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1.
J Dent Sci ; 19(2): 945-951, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38618100

RESUMO

Background/Purpose: In vat photopolymerization, post-polymerization of the three-dimensional (3D) printing resin is necessary to ensure the optimum physical properties of the printed objects. This study aimed to evaluate the potential use of a handheld polywave light-emitting diode (LED) dental light-curing unit (LCU) for post-polymerizing 3D printed resins by measuring the microhardness and biaxial flexural strength of the post-polymerized resin. Material and methods: 3D printed 1- and 2-mm-thick disks were irradiated with a dental LCU at 3200 mW/cm2. Post-polymerization was repeated either on one side from the top surface: two cycles (T2), four cycles (T4), and eight cycles (T8), or on both sides from the top and bottom surfaces: one cycle (T1B1), two cycles (T2B2), and four cycles (T4B4) for each side. The microhardness and biaxial strength of the disks were compared to those post-polymerized by a conventional desktop polymerizing unit (PC) and those without post-polymerization (NC). Results: Microhardness of the disks varied between the top and bottom surfaces of the 1-mm and 2-mm-thick disks, depending on the post-polymerization methods. T8 and T4B4 produced comparable microhardness on the top surface to PC for both thicknesses. In contrast, PC, T2B2, and T4B4 exhibited the highest microhardness on the bottom surface. Except for NC, the 1-mm-thick disks had a higher biaxial flexural strength than the 2-mm-thick disks. T4B4 resulted in the highest biaxial flexural strength for both thicknesses, which was comparable to that of the desktop polymerizing unit. Conclusion: The microhardness and biaxial flexural strengths of the post-polymerized 3D-printed disks increase with polymerization time. With sufficient polymerization from both sides, the polywave LCU has the potential to be a viable alternative to desktop polymerization units.

2.
Angew Chem Int Ed Engl ; : e202402453, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38622832

RESUMO

Fabrication of large-area thin films through irreversible reactions remains a formidable task. This study reports a breakthrough strategy for in situ synthesis of large-area, free-standing, robust and multi-stimulus responsive thin films through a catalyst-free and irreversible Katritzky reaction at a liquid-liquid interface. The as resulted films are featured with adjustable thickness of 1-3 µm and an area up to 50 cm². The thin films exhibit fast photo-mechanical motions (a response time of ca 0.1 s), vapor-mechanical motions, as well as photo-chromic and solvato-chromic behaviors. It was revealed that the reason behind the observable motions is proton transfer from the imine groups to the carbonyl structures within the film induced by photo- and/or dimethyl sulfoxide-stimulus. In addition, the films can harvest anionic radicals and the radicals as captured can be efficiently degraded under UV light illumination. This study provides a new strategy for fabricating smart thin films via interfacially confined irreversible Katritzky reaction.

3.
ACS Nano ; 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38623861

RESUMO

The key to any controlled supramolecular polymerization (CSP) process lies in controlling the nucleation step, which is typically achieved by sequestering monomers in a kinetically trapped state. However, kinetic traps that are shallow cannot prevent spontaneous nucleation, thus limiting the applicability of the CSP in such systems. We use a molecular additive to overcome this limitation by modifying the energy landscape of a competitive self-assembly process and increasing the kinetic stability of an otherwise short-lived trap state. The additive achieves this by simultaneously catalyzing OFF-pathway nucleation and inhibiting ON-pathway aggregation. In the process, it guides the molecular assembly exclusively toward the OFF-pathway aggregate analogue. The mechanisms of OFF-pathway catalysis and ON-pathway inhibition are elucidated. By specifically targeting the nucleation step, it was possible to achieve pathway selection at an extremely low additive-to-monomer ratio of 1:100. The generality of our approach is also demonstrated for other related molecular systems. Finally, removing the additive triggers the cross-nucleation of the ON-pathway aggregate on the surface of a less stable, OFF-pathway aggregate analogue. The resultant supramolecular polymer not only exhibits a more uniform morphology but more importantly, a marked improvement in the structural order that leads to an amplification of chiral asymmetry and a high absorption dissymmetry factor (gAbs) of ∼0.05.

