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An alkali-soluble ß-glucan (AHEP-A-b, 20 kDa) purified from Hericium erinaceus fruiting bodies, was structurally characterized and examined for antioxidant activity. Methylation analysis and NMR spectroscopy show that the backbone of AHEP-A-b is composed of (1→6)-linked-D-ß-glucopyran residues, branched at O-3 of glucopyranose (Glcp) residues with [→3)-ß-D-Glcp-(1→] oligosaccharides or single unit of ß-Glcp. Periodate oxidation analysis and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) indicate that the degree of polymerization (DP) of [→3)-ß-D-Glcp-(1→] side chains is 2 to 8. Functionally, AHEP-A-b is a relatively strong antioxidant as demonstrated by using 2, 2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) free radical (ABTS·+), 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals, and hydroxyl radicals scavenging assays. The present study lays the foundation for further studies into structure-activity relationships of polysaccharides from H. erinaceus.

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Gelation is a critical property of citrus pectin. However, the roles played by neutral sugar side-chains on acid-induced pectin gelation remain poorly understood. Herein, galactan- or/and arabinan-eliminated pectins (P-G, P-A, and P-AG) were used to investigate the effects of side-chains on gelation. The gel hardness values of citrus pectin, P-G, P-A, and P-AG were 42.6, 39.9, 5.3, and 2.1 g, respectively, suggesting that arabinan contributed more to gelation than galactan. We next found that arabinan branches promoted pectin chain entanglement more effectively than arabinan backbones. Destabilizer addition experiments showed that hydrogen bonding, electrostatic interaction, and hydrophobic interaction were the main forces affecting pectin gel networks and strength, which was further validated by molecular dynamic simulations. The total number of hydrogen bonds between the arabinan branches and galactan/HG (65.7) was significantly higher than that between the arabinan backbones and galactan/HG (39.1), indicating that arabinan branches predominated in terms of such interactions. This study thus elucidated the roles played by neutral-sugar side-chains, especially the arabinan branches of acid-induced pectin gels, in term of enhancing high-methoxyl pectin gelation, and offers novel insights into the structure-gelling relationships of citrus pectin.

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Rational molecular design and suitable device engineering are two important strategies to boost the efficiencies in organic solar cells (OSCs). Yet these two approaches are independently developed, while their synergy is believed to be more productive. Herein, a branched polyfluoride moiety, heptafluoroisopropoxyl group, is introduced into the side chains of conjugated polymers for the first time. Compared with the conventional alkyl chain, this polyfluoride chain can endow the resulting polymer namely PF7 with highly packing order and strong crystallinity owing to the strong polarization and fluorine-induced interactions, while good solubility and moderate miscibility are retained. As a result, PF7 comprehensively outperforms the state-of-the-art polymer PM6 in photovoltaic properties. More importantly, based on the solubility of heptafluoroisopropoxyl groups in fluorous solvents, a new post-treatment denoted as fluorous solvent vapor annealing (FSVA) is proposed to match PF7. Differing from the existing post-treatments, FSVA can selectively reorganize fluoropolymer molecules but less impact small molecules in blend films. By employing the synergy of fluoropolymer and fluorous solvent, the device achieves a remarkable efficiency of 19.09%, which is among the best efficiencies in binary OSCs. The polymer PF7 and the FSVA treatment exhibit excellent universality in various OSCs with different material combinations or device architectures.

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Indoor photovoltaics (IPVs) are garnering increasing attention from both the academic and industrial communities due to the pressing demand of the ecosystem of Internet-of-Things. All-polymer solar cells (all-PSCs), emerging as a sub-type of organic photovoltaics, with the merits of great film-forming properties, remarkable morphological and light stability, hold great promise to simultaneously achieve high efficiency and long-term operation in IPV's application. However, the dearth of polymer acceptors with medium-bandgap has impeded the rapid development of indoor all-PSCs. Herein, a highly efficient medium-bandgap polymer acceptor (PYFO-V) is reported through the synergistic effects of side chain engineering and linkage modulation and applied for indoor all-PSCs operation. As a result, the PM6:PYFO-V-based indoor all-PSC yields the highest efficiency of 27.1% under LED light condition, marking the highest value for reported binary indoor all-PSCs to date. More importantly, the blade-coated devices using non-halogenated solvent (o-xylene) maintain an efficiency of over 23%, demonstrating the potential for industry-scale fabrication. This work not only highlights the importance of fine-tuning intramolecular charge transfer effect and intrachain coplanarity in developing high-performance medium-bandgap polymer acceptors but also provides a highly efficient strategy for indoor all-PSC application.

