Dynamic bonds enable high toughness and multifunctionality in gelatin/tannic acid-based hydrogels with tunable mechanical properties.

Biopolymer-based functional hydrogels with excellent mechanical properties are desired, but their fabrication remains a challenge. Learning from the tofu-making process, we developed a freely formable hydrogel with high toughness and stiffness from the hydrogen bond-rich coacervation of tannic acid and gelatin through a simple hot-pressing process that transforms the coacervate particles into a bulk hydrogel. The mechanical properties of the obtained gelatin/tannic acid hydrogel (G/T gel) can be controlled by tuning the weight ratio of tannic acid to gelatin in the gel. The G/T gel with optimum mechanical properties possesses high Young's modulus, fracture strain, and fracture energy of ∼60 MPa, ∼10, and ∼24 kJ m-2, respectively. These properties arise from the phase-separated structure and high concentration of dynamic hydrogen bonds with widely distributed bond strengths. These dynamic hydrogen bonds also enable multifunctional properties of the gel, such as self-recovery, self-healing, rebuildability and shape memory. The combination of excellent mechanical properties, good biocompatibility, and useful functionalities into one hydrogel that comes from renewable sources demonstrates the great potential of G/T gels.

Developing super tough gelatin-based hydrogels by incorporating linear poly(methacrylic acid) to facilitate sacrificial hydrogen bonding.

Mechanically robust protein-based hydrogels are strongly desired but their construction remains a significant challenge. In this work, gelatin, together with methacrylic acid, is used to construct a novel hydrogen-bonded hydrogel through a facile low-temperature polymerization and a subsequent dry-swell process. The obtained gel is extremely stiff and tough with a high Young's modulus and a fracture energy of 11 MPa and 8.5 kJ m-2, respectively, which are comparable to the performance of tough synthetic hydrogels, rubber, cartilage, and skin. These gels also show recovery and healing properties as well as biocompatibility and stability in physiological saline solutions. The gel is easy to prepare and exhibits a wide range of functional properties, making it a promising load-bearing material for medical applications.

Paclitaxel/sunitinib-loaded micelles promote an antitumor response in vitro through synergistic immunogenic cell death for triple-negative breast cancer.

Chemotherapy-induced immunogenic cell death (ICD) may offer a strategy to improve the effect of the therapeutic treatment of triple-negative breast cancer (TNBC) by eliciting broad antitumor immunity. However, chemotherapy shows a limited therapeutic effect because of multi-drug resistance and the immunosuppressive tumor microenvironment (TME) of TNBC. The unique pharmacological actions of sunitinib (SUN) indicate its possible synergies with paclitaxel (PTX) to enhance chemo-immunotherapy for TNBC. Here, we prepared a co-delivery platform composed of poly(styrene-co-maleic anhydride) (SMA) via a self-assembly process for a combination of PTX and SUN, which was able to induce a higher synergistic ICD. The nanomicellar delivery of PTX and SUN loaded at an optimal ratio of 1:5 (PTX:SUN) presented the characteristics of an appropriate particle size, long-term stability, and time sequence release which synergistically promoted the apoptosis of MDA-MB-231 tumor cells. Moreover, we demonstrated that the combination of PTX and SUN could significantly induce a synergistic effect because it promoted an ICD response, improved tumor immunogenicity, and regulated immunosuppressive factors in the TME. Overall, PTX and SUN with synergistic effects entrapped in a self-assembly nano-delivery system could offer the potential for clinical applicationof a combination chemo-immunotherapy strategy to improve the effect of the therapeutic treatment of TNBC.

A Light-Up Probe for Detection of Adenosine in Urine Samples by a Combination of an AIE Molecule and an Aptamer.

A light-up fluorescent probe for the detection of adenosine was constructed with an AIE (aggregation-induced emission) molecule and a DNA aptamer. The AIE molecule was used as a signal generator, and the DNA aptamer was used as a recognition element for adenosine. The emission of the AIE molecule was due to its intramolecular rotation restriction induced by the aptamer upon binding of adenosine. The optimal component ratio of the probe was AIE molecule / DNA aptamer = 100 (µM/µM). The calibration curve of adenosine detection showed a linear range of 10 pM to 0.5 µM with an R² of 0.996, and the detection limit of the probe was 10 pM. The probe exhibited a good selectivity to adenosine against its analogs (uridine, guanosine, and cytidine). The probe was used to detect adenosine in urine samples, a recovery from 86.8% to 90.0% for the spiked concentrations of adenosine (0.01, 0.05, 0.1 µM). The relative standard deviation from 1.2% to 2.0% was obtained. The intra-day and inter-day tests also showed good precisions, with measurement RSD values of 2.3% and 2.1%, respectively.