4.
Small Methods ; : e2400185, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38616739

RESUMO

Developing the films of N-containing unsubstituted poly(p-phenylene) (PPP) films for diverse applications is significant and highly desirable because the replacement of sp2 C atoms with sp2 N atoms will bring novel properties to the as-prepared polymers. In this research, an electrochemical-dehalogenation polymerization strategy is employed to construct two N-containing PPP films under constant potentials, where 2,5-diiodopyridine (DIPy) and 2,5-dibromopyrazine (DBPz) are used as starting agents. The corresponding polymers are named CityU-23 (for polypyridine) and CityU-24 (for polypyrazine). Moreover, it is found that both polymers can form films in situ on different conductive substrates (i.e., silicon, gold, ITO, and nickel), satisfying potential device fabrication. Furthermore, the as-obtained thin films of CityU-23 and CityU-24 exhibit good performance of alkaline hydrogen evolution reaction with the overpotential of 212.8 and 180.7 mV and the Tafel slope of 157.0 and 122.4 mV dec-1, respectively.

5.
Polymers (Basel) ; 16(7)2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38611129

RESUMO

Secondary reactions in radical polymerization pose a challenge when creating kinetic models for predicting polymer structures. Despite the high impact of these reactions in the polymer structure, their effects are difficult to isolate and measure to produce kinetic data. To this end, we used solvation-corrected M06-2X/6-311+G(d,p) ab initio calculations to predict a complete and consistent data set of intrinsic rate coefficients of the secondary reactions in acrylate radical polymerization, including backbiting, ß-scission, radical migration, macromonomer propagation, mid-chain radical propagation, chain transfer to monomer and chain transfer to polymer. Two new approaches towards computationally predicting rate coefficients for secondary reactions are proposed: (i) explicit accounting for all possible enantiomers for reactions involving optically active centers; (ii) imposing reduced flexibility if the reaction center is in the middle of the polymer chain. The accuracy and reliability of the ab initio predictions were benchmarked against experimental data via kinetic Monte Carlo simulations under three sufficiently different experimental conditions: a high-frequency modulated polymerization process in the transient regime, a low-frequency modulated process in the sliding regime at both low and high temperatures and a degradation process in the absence of free monomers. The complete and consistent ab initio data set compiled in this work predicts a good agreement when benchmarked via kMC simulations against experimental data, which is a technique never used before for computational chemistry. The simulation results show that these two newly proposed approaches are promising for bridging the gap between experimental and computational chemistry methods in polymer reaction engineering.

6.
Polymers (Basel) ; 16(7)2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38611131

RESUMO

Traditional polymer curing techniques present challenges such as a slow processing speed, high energy consumption, and considerable initial investment. Frontal polymerization (FP), a novel approach, transforms monomers into fully cured polymers through a self-sustaining exothermic reaction, which enhances speed, efficiency, and safety. This study focuses on acrylamide hydrogels, synthesized via FP, which hold significant potential for biomedical applications and 3D printing. Heat conduction is critical in FP, particularly due to its influence on the temperature distribution and reaction rate mechanisms, which affect the final properties of polymers. Therefore, a comprehensive analysis of heat conduction and chemical reactions during FP is presented through the establishment of mathematical models and numerical methods. Existing research on FP hydrogel synthesis primarily explores chemical modifications, with limited studies on numerical modeling. By utilizing Differential Scanning Calorimetry (DSC) data on the curing kinetics of polymerizable deep eutectic solvents (DES), this paper employs Malek's model selection method to establish an autocatalytic reaction model for FP synthesis. In addition, the finite element method is used to solve the reaction-diffusion model, examining the temperature evolution and curing degree during synthesis. The results affirm the nth-order autocatalytic model's accuracy in studying acrylamide monomer curing kinetics. Additionally, factors such as trigger temperature and solution initial temperature were found to influence the FP reaction's frontal propagation speed. The model's predictions on acrylamide hydrogel synthesis align with experimental data, filling the gap in numerical modeling for hydrogel FP synthesis and offering insights for future research on numerical models and temperature control in the FP synthesis of high-performance hydrogels.