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Utilizing one molecule to realize combinational photodynamic and photothermal therapy upon single-wavelength laser excitation, which relies on a multifunctional phototherapy agent, is one of the most cutting-edge research directions in tumor therapy owing to the high efficacy achieved over a short course of treatment. Herein, a simple strategy of "suitable isolation side chains" is proposed to collectively improve the fluorescence intensity, reactive oxygen species production, photothermal conversion efficiency, and biodegradation capacity. Both in vitro and in vivo results reveal the practical value and huge potential of the designed biodegradable conjugated polymer PTD-C16 with suitable isolation side chains in fluorescence image-guided combinational photodynamic and photothermal therapy. These improvements are achieved through manipulation of aggregated states by only side chain modification without changing any conjugated structure, providing new insight into the design of biodegradable high-performance phototherapy agents.

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Balancing the rigid backbones and flexible side chains of light-harvesting materials is crucially important to reach optimized intermolecular packing, micromorphology, and thus photovoltaic performance of organic solar cells (OSCs). Herein, based on a distinctive CH-series acceptor platform with 2D conjugation extended backbones, a series of nonfullerene acceptors (CH-6F-Cn) are synthesized by delicately tuning the lengths of flexible side chains from n-octyl to n-amyl. A systemic investigation has revealed that the variation of the side chain's length can not only modulate intermolecular packing modes and crystallinity but also dramatically improve the micromorphology of the active layer and eventual photovoltaic parameters of OSCs. Consequently, the highest PCE of 18.73% can be achieved by OSCs employing D18:PM6:CH-6F-C8 as light-harvesting materials.

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DNA three-way junction (3WJ) structures with three amino acid side chains in the core have been synthesized via post-synthetic DNA modification. Amide condensation reactions of oligonucleotides containing 2'-aminouridine with activated esters yielded DNA strands modified with His, Cys and Asp side chains to form modified 3WJs. Even a 3WJ with three negatively charged Asp side chains formed stably at room temperature. Furthermore, DNA hybridization alone placed two (His and Asp) and three (His, Cys, and Asp) side chains within the 3WJs, indicating that the DNA 3WJs are a useful platform for spatial arrangement of amino acid side chains.

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Side chain engineering plays a vital role in exploring high-performance small molecule acceptors (SMAs) for organic solar cells (OSCs). In this work, we designed and synthesized a series of A-DA'D-A type SMAs by introducing different N-substituted alkyl and ester alkyl side chains on benzotriazole (BZ) central unit and aimed to investigate the effect of different ester substitution positions on photovoltaic performances. All the new SMAs with ester groups exhibit lower the lowest unoccupied molecular orbital (LUMO) energy levels and more blue-shifted absorption, but relatively higher absorption coefficients than alkyl chain counterpart. After blending with the donor PM6, the ester side chain-based devices demonstrate enhanced charge mobility, reduced amorphous intermixing domain size and long-lived charge transfer state compared to the alkyl chain counterpart, which are beneficial to achieve higher short-circuit current density (Jsc ) and fill factor (FF), simultaneously. Thereinto, the PM6 : BZ-E31 based device achieves a higher power conversion efficiency (PCE) of 18.33 %, which is the highest PCE among the OSCs based on the SMAs with BZ-core. Our work demonstrated the strategy of ester substituted side chain is a feasible and effective approach to develop more efficient SMAs for OSCs.

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In the development of high-performance organic solar cells (OSCs), the self-organization of organic semiconductors plays a crucial role. This study focuses on the precisely manipulation of molecular assemble via tuning alkyl side-chain topology in a series of low-cost nonfused-ring electron acceptors (NFREAs). Among the three NFREAs investigated, DPA-4, which possesses an asymmetric alkyl side-chain length, exhibits a tight packing in the crystal and high crystallinity in the film, contributing to improved electron mobility and favorable film morphology for DPA-4. As a result, the OSC device based on DPA-4 achieves an excellent power conversion efficiency of 16.67 %, ranking among the highest efficiencies for NFREA-based OSCs.