Hybrid silencers with micro-perforated panels and internal partitions.

A sub-structuring approach, along with a unit cell treatment, is proposed to model expansion chamber silencers with internal partitions and micro-perforated panels (MPPs) in the absence of internal flow. The side-branch of the silencer is treated as a combination of unit cells connected in series. It is shown that, by connecting multiple unit cells with varying parameters, the noise attenuation bandwidth can be enlarged. With MPPs, the hybrid noise attenuation mechanism of the silencer is revealed. Depending on the size of the perforation hole, noise attenuation can be dominated by dissipative, reactive, or combined effects together. For a broadband sound absorption, the hole size, together with the perforation ratio and other parameters, can be optimized to strike a balance between the dissipative and reactive effect, for ultimately achieving the desired noise attenuation performance within a prescribed frequency region. The modular nature of the proposed formulation allows doing this in a flexible, accurate, and cost effective manner. The accuracy of the proposed approach is validated through comparisons with finite element method and experiments.

Insulin-like growth factor 1 opposes the effects of C-reactive protein on endothelial cell activation.

Emerging evidence demonstrates that high plasma C-reactive protein (CRP) levels or low plasma insulin-like growth factor 1 (IGF-1) concentrations may be separately associated with the increased risk of coronary artery disease or myocardial infarction. Interestingly, animal model studies and epidemiological investigations indicate that circulating IGF-1 and CRP levels have an inverse correlation. The present study aims to evaluate if IGF-1 can directly oppose the effects of CRP on endothelial cell (EC) activation. We found that IGF-1 rescues endothelial nitric oxide synthase activity and decreases the release of intercellular adhesion molecule-1 and vascular cell adhesion molecule-1 from ECs. We also showed that IGF-1 antagonizes the effects of CRP by activating the PI3K/Akt pathway and suppressing the JNK/c-Jun and MAPK p38/ATF2 signaling pathways, rather than inhibiting ERK1/2 activity. These findings provide evidence of the physiopathological mechanisms of endothelial activation and novel insights into the protective properties of IGF-1.

HMGA1 is a new target of miR-195 involving isoprenaline-induced cardiomyocyte hypertrophy.

Emerging data have shown that microRNAs (miRNAs) have important functions in the processes of cardiac hypertrophy and heart failure that occur during the postnatal period. Cardiac overexpression of miR-195 results in pathological cardiac growth and heart failure in transgenic mice. In the present study, we analyzed the roles of miR-195 in cardiomyocyte hypertrophy and found that miR-195 was greatly upregulated during isoprenaline-induced cardiomyocyte hypertrophy. By using mRNA microarray and molecular approach, we identified a novel putative target of miR-195 called high-mobility group A1 (HMGA1). Total mRNA microarray showed that HMGA1 was downregulated in primary cardiomyocytes that overexpressed miR-195. Using luciferase activity assay, we demonstrated that miR-195 interacts with the 3'-untranslated region of HMGA1 mRNA. Moreover, we showed that miR-195 in primary cardiomyocytes downregulates the expression of HMGA1 at the protein level. Taken together, our data demonstrated that miR-195 can negatively regulate a new target, HMGA1, which is involved in cardiomyocyte hypertrophy.

Enhancing Mechanical Performance of High-Lignin-Filled Polypropylene via Reactive Extrusion.

Polypropylene (PP) is one of the most extensively used commodity plastics. In terms of eco-friendliness, it is worth considering preparing high-lignin-filled PP. This study explores the incorporation of high lignin content, derived from acetic acid lignin (AAL) and Kraft lignin (KL), into PP through twin-screw extrusion and injection molding. The challenge lies in maintaining mechanical performance. A compatibilizer-specifically, maleic anhydride-grafted polypropylene (MAPP)-is employed to enhance lignin-PP compatibility by chemically bonding with lignin and physically associating with the PP phase. Results indicate that KL maintains better dispersity than AAL. Compatibilizers with a high maleic anhydride (MA) level (≥0.8 wt.%) and moderate melt flow index (MFI) in the range of 60-100 g 10 min⁻¹ prove favorable in constructing a reinforced PP/KL network. Optimizing with 40 wt.% lignin content and 10 parts per hundred (pph) of compatibilizer yields blends with mechanical performance comparable to neat PP, exhibiting a notable increase in modulus and heat deflection temperature (HDT). Furthermore, utilizing PP/lignin blends can lead to a 20% reduction in expenses and approximately 40% reduction in PP-induced greenhouse gas (GHG) emissions. This approach not only reduces PP costs but also adds value to lignin utilization in a sustainable and cost-effective manner.