7.
Polymers (Basel) ; 16(7)2024 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-38611160

RESUMO

A family of titanium complexes (Ti1-Ti7) with the general formula LTiCl3, supported by tridentate phenoxyimine [O-NO] ligands (L1-L7) bearing bulky sidearms, were synthesized by treating the corresponding ligands with stoichiometric amount of TiCl4. All the ligands and complexes were well characterized by 1H and 13C NMR spectroscopies, in which ortho- methoxyl groups on N-aryl moieties shifted to downfield, corroborating the successful coordination reaction. Structural optimization by DFT calculations revealed that one of the phenyl groups on dibenzhydryl moiety could form π-π stacking interaction with the salicylaldimine plane, because of which the obtained titanium complexes revealed good thermal stabilities for high-temperature polymerization of ethylene. The thermal robustness of the complexes was closely related to the strength of π-π stacking interactions, which were mainly influenced by the substituents on the dibenzhydryl moieties; Ti1, Ti4 and Ti5 emerged as the three best-performing complexes at 110 °C. With the aid of such π-π stacking interactions, the complexes were also found to be active at >150 °C, although decreased activities were witnessed. Besides homopolymerizations, complexes Ti1-Ti7 were also found to be active for the high-temperature copolymerization of ethylene and 1-octene, but with medium incorporation percentage, demonstrating their medium copolymerization capabilities.

8.
Polymers (Basel) ; 16(7)2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38611167

RESUMO

Tung oil (TO) microcapsules (MCs) with a poly(urea-formaldehyde) (PUF) shell were synthesized via one-step in situ polymerization, with the addition of graphene nanoplatelets (GNPs) (1-5 wt. %). The synergistic effects of emulsifiers between gelatin (gel) and Tween 80 were observed, with gel chosen to formulate the MCs due to its enhanced droplet stability. SEM images then displayed an increased shell roughness of the TO-GNP MCs in comparison to the pure TO MCs due to the GNP species on the shell. At the same time, high-resolution transmission electron microscopy (TEM) images also confirmed the presence of GNPs on the outer layer of the MCs, with the stacked graphene layers composed of 5-7 layers with an interlayer distance of ~0.37 nm. Cross-sectional TEM imaging of the MCs also confirmed the successful encapsulation of the GNPs in the core of the MCs. Micromanipulation measurements displayed that the 5% GNPs increased the toughness by 71% compared to the pure TO MCs, due to the reduction in the fractional free volume of the core material. When the MCs were dispersed in an epoxy coating and applied on a metallic substrate, excellent healing capacities of up to 93% were observed for the 5% GNP samples, and 87% for the pure TO MC coatings. The coatings also exhibited excellent corrosion resistance for all samples up to 7 days, with the GNP samples offering a more strenuous path for the corrosive agents.

9.
Polymers (Basel) ; 16(7)2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38611178

RESUMO

Conductive polymers such as polypyrrole have been widely used as pseudo-capacitive electrodes for supercapacitors. This work demonstrates a simple method to improve the performance of conductive polymer electrodes by adding montmorillonite in order to perform capacitive behavior. Conductive composite polymers (CCPs) based on montmorillonite/polypyrrole (MMT/PPy(Cl)) have been synthesized by polymerization using FeCl3 as an oxidizing agent. During the preparation of CCP, the effect of MMT/pyrrole mass ratio and the influence of the amount of added H+ and temperature of the synthesis medium on the electrochemical performance of the composite have been investigated. The investigation associated with conductivity measurement allowed us to determine the best conditions to reach a high specific capacitance of 465 F gr-1 measured by cyclic voltammetry with respect to the CCP synthesized at ambient temperature (220 F gr-1) and a 35% increase in capacity compared to its homologue synthesized in neutral conditions at a low temperature. These performances have been advantageously correlated both to the edge acidity of the host material and to the evolution of its conductivity according to the preparation conditions. The galvanostatic charge/discharge tests also confirm the stability of the obtained composite, and a capacitance of 325 F g-1 for the best CCP is recorded with a regime of 1 A g-1. In addition, the durability of the device shows that the proposed material has a relatively good stability during cycling.

10.
Polymers (Basel) ; 16(7)2024 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-38611203

RESUMO

Reverse engineering is applied to identify optimum polymerization conditions for the synthesis of polymers with pre-defined properties. The proposed approach uses multi-objective optimization (MOO) and provides multiple candidate polymerization procedures to achieve the targeted polymer property. The objectives for optimization include the maximal similarity of molar mass distributions (MMDs) compared to the target MMDs, a minimal reaction time, and maximal monomer conversion. The method is tested for vinyl acetate radical polymerizations and can be adopted to other monomers. The data for the optimization procedure are generated by an in-house-developed kinetic Monte-Carlo (kMC) simulator for a selected recipe search space. The proposed reverse engineering algorithm comprises several steps: kMC simulations for the selected recipe search space to derive initial data, performing MOO for a targeted MMD, and the identification of the Pareto optimal space. The last step uses a weighted sum optimization function to calculate the weighted score of each candidate polymerization condition. To decrease the execution time, clustering of the search space based on MMDs is applied. The performance of the proposed approach is tested for various target MMDs. The suggested MOO-based reverse engineering provides multiple recipe candidates depending on competing objectives.

