carboxylic acid tert‐butyl ester (NB‐TBE), and 5‐norbornene‐2,3‐dicarboxylic anhydride (NA) improved interfacial interactions between CFs and poly(dicyclopentadiene) (PDCPD) resin. The ring‐opening metathesis polymerization (ROMP) of DCPD, catalyzed by Grubbs catalyst II, enabled the fabrication of PDCPD/CF layered composite materials with resin and fibers tightly adhered. The optimal composite exhibited remarkable mechanical properties, with a tensile strength of 654.6 MPa and flexural strength of 510.7 MPa. Excellent thermal stability with a maximum weight loss rate in temperatures above 450°C and good chemical resistance with a weight change of about 1% in both acidic and alkaline media highlight the promising potential of these materials for use in harsh environments. The simple yet efficient approach of TOS, NB‐TBE, and NA‐enhanced layered CF shows great promise as advanced composite materials for industrial applications.Highlights Norbornene derivatives such as TOS, NB‐TBE, and NA are suitable modifiers for CF. ROMP of DCPD and norbornene group onto CFs, fabrication of PDCPD/CF composite materials. The composite exhibited remarkable interfacial adhesion and mechanical properties.

Operando insights into ammonium-mediated lithium metal stabilization: surface morphology modulation and enhanced SEI development

Lithium-ion batteries (LiBs) with graphite as an anode and lithiated transition metal oxide as a cathode are approaching their specific energy and power theoretical values. To overcome the limitations of LiBs, lithium metal anode with high specific capacity and low negative redox potential is necessary. However, practical application in rechargeable cells is hindered by uncontrolled lithium deposition manifesting, for instance, as Li dendrite growth which can cause formation of dead Li, short circuits and cell failure.The electrochemical behaviour of a protic additive (NH4PF6) in a carbonate-based electrolyte has been investigated by operando confocal Raman spectroscopy, in situ optical microscopy, and X-ray photoelectron spectroscopy, elucidating its functional mechanism. The ammonium cation promotes a chemical modification of the lithium metal anode-electrolyte interphase by producing an N-rich solid electrolyte interphase and chemically modifying the lithium surface morphology by electrochemical pitting. This novel method results in stable lithium deposition and stripping by a decreasing the local current density on the electrode, thus limiting dendritic deposition.

Effect of the ex situ physical and in situ chemical modification of bacterial nanocellulose on mechanical properties in the context of its potential applications in heart valve design

Bacterial nanocellulose (BNC) is a promising material for heart valve prostheses. However, its low strength properties limit its applicability in cardiovascular surgery. To overcome these limitations, the mechanical properties of BNC can be improved through modifications. The aim of the research was to investigate the extent to which the mechanical properties of BNC can be altered by modifying its structure during its production and after synthesis. The study presents the results of various analyses, including tensile tests, nanoindentation tests, X-ray diffraction (XRD) tests, scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy, conducted on BNC chemically modified in situ with hyaluronic acid (BNC/HA) and physically modified ex situ through a dehydration/rehydration process (BNC 25DR, BNC105DR, BNC FDR and BNC/HA 25DR, BNC/HA 105DR, BNC/HA FDR). The results demonstrate that both chemical and physical modifications can effectively shape the mechanical properties of BNC. These modifications induce changes in the crystalline structure, pore size and distribution, and residual stresses of BNC. Results show the effect of the crystalline structure of BNC on its mechanical properties. There is correlation between hardness and Young's modulus and Iα/Iβ index for BNC/HA and between creep rate of BNC/HA, and Young's modulus for BNC vs Iα/Iβ index.

Synchronous Regulation of Hydrophobic Molecular Architecture and Interface Engineering for Robust WORM‐Type Memristor

Synchronous Regulation of Hydrophobic Molecular Architecture and Interface Engineering for Robust WORM‐Type Memristor

A bisulfite-assisted and ligation-based qPCR amplification technology for locus-specific pseudouridine detection at base resolution.

Over 150 types of chemical modifications have been identified in RNA to date, with pseudouridine (Ψ) being one of the most prevalent modifications in RNA. Ψ plays vital roles in various biological processes, and precise, base-resolution detection methods are fundamental for deep analysis of its distribution and function. In this study, we introduced a novel base-resolution Ψ detection method named pseU-TRACE. pseU-TRACE relied on the fact that RNA containing Ψ underwent a base deletion after treatment of bisulfite (BS) during reverse transcription, which enabled efficient ligation of two probes complementary to the cDNA sequence on either side of the Ψ site and successful amplification in subsequent real-time quantitative PCR (qPCR), thereby achieving selective and accurate Ψ detection. Our method accurately and sensitively detected several known Ψ sites in 28S, 18S, 5.8S, and even mRNA. Moreover, pseU-TRACE could be employed to measure the Ψ fraction in RNA and explore the Ψ metabolism of different pseudouridine synthases (PUSs), providing valuable insights into the function of Ψ. Overall, pseU-TRACE represents a reliable, time-efficient and sensitive Ψ detection method.

Influence of Silsesquioxane-Containing Ultra-Thin Polymer Films on Metal Oxide Gas Sensor Performance for the Tunable Detection of Biomarkers

Influence of Silsesquioxane-Containing Ultra-Thin Polymer Films on Metal Oxide Gas Sensor Performance for the Tunable Detection of Biomarkers

Engineering peptide drug therapeutics through chemical conjugation and implication in clinics.