miR-10a restores human mesenchymal stem cell differentiation by repressing KLF4.

miRNAs have recently been shown to play a significant role in human aging. However, data demonstrating the effects of aging-related miRNAs in human mesenchymal stem cells (hMSCs) are limited. We observed that hMSC differentiation decreased with aging. We also identified that miR-10a expression was significantly decreased with age by comparing the miRNA expression of hMSCs derived from young and aged individuals. Therefore, we hypothesized that the downregulation of miR-10a may be associated with the decreased differentiation capability of hMSCs from aged individuals. Lentiviral constructs were used to up- or downregulate miR-10a in young and old hMSCs. Upregulation of miR-10a resulted in increased differentiation to adipogenic, osteogenic, and chondrogenic lineages and in reduced cell senescence. Conversely, downregulation of miR-10a resulted in decreased cell differentiation and increased cell senescence. A chimeric luciferase reporter system was generated, tagged with the full-length 3'-UTR region of KLF4 harboring the seed-matched sequence with or without four nucleotide mutations. These constructs were cotransfected with the miR-10a mimic into cells. The luciferase activity was significantly repressed by the miR-10a mimic, proving the direct binding of miR-10a to the 3'-UTR of KLF4. Direct suppression of KLF4 in aged hMSCs increased cell differentiation and decreased cell senescence. In conclusion, miR-10a restores the differentiation capability of aged hMSCs through repression of KLF4. Aging-related miRNAs may have broad applications in the restoration of cell dysfunction caused by aging.

Antioxidant mechanisms and products of four 4',5,7-trihydroxyflavonoids with different structural types.

4',5,7-OHs are common substituents of natural flavonoids, a type of effective phenolic antioxidant. However, the antioxidant processes between 4',5,7-trihydroxyflavonoids with different structural types have not been compared systematically, and the antioxidant products are challenging to determine. This study compared four 4',5,7-trihydroxyflavonoids, including apigenin, genistein, kaempferol, and naringenin. In quantum chemical analyses, the four 4',5,7-trihydroxyflavonoids showed different thermodynamic properties, and the C4'-OH (or C3-OH of kaempferol) possessed the strongest activity. Moreover, the reaction rate constants were larger when a hydrogen atom was transferred from C4'-OH (or C3-OH of kaempferol) than from C5-OH. When different atoms were linked to 2,2-diphenyl-1-picrylhydrazyl radical (DPPH˙), the C3'-DPPH adducts showed the smallest energy. In experimental assays, the scavenging ability for neutral free radicals, radical cations, and radical anions was negatively correlated with the corresponding theoretical parameters. Finally, mass spectroscopy detected the apigenin-DPPH˙, genistein-DPPH˙, and naringenin-DPPH˙ adduct peaks. In conclusion, the structural type of 4',5,7-trihydroxyflavonoids can affect the antioxidant ability, site, and speed, but not the mechanism. After hydrogen abstraction at C4'-OH, 4',5,7-trihydroxyflavones, 4',5,7-trihydroxyisoflavones, and 4',5,7-trihydroxyflavanones will produce antioxidant products via C3'-radical linking.

Fabrication of Graphitized Carbon Fibers from Fusible Lignin and Their Application in Supercapacitors.

Lignin-based carbon fibers (LCFs) with graphitized structures decorated on their surfaces were successfully prepared using the simultaneous catalyst loading and chemical stabilization of melt-spun lignin fibers, followed by quick carbonization functionalized as catalytic graphitization. This technique not only enables surficial graphitized LCF preparation at a relatively low temperature of 1200 °C but also avoids additional treatments used in conventional carbon fiber production. The LCFs were then used as electrode materials in a supercapacitor assembly. Electrochemical measurements confirmed that LCF-0.4, a sample with a relatively low specific surface area of 89.9 m2 g-1, exhibited the best electrochemical properties. The supercapacitor with LCF-0.4 had a specific capacitance of 10.7 F g-1 at 0.5 A g-1, a power density of 869.5 W kg-1, an energy density of 15.7 Wh kg-1, and a capacitance retention of 100% after 1500 cycles, even without activation.

Fabrication of superhydrophilic porous carbon materials through a porogen-free method: Surface and structure modification promoting the two-electron oxygen reduction activity.