11.
Int J Biol Macromol ; 267(Pt 1): 131539, 2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38608994

RESUMO

Sustainable strategies to improve the water resistance of cellulose paper are actively sought. In this work, polymeric microspheres (PMs), prepared through emulsion polymerization of cellulose nanofibers stabilized rubber seed oil-derived monomer, were investigated as coatings on corrugated medium paper (CMP). After infiltrating porous paper with PMs, the water-resistant corrugated papers (WRCPn) with enhanced mechanical properties were obtained. When 30 wt% PMs were introduced, WRCP30 turned out to be highly compacted with an increased water contact angle of 106.3° and a low water vapor transmission rate of 81 g/(m2 d) at 23 °C. Meanwhile, the tensile strength of WRCP30 increased to 22.2 MPa, a 4-fold increase from CMP. When tested in a well-hydrated state, 71% of its mechanical strength in the dry state was maintained. Even with a low content of 10 wt% PMs, WRCP10 also exhibited stable tensile strength and water wettability during the cyclic soaking-drying process. Thus, the plant oil based sustainable emulsion polymers provide a convenient route for enhancing the overall performance of cellulose paper.

12.
ACS Appl Mater Interfaces ; 16(15): 19463-19471, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38573871

RESUMO

Covalent organic frameworks have great potential for energy-efficient molecular sieving-based separation. However, it remains challenging to implement COFs as an alternative membrane material due to the lack of a scalable and cost-effective fabrication mechanism. This work depicts a new method for fabricating a scalable in situ COF hollow fiber (HF) membrane by an interfacial polymerization (IP) approach at room temperature. The 2D COF film was constructed on a polyacrylonitrile HF substrate using aldehyde (1,3,5-trimethylphloroglucinol, Tp) and amine (4,4'-azodianiline (Azo) and 4,4',4″-(1,3,5-triazine- 2,4,6-triyl) trianiline (Tta)) as precursors. The COF membrane on the PAN substrate showed 99% rejection of Direct red-80 with remarkable solvent permeance. The rejection analysis revealed that the structural aspects of the solute molecule play a major role in rejection rather than the molecular weight. We further optimized the precursor concentrations to improve the permeation performance of the resulting membrane. The durability study reveals excellent stability of the membrane toward organic solvents. This study also demonstrated the easy scalability of the membrane fabrication approach. The approach was further extrapolated to fabricate a cation-based COF membrane. These charged membranes exhibited an enhanced rejection performance. Finally, this approach can facilitate industrially challenging molecular sieving applications using COF-based membranes.

13.
Chemistry ; : e202304375, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38563634

RESUMO

The clinical translation of polysarcosine (pSar) as polyethylene glycol (PEG) replacement in the development of novel nanomedicines creates a broad demand of polymeric material in high-quality making high-purity sarcosine N-carboxyanhydride (Sar-NCA) as monomer for its production inevitable. Within this report, we present the use of triethyloxonium tetrafluoroborate in Sar-NCA synthesis with focus on amino acid and chloride impurities to avoid the sublimation of Sar-NCAs. With a view towards upscaling into kilogram or ton scale, a new methodology of monomer purification is introduced by utilizing the Meerwein's Salt triethyloxonium tetrafluoroborate to remove chloride impurities by covalent binding and converting chloride ions into volatile products within a single step. The novel straightforward technique enables access to monomers with significantly reduced chloride content (<100 ppm) compared to Sar-NCA derived by synthesis or sublimation. The derived monomers enable the controlled-living polymerization in DMF and provide access to pSar polymers with Poisson-like molecular weight distribution within a high range of chain lengths (Xn 25-200). In conclusion, the reported method can be easily applied to Sar-NCA synthesis or purification of commercially available pSar-NCAs and eases access to well-defined hetero-telechelic pSar polymers.