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Up to now, researches on the mobility-stretchability of semiconducting polymers are extensively investigated, but little attention was  paid to their morphology and field-effect transistor characteristics under compressive strains, which is equally crucial in wearable electronic applications. In this work, a contact film transfer method is applied to evaluate the mobility-compressibility properties of conjugated polymers. A series of isoindigo-bithiophene conjugated polymers with symmetric carbosilane side chains (P(SiSi)), siloxane-terminated alkyl side chains (P(SiOSiO)), and combined asymmetric side chains (P(SiOSi)) are investigated. Accordingly, a compressed elastomer slab is used to transfer and compress the polymer films by releasing prestrain, and the morphology and mobility evolutions of these polymers are tracked. It is found that P(SiOSi) outperforms the other symmetric polymers including P(Si─Si) and P(SiO─SiO), having the ability to dissipate strain with its shortened lamellar spacing and orthogonal chain alignment. Notably, the mechanical durability of P(SiOSi) is also enhanced after consecutive compress-release cycles. In addition, the contact film transfer technique is demonstrated to be applicable to investigate the compressibility of different semiconducting polymers. These results demonstrate a comprehensive approach to understand the mobility-compressibility properties of semiconducting polymers under tensile and compressive strains.

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In recent decades, polymer semiconductors, extensively employed as charge transport layers in devices like organic field-effect transistors (OFETs), have undergone thorough investigation due to their capacity for large-area solution processing, making them promising for mass production. Research efforts have been twofold: enhancing the charge mobilities of polymer semiconductors and augmenting their mechanical properties to meet the demands of flexible devices. Significant progress has been made in both realms, propelling the practical application of polymer semiconductors in flexible electronics. However, integrating excellent semiconducting and mechanical properties into a single polymer still remains a significant challenge. This review intends to introduce the design strategies and discuss the properties of high-charge mobility stretchable conjugated polymers. In addition, another key challenge faced in this cutting-edge field is maintaining stable semiconducting performance during long-term mechanical deformations. Therefore, this review also discusses the development of healable polymer semiconductors as a promising avenue to improve the lifetime of stretchable device. In conclusion, challenges and outline future research perspectives in this interdisciplinary field are highlighted.

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Amino acid substitutions and post-translational modifications (PTMs) play a crucial role in many cellular processes by directly affecting the structural and dynamic features of protein interaction. Despite their importance, the understanding of protein PTMs at the structural level is still largely incomplete. The Protein Data Bank contains a relatively small number of 3D structures having post-translational modifications. Although recent years have witnessed significant progress in three-dimensional modeling (3D) of proteins using neural networks, the problem related to predicting accurate PTMs in proteins has been largely ignored. Predicting accurate 3D PTM models in proteins is closely related to another fundamental problem: predicting the correct side-chain conformations of amino acid residues in proteins. An analysis of publications as well as the paid and free software packages for modeling three-dimensional structures showed that most of them focus on working with unmodified proteins and canonical amino acid residues; the number of articles and software packages placing emphasis on modeling three-dimensional PTM structures is an order of magnitude smaller. This paper focuses on modeling the side-chain conformations of proteins containing PTMs (nonstandard amino acid residues). We collected our own libraries comprising the most frequently observed PTMs from the PDB and implemented a number of algorithms for predicting the side-chain conformation at modification points and in the immediate environment of the protein. A comprehensive analysis of both the algorithms per se and compared to the common Rosetta and FoldX structure modeling packages was also carried out. The proposed algorithmic solutions are comparable in their characteristics to the well-known Rosetta and FoldX packages for the modeling of three-dimensional structures and have great potential for further development and optimization. The source code of algorithmic solutions has been deposited to and is available at the GitHub source.

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We present a model, based on symmetry and geometry, for proteins. Using elementary ideas from mathematics and physics, we derive the geometries of discrete helices and sheets. We postulate a compatible solvent-mediated emergent pairwise attraction that assembles these building blocks, while respecting their individual symmetries. Instead of seeking to mimic the complexity of proteins, we look for a simple abstraction of reality that yet captures the essence of proteins. We employ analytic calculations and detailed Monte Carlo simulations to explore some consequences of our theory. The predictions of our approach are in accord with experimental data. Our framework provides a rationalization for understanding the common characteristics of proteins. Our results show that the free energy landscape of a globular protein is pre-sculpted at the backbone level, sequences and functionalities evolve in the fixed backdrop of the folds determined by geometry and symmetry, and that protein structures are unique in being simultaneously characterized by stability, diversity, and sensitivity.