HYPOTHESIS: Electrochemical manufacture of H2O2 through the two-electron oxygen reduction reaction (2e- ORR), providing prospects of the distributed production of H2O2 in remote regions, is considered a promising alternative to the energy-intensive anthraquinone oxidation process. EXPERIMENTS: In this study, one glucose-derived oxygen-enriched porous carbon material (labeled as HGC500) is developed through a porogen-free strategy integrating structural and active site modification. FINDINGS: The superhydrophilic surface and porous structure together promote the mass transfer of reactants and accessibility of active sites in the aqueous reaction, while the abundant CO species (e.g., aldehyde groups) are taken for the main active site to facilitate the 2e- ORR catalytic process. Benefiting from the above merits, the obtained HGC500 possesses superior performance with a selectivity of 92 % and mass activity of 43.6 A gcat-1 at 0.65 V (vs. RHE). Besides, the HGC500 can operate steadily for 12 h with the accumulation of H2O2 reaching up to 4090±71 ppm and a Faradic efficiency of 95 %. The H2O2 generated from the electrocatalytic process in 3 h can degrade a variety of organic pollutants (10 ppm) in 4-20 min, displaying the potential in practical applications.

Research on Metal Corrosion Resistant Bioinspired Special Wetting Surface Based on Laser Texturing Technology: A Review.

Metal substrates are widely used in engineering production. However, material life reduction and economic loss due to chemical and electrochemical corrosion are a major problem facing people. Electrochemical corrosion is the main corrosion mode of metals, such as seawater corrosion. It is found that the superhydrophobic surface treated by laser texturing plays an important role in the corrosion resistance of the substrate, with the laser texturing process and post-treatment affecting the corrosion resistance. The corrosion resistance is positively correlated with the superhydrophobic property of the surface. For the mechanism of corrosion resistance, this paper summarizes the effect of micro-nano structure, surface-modified coating, oxidation layer or new product layer, surface inhomogeneity, crystal structure, and slippery surface on corrosion resistance. Superhydrophobic surface and slippery surface are two common types of bioinspired, special wetting surfaces. In order to prepare better superhydrophobic and corrosion-resistant surfaces, this paper summarizes the selection and optimization of laser parameters, surface structure, processing media, and post-treatment from the point of view of mechanism and law. In addition, after summarizing the corrosion resistance mechanism, this paper introduces a series of characterization experiments that can measure the corrosion resistance, providing a reference for preparation and evaluation of the surface.

[Characteristics and Source Apportionment of Volatile Organic Compounds in August in the Chang-Zhu-Tan Urban Area].

Continuous sampling using the tank sampling method were conducted in Changsha, Zhuzhou, and Xiangtan cities from August 18 to 27, 2020, and 106 VOCs species were analyzed using GC-MS analysis. Then, the regional VOCs concentrations, generation potential, and source of VOCs were studied. The results showed that the average φ(VOCs) was (20.5±10.5)×10-9 in the Changsha-Zhuzhou-Xiangtan area, in which OVOCs (33.5%) and alkanes (28.2%) accounted for the highest proportion. The ozone formation potential (OFP) of VOCs was 118.5 µg·m-3, and the contributions of aromatic hydrocarbons, olefin, and OVOCs to OFP were 37.4%, 24.2%, and 23.6%, respectively. The average secondary organic aerosol formation potential (SOAp) of the VOCs was 0.5 µg·m-3, and the contribution of aromatic hydrocarbons to SOAp was 97.0%, among which C8 aromatic hydrocarbons contributed 41.7%. Toluene, m/p-xylene, and o-xylene were the common dominant species that contributed significantly to OFP and SOAp. The characteristic ratio results showed that VOCs in Changsha were relatively influenced by industrial processes and solvent use, whereas Zhuzhou and Xiangtan were more affected by coal and biomass combustion. The PMF results showed that the VOCs mainly came from vehicle exhaust and oil and gas volatilization (27.2%), coal and biomass combustion (23.7%), industrial processes (20.4%), solvent use (17.2%), and natural sources (11.5%) in the Changsha-Zhuzhou-Xiangtan area.

Colorimetric detection of melamine in complex matrices based on cysteamine-modified gold nanoparticles.

A sensitive assay for melamine in complex matrices is built using cysteamine-modified gold nanoparticles (AuNPs) and an effective sample pretreatment protocol. Citrate-stabilized AuNPs were modified by cysteamine in order to weaken the electrostatic repulsion force between the gold nanoparticles. Detection sensitivity gained through this modification increased about 100 fold compared with the result using the unmodified AuNPs. Direct colorimetric visualizations of melamine in milk products, eggs and feeds was successfully demonstrated within the linear ranges of 1-200 mg L(-1) and detection limits below 1 mg L(-1). The proposed scheme could be an alternative means for onsite detection of melamine without costly instruments.

Degradable Gelatin-Based Supramolecular Coating for Green Paper Sizing.