14.
Dent Mater ; 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38570242

RESUMO

OBJECTIVES: to assess the impact of universal adhesives, cured with single-peak and polywave LEDs, on the metabolic activity and cytokine release of human dental pulp stem cells (hDPSCs). In addition, analyze the degree of conversion (DC) of the adhesives cured with the different LEDs. METHODS: Discs (5 mm diameter, 1 mm thick) were prepared using three universal adhesives: Single Bond Universal (SBU, 3 M ESPE), Optibond Universal (OBU, Kerr), and Zipbond Universal (ZBU, SDI). These discs were cured for 40 s using a single-peak (DeepCure, 3 M ESPE) or a polywave light-emmiting diode (LED) curing unit (Valo Grand, Ultradent). After 24 h, the specimens were placed in 24-well culture plates, each containing 1 mL of culture medium for 24 h. hDPSCs (1.8 ×104) were seeded in 96-well plates and allowed to grow for 24 h. Subsequently, the cells were exposed to the extracts (culture medium containing eluates from the adhesive discs) for an additional 24 h. Cells not exposed to the extracts were used as a control group. The mitochondrial metabolism was assessed using the MTT assay and the cytokine release evaluated through MAGPIX. The degree of conversion of the adhesives was analyzed using FTIR (n = 5). The results were analyzed by ANOVA two-way and Tukey's test. RESULTS: OBU and ZBU eluates caused a statistically significant reduction in mitochondrial metabolism, regardless of the LED used, indicating their cytotoxicity. In contrast, SBU did not significantly affect the MTT results, resembling the control group. A higher release of cytokines IL-1, IL-6, IL-10, and TNF-α were found in association to ZBU. SBU, on the other hand, increased the release of IL-8. OBU did not influenced the cytokine release. SBU presented the higher DC, while OBU and ZBU had similar DC, lower than SBU. SIGNIFICANCE: In conclusion, universal adhesives exhibit toxicity towards hDPSCs, but the extent of toxicity varies depending on the adhesive material. ZBU was associated with increased cytokine release, particularly pro-inflammatory mediators, from hDPSCs. The different LEDs did not influenced the cytotoxicity of the evaluated adhesives.

15.
Mass Spectrom Rev ; 2024 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-38556789

RESUMO

Zwitterionic ring-expansion polymerization (ZREP) is a polymerization method in which a cyclic monomer is converted into a cyclic polymer through a zwitterionic intermediate. In this review, we explored the ZREP of various cyclic polymers and how mass spectrometry assists in identifying the product architectures and understanding their intricate reaction mechanism. For the majority of polymers (from a few thousand to a few million Da) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry is the most effective mass spectrometry technique to determine the true molecular weight (MW) of the resultant product, but only when the dispersity is low (approximately below 1.2). The key topics covered in this study were the ZREP of cyclic polyesters, cyclic polyamides, and cyclic ethers. In addition, this study also addresses a number of other preliminary topics, including the ZREP of cyclic polycarbonates, cyclic polysiloxanes, and cyclic poly(alkylene phosphates). The purity and efficiency of those syntheses largely depend on the catalyst. Among several catalysts, N-heterocyclic carbenes have exhibited high efficiency in the synthesis of cyclic polyesters and polyamides, whereas tris(pentafluorophenyl)borane [B(C6F5)3] is the most optimal catalyst for cyclic polyether synthesis.

16.
Artigo em Inglês | MEDLINE | ID: mdl-38605517

RESUMO

Polymer polyacrylonitrile (PAN), with exceptional mechanical strength and ionic conductivity, is considered a potential electrolyte. However, the huge interfacial impedance of PAN-derived C≡N polar nitrile groups and Li anode limited its application. In this study, a double-stabilized interface was integrated by in situ polymerization of DOL between electrodes and a three-dimensional (3D) porous PAN polymer matrix containing SN plasticizer and LLZTO ceramic fillers to optimize the challenge of interfacial instability. The fabricated PDOL-PAN(SN/LLZTO)-PDOL composite solid electrolyte (CSE) exhibited the maximum ionic conductivities of 1.9 × 10-3 S cm-1 at room temperature and 2.5 × 10-3 S cm-1 at 60 °C, an electrochemical stability window (ESW) of 4.9 V, and a high Li+ transference number (tLi+) of 0.65. In addition, the side reactions of the PAN/Li metal were effectively prevented by inserting PDOL between the 3D porous membrane and Li electrode. Benefiting from the superior interface compatibility and ion conductivity, the Li symmetric battery showed more than 2000 h of cyclability. The solid Li/LiFePO4 full battery delivered excellent cycling performance, showing an original specific capacity of 136.2 mAh g-1 with a capacity retention of 90.1% after 350 cycles at 1C and 60 °C. Furthermore, the cycling of solid-state Li/NCM622 batteries also proved their application potential. This work presents an effective approach to solving interface problems of the PAN electrolyte for solid lithium-metal batteries (LMBs).