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This study investigates the solid-state charge transport properties of the oxidized forms of dioxythiophene-based alternating copolymers consisting of an oligoether-functionalized 3,4-propylenedioxythiophene (ProDOT) copolymerized with different aryl groups, dimethyl ProDOT (DMP), 3,4-ethylenedioxythiophene (EDOT), and 3,4-phenylenedioxythiophene (PheDOT), respectively, to yield copolymers P(OE3)-D, P(OE3)-E, and P(OE3)-Ph. At a dopant concentration of 5 mM FeTos3, the electrical conductivities of these copolymers vary significantly (ranging between 9 and 195 S cm-1) with the EDOT copolymer, P(OE3)-E, achieving the highest electrical conductivity. UV-vis-NIR and X-ray spectroscopies show differences in both susceptibility to oxidative doping and extent of oxidation for the P(OE3) series, with P(OE3)-E being the most doped. Wide-angle X-ray scattering measurements indicate that P(OE3)-E generally demonstrates the lowest paracrystallinity values in the series, as well as relatively small π-π stacking distances. The significant (i.e., order of magnitude) increase in electrical conductivity of doped P(OE3)-E films versus doped P(OE3)-D or P(OE3)-Ph films can therefore be attributed to P(OE3)-E exhibiting both the highest carrier ratios in the P(OE3) series, along with good π-π overlap and local ordering (low paracrystallinity values). Furthermore, these trends in the extent of doping and paracrystallinity are consistent with the reduced Fermi energy level and transport function prefactor parameters calculated using the semilocalized transport (SLoT) model. Observed differences in carrier ratios at the transport edge (ct) and reduced Fermi energies [η(c)] suggest a broader electronic band (better overlap and more delocalization) for the EDOT-incorporating P(OE3)-E polymer relative to P(OE3)-D and P(OE3)-Ph. Ultimately, we rationalize improvements in electrical conductivity due to microstructural and doping enhancements caused by EDOT incorporation, a structure-property relationship worth considering in the future design of highly electrically conductive systems.

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Power conversion efficiency (PCE) of organic solar cells (OSCs) processed by nonhalogenated solvents is unsatisfactory due to the unfavorable morphology. Herein, two new small molecule acceptors (SMAs) Y6-Ph and L8-Ph are synthesized by introducing a phenyl end group in the inner side chains of the SMAs of Y6 and L8-BO, respectively, for overcoming the excessive aggregation of SMAs in the long-time film forming processed by nonhalogenated solvents. First, the effect of the film forming time on the aggregation property and photovoltaic performance of Y6, L8-BO, Y6-Ph, and L8-Ph is studied by using the commonly used solvents: chloroform (CF) (rapid film forming process) and chlorobenzene (CB) (slow film forming process). It is found that Y6- and L8-BO-based OSCs exhibit a dramatic drop in PCE from CF- to CB-processed devices owing to the large phase separation, while the Y6-Ph and L8-Ph based OSCs show obviously increased PCEs Furthermore, L8-Ph-based OSCs processed by nonhalogenated solvent o-xylene (o-XY) achieved a high PCE of 18.40% with an FF of 80.11%. The results indicate that introducing a phenyl end group in the inner side chains is an effective strategy to modulate the morphology and improve the photovoltaic performance of the OSCs processed by nonhalogenated solvents.

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Lactic acid bacteria of the genus Weissella contribute to spontaneous fermentation in, e.g., sourdough or sauerkraut, but are not registered as starter cultures because of their pending safety assessment. Some strains are able to produce high amounts of exopolysaccharides. This study aims to demonstrate the techno-functionality of five dextrans from W. cibaria DSM14295, produced under varying cultivation conditions, with respect to structural and macromolecular properties. A maximum of 23.1 g/L dextran was achieved by applying the "cold shift" temperature regime. The dextrans differed in molecular mass (9-22∙108 Da, determined by HPSEC-RI/MALLS), intrinsic viscosity (52-73 mL/g), degree of branching (3.8-5.7 % at position O3, determined by methylation analysis) and their side chain length and architecture, determined by HPAEC-PAD after enzymatic hydrolysis. Stiffness of acid gels from milk spiked with these dextrans increased linearly with dextran concentration. Principal component analysis showed that dextrans produced in a semi-defined medium are primarily described by moisture sorption and branching properties, whereas dextrans produced in whey permeate were similar because of their functional and macromolecular properties. Overall, dextrans from W. cibaria DSM14295 have a high potential because of the high production yield and their functionality which can be tailored by the conditions during fermentation.