The development of peptide drugs has made tremendous progress in the past few decades because of the advancements in modification chemistry and analytical technologies. The novel-designed peptide drugs have been modified through various biochemical methods with improved diagnostic, therapeutic, and drug-delivery strategies. Researchers found it a helping hand to overcome the inherent limitations of peptides and bring continued advancements in their applications. Furthermore, the emergence of peptide-drug conjugates (PDCs)-utilizes target-oriented peptide moieties as a vehicle for cytotoxic payloads via conjugation with cleavable chemical agents, resulting in the key foundation of the new era of targeted peptide drugs. This review summarizes the various classifications of peptide drugs, suitable chemical modification strategies to improve the ADME (adsorption, distribution, metabolism, and excretion) features of peptide drugs, and recent (2015-early 2024) progress/achievements in peptide-based drug delivery systems as well as their fruitful implication in preclinical and clinical studies. Furthermore, we also summarized the brief description of other types of PDCs, including peptide-MOF conjugates and peptide-UCNP conjugates. The principal aim is to provide scattered and diversified knowledge in one place and to help researchers understand the pinching knots in the science of PDC development and progress toward a bright future of novel peptide drugs.

Cellulose-Based Hydrogels for Wastewater Treatment: A Focus on Metal Ions Removal.

The rapid worldwide industrial growth in recent years has made water contamination by heavy metals a problem that requires an immediate solution. Several strategies have been proposed for the decontamination of wastewater in terms of heavy metal ions. Among these, methods utilizing adsorbent materials are preferred due to their cost-effectiveness, simplicity, effectiveness, and scalability for treating large volumes of contaminated water. In this context, heavy metal removal by hydrogels based on naturally occurring polymers is an attractive approach for industrial wastewater remediation as they offer significant advantages, such as an optimal safety profile, good biodegradability, and simple and low-cost procedures for their preparation. Hydrogels have the ability to absorb significant volumes of water, allowing for the effective removal of the dissolved pollutants. Furthermore, they can undergo surface chemical modifications which can further improve their ability to retain different environmental pollutants. This review aims to summarize recent advances in the application of hydrogels in the treatment of heavy metal-contaminated wastewater, particularly focusing on hydrogels based on cellulose and cellulose derivatives. The reported studies highlight how the adsorption properties of these materials can be widely modified, with a wide range of adsorption capacity for different heavy metal ions varying between 2.3 and 2240 mg/g. The possibility of developing new hydrogels with improved sorption performances is also discussed in the review, with the aim of improving their effective application in real scenarios, indicating future directions in the field.

Effects of UV-C exposure on composite materials made of recycled carbon fibers

Carbon fiber-reinforced polymers are widely used in space applications since they combine outstanding mechanical properties with low material density. However, the development of composite components involves raw materials that are becoming increasingly scarce and contributes significantly to carbon emissions during the manufacturing process. Indeed, the fabrication of fibers is energy-intensive and requires very high temperatures, high costs, and usually precursor materials derived from fossil fuels. In addition to the negative environmental impact due to the manufacturing process, there are critical issues related to the disposal of components fabricated using carbon/glass fiber composites. Therefore, the use of efficient recycling strategies becomes necessary, according to economic reasons and legislation. The recycled fibers exhibit different properties from virgin fibers, generally lower, due to adverse effects of the current recycling methods. In this study, we investigated the potential application of recovered carbon fibers in satellite platforms, using recycled fibers from our laboratory obtained with a subcritical solvolysis method that we have previously developed. Composite materials reinforced with recycled and virgin carbon fibers were exposed to UV-C, and the effects of irradiation were analyzed in terms of structural performance, surface morphology, and chemical modifications of the samples. Results were used to evaluate the possibility of effectively using recycled fibers in space applications, without significant loss of performance.

Investigating of epoxy nanocomposites structure and properties that contain both pristine and aminosilane-treated silicon carbide (SiC) particles

This article presents a methodology for functionalization of silicon carbide (SiC) through chemical modification using γ-aminopropyltriethoxysilane (APTES) and its subsequent dispersion in an epoxy composition. The research revealed that functionalizing SiC particles with γ-aminopropyltriethoxysilane (SiC(APTES)) enhanced their chemical compatibility with the epoxy composition, facilitating the dispersion of SiC particles. Furthermore, it was observed that the functionalization of the filler had a profound impact on the structure, curing kinetics, and physical and mechanical properties of epoxy nanocomposites. The addition of SiC(APTES) into the epoxy composition resulted in a significant reinforcement of the material. Specifically, the flexural stress and flexural modulus of elasticity increased by 179% and 74%, respectively, while the impact strength experienced a remarkable improvement of 462%. Additionally, the tensile strength and tensile modulus of elasticity increased by 83% and 70%, respectively, compared to the epoxy composite without SiC. The application of SiC(APTES) also played a crucial role in initiating the polymerization process through the involvement of reactive amino groups, leading to a reduction in the initial curing temperature and an amplification of the thermal effects of the polymerization reaction. Moreover, the presence of functionalized SiC significantly influenced the structure of the epoxy composite, thereby contributing to its enhanced strength. In summary, the inclusion of SiC in the epoxy composition not only bolstered the material but also improved its thermal stability.