17.
Chempluschem ; : e202400161, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38593244

RESUMO

Hierarchical self-assembly has been recently employed in the construction of anion-coordination-driven gel materials. However, the post-assembly modification strategy, which may be a highly efficient strategy to realize the functionalization of discrete 'aniono' supramolecular architectures, has not been employed yet. Herein we report the first example of anion-coordination-driven gel material cross-linked by well-defined 'aniono' triple helicate through post-assembly polymerization. The obtained gel shows self-healing property and excellent compatibility with various surfaces, including glass, rubber, leaf, PP, and metal. The viscoelastic gel constructed through the post-assembly modification strategy enriches the method to construct the anion-coordination-driven smart materials.

18.
Small ; : e2400714, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38593314

RESUMO

Albeit microemulsion systems have emerged as efficient platforms for fabricating tunable nano/microstructures, lack of understanding on the emulsion-interfacial assembly hindered the control of fabrication. Herein, a nucleation-inhibited microemulsion interfacial assembly method is proposed, which deviates from conventional interfacial nucleation approaches, for the synthesis of polydopamine microvesicles (PDA MVs). These PDA MVs exhibit an approximate diameter of 1 µm, showcasing a pliable structure reminiscent of cellular morphology. Through modifications of antibodies on the surface of PDA MVs, their capacity as artificial antigen presentation cells is evaluated. In comparison to solid nanoparticles, PDA MVs with cell-like structures show enhanced T-cell activation, resulting in a 1.5-fold increase in CD25 expression after 1 day and a threefold surge in PD-1 positivity after 7 days. In summary, the research elucidates the influence of nucleation and interfacial assembly in microemulsion polymerization systems, providing a direct synthesis method for MVs and substantiating their effectiveness as artificial antigen-presenting cells.

19.
Small ; : e2311951, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38593355

RESUMO

Soft actuators have assumed vital roles in a diverse number of research and application fields, driving innovation and transformative advancements. Using 3D molding of smart materials and combining these materials through structural design strategies, a single soft actuator can achieve multiple functions. However, it is still challenging to realize soft actuators that possess high environmental adaptability while capable of different tasks. Here, the response threshold of a soft actuator is modulated by precisely tuning the ratio of stimulus-responsive groups in hydrogels. By combining a heterogeneous bilayer membrane structure and in situ multimaterial printing, the obtained soft actuator deformed in response to changes in the surrounding medium. The response medium is suitable for both biotic and abiotic environments, and the response rate is fast. By changing the surrounding medium, the precise capture, manipulation, and release of micron-sized particles of different diameters in 3D are realized. In addition, static capture of a single red blood cell is realized using biologically responsive medium changes. Finally, the experimental results are well predicted using finite element analysis. It is believed that with further optimization of the structure size and autonomous navigation platform, the proposed soft microactuator has significant potential to function as an easy-to-manipulate multifunctional robot.

20.
J Agric Food Chem ; 2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38597640

RESUMO

This study examined the impact of grape flesh polysaccharide, protein, and amino acid contents on polyphenol retention from skins and seeds in Pinot noir (Vitis vinifera) and cold-hardy interspecific cultivars Marquette and Frontenac (Vitis spp.). After isolating grape tissues (skin, seed, and flesh), they were soaked either individually or combined with other tissues in a wine-like solution for up to 7 days. Findings revealed that flesh significantly reduces the concentration of condensed tannin, and mono- and diglucoside forms of anthocyanins in the supernatants, due to its rich content in polysaccharides and proteins. Frontenac skin and flesh tissues were the main sources of soluble proteins, amino acids, and soluble polysaccharides. Surprisingly, Marquette exhibited a higher retention of skin tannin than Pinot noir, likely due to its smaller tannin molecular mass, and a potential competitive effect with anthocyanins for the binding sites of flesh.

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