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To realize efficient, green solvent-processable organic solar cells (OSCs), considerable effort has been expended on the development of conjugated materials with both superior optoelectrical properties and processability. However, molecular design strategies that enhance solubility often reduce crystalline/electrical properties of the materials. In this study, we develop three new guest small-molecule acceptors (SMAs) (Y-4C-4O, Y-6C-4O, and Y-12C-4O) featuring inner side chains consisting of terminal oligo(ethylene glycol) (OEG) groups and alkyl spacers of different lengths. When a host SMA (Y6) and guest SMA (Y-nC-4O) are mixed, favorable interactions between these materials lead to the formation of "alloy-like" composites. The alloy-like SMA composites enable sufficient processing in o-xylene to afford suitable blend-film morphologies. It is also found that the lengths of the alkyl spacers in guest SMAs have a significant impact on the performance of the o-xylene-processed OSCs. The PM6:Y6:Y-4C-4O blend achieves a maximum power conversion efficiency (PCE) of 17.03%, outperforming PM6:Y6:Y-6C-4O (PCE = 15.85%) and PM6:Y6:Y-12C-4O (PCE = 12.12%) OSCs. The high PCE of the PM6:Y6:Y-4C-4O device is mainly attributed to the well-intermixed morphology and superior crystalline/electrical properties, which result from the high compatibility of the Y6:Y-4C-4O composites with PM6. Thus, we demonstrate that an alloy-like SMA composite based on well-designed OEG-incorporated Y-series SMAs can afford green solvent-processable, high-performance OSCs.

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By binding to its receptor, glucagon-like peptide-1 (GLP-1) plays various physiological roles, including activating glucose-dependent insulin secretion, inhibiting gastric emptying, and reducing appetite. This suite of activities makes GLP-1 and its analogs an attractive choice for treating type 2 diabetes mellitus in the context of overweight or obesity. This study used different types and lengths of fatty acids to design dual fatty acid side chains for GLP-1 receptor agonists including decanoic, dodecanoic, tetradecanoic, hexadecanoic, dodecanedioic, tetradecanedioic, hexadecanedioic, and octadecanedioic acids. Sixteen GLP-1 receptor agonists (conjugates 13-28) with dual fatty acid side chains were obtained by liquid-phase synthesis. After structural confirmation using high-resolution mass spectrometry, peptide mapping, and circular dichroism, the biological activities of the conjugates were screened. First, the conjugates were screened for albumin binding and activity in GLP-1R-CRE-bla CHO-K1 cells. Albumin binding results suggested a synergistic effect between the two fatty acids in the conjugates. Next, conjugates 18, 19, and 21 selected after primary screening were assessed for receptor affinity, activity in INS-1 cells, plasma stability across different species, and efficacy and pharmacokinetics in normal and db/db mice. One candidate (conjugate 19) was found to have albumin binding of >99 %, good receptor affinity, activities of INS-1 cells, and plasma stability. We found that cellular activities in GLP-1R-CRE-bla CHO-K1 cells and pharmacodynamics and pharmacokinetics in normal and db/db mice for conjugate 19 were superior to those of semaglutide.

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Processing additive plays an important role in the standard operation procedures for fabricating top performing polymer solar cells (PSCs) through efficient interactions with key photovoltaic materials. However, improving interaction study of acceptor materials to high performance halogenated aromatic additives such as diiodobenzene (DIB) is a widely neglected route for molecular engineering toward more efficient device performances. In this work, two novel Y-type acceptor molecules of BTP-TT and BTP-TTS with different aromatic side chains on the outer positions are designed and synthesized. The resulting aromatic side chains significantly enhanced the interactions between the acceptor molecules and DIB through an arene/halogenated arene interaction, which improved the crystallinity of the acceptor molecules and induced a polymorph with better photovoltaic performances. Thus, high power conversion efficiencies (PCEs) of 18.04% and 19.22% are achieved in binary and ternary blend devices using BTP-TTS as acceptor and DIB as additive. Aromatic side chain engineering for improving additive interactions is proved to be an effective strategy for achieving much higher performance photovoltaic materials and devices.

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Intrinsically stretchable conjugated polymers (CPs) have extensively been studied for the development of novel flexible electronic devices. In this work, a method to control the elastic properties of CPs has been proposed via regulation of spacer length between the siloxane side-chain and the backbone. The target polymers were CP films with the structure P(mC-Si) for four different numbers of the spacer methylene groups, namely, m = 5, 6, 7, and 8. The effect of spacer length on the aggregation state as well as on electrical and elastic properties of the prepared films was then investigated. An adjustable lamellar spacing (dL-L), in addition to improved elastic properties, was achieved as the spacer length was changed in the prepared polymer films. Moreover, P(7C-Si) has a sufficient dL-L value of 35.77 Å, which provides enough space for inter-chain sliding to dissipate stress. This facilitated the dissipation of stress during the straining process. At a strain value of 100% in the vertical direction, the mobility of the P(7C-Si) film was 0.79 cm2 V-1 s-1 and reduced to 84.0% of the initial value without any applied strain. The study provides clear evidence that tuning the spacer length between the silicone endgroup and backbone is an effective way to improve the intrinsic stretchability of CPs with siloxane side chains.