Developing a paper sizing agent to meet the requirements of low cost, high quality of the paper, and environmental sustainability is significant but remains a challenge. Herein, a novel degradable gelatin-based coating emulsion for paper surface sizing was developed by a simple one-step polymerization and blending process. Poly(methacrylic acid) (PMAA) was first introduced to a gelatin solution to form gelatin-PMAA emulsion (G-PMAA) through the formation of hydrogen bonds between PMAA and gelatin. The addition of PMAA endowed gelatin with the increased hydrophobicity and the decreased upper critical solution temperature. Then, a relatively small amount of the flexible poly(butyl acrylate) (PBA), which imparted the toughness of the formed film, was blended with the G-PMAA emulsion to form G-PMAA/PBA emulsion. The G-PMAA/PBA emulsion with a high gelatin content of 0.2 g/mL was in the sol state at room temperature, which facilitated the application of the G-PMAA/PBA emulsion. The corrugated papers sized by G-PMAA/PBA emulsion exhibited excellent mechanical properties and water resistance.

Self-Healable, High-Strength Hydrogel Electrode for Flexible Sensors and Supercapacitors.

Flexible energy storage materials and sensors have become the key equipment of human-machine interface technology. For the preparation of these devices, hydrogel electrodes are relevant because of their unique porous structure, high capacitance, flexibility, small size, and lightweight. In this paper, regular polypyrrole (PPy) is synthesized on a heat-induced phase-separated gel (H-Gel/AS) by the template degradation method, and a gelatin-based PPy hydrogel with high strength, high strain rate, and high conductivity is prepared. Moreover, by adding multiwalled carbon nanotubes (MWCNTs) into a gelatin solution according to the H-Gel/AS method, the electrochemical performance of the resulting H-Gel/AS-MWCNTs-PPy electrode is greatly improved. When the H-Gel/AS-MWCNTs-PPy gel is immersed in an ammonium sulfate solution, wrinkles appear on the surface, resulting in further enhancement of the capacitance. On this basis, a flexible sensor and a solid-state supercapacitor are assembled, and their performance is tested. The sensor can detect tensile, bending, and twisting strains with high sensitivity. Meanwhile, as a flexible solid-state supercapacitor, the specific capacitance is 75 F g-1, and the capacitance retention rate after 5000 cycles is 98.1% under bending conditions. More importantly, the gelatin-based hydrogel shows great potential for application in wearable devices.

Interface Engineering of Flexible Piezoresistive Sensors via Near-Field Electrospinning Processed Spacer Layers.

The interface contact between the active material and its neighboring metal electrodes dominates the sensing response of mainstream high-sensitivity piezoresistive pressure sensors. However, the properties of such interface are often difficult to control and preserve owing to the limited strategies to precisely engineer the surface structure and mechanical property of the active material. Here, a top-down fabrication method to create a grid-like polyurethane fiber-based spacer layer at the interface between a piezoresistive layer and its contact electrodes is proposed. The tuning of the period and thickness of the spacer layer is conveniently achieved by a programmable near-field electrospinning process, and the influence of the spacer structure on the sensing performance is systematically investigated. The sensor with the optimized spacer layer shows a widened sensing range (230 kPa) while maintaining a high sensitivity (1.91 kPa-1 ). Furthermore, the output current fluctuation of the sensors during a 74 000-cycle test is drastically reduced from 14.28% (without a spacer) to 3.63% (with a spacer), demonstrating greatly enhanced long-term reliability. The new near-field electrospinning-based strategy is capable of tuning sensor responses without changing the active material, providing a universal and scalable path to engineer the performances of contact-dominant sensors.

Plant-based nanocellulose: A review of routine and recent preparation methods with current progress in its applications as rheology modifier and 3D bioprinting.

"Nanocellulose" have captivated the topical sphere of sturdily escalating market for sustainable materials. The review focuses on the comprehensive understanding of the distinct surface chemistry and functionalities pertaining to the renovation of macro-cellulose at nanodimensional scale to provide an intuition of their processing-structure-function prospective. The abundant availability, cost effectiveness and diverse properties associated with plant-based resources have great economical perspective for developing sustainable cellulose nanomaterials. Hence, emphasis has been given on nanocellulose types obtained from plant-based sources. An overarching goal is to provide the recent advancement in the preparation routes of nanocellulose. Considering the excellent shear thinning/thixotropic/gel-like behavior, the review provids an assemblage of publications specifically dealing with its application as rheology modifier with emphasis on its use as bioink for 3D bioprinting for various biomedical applications. Altogether, this review has been oriented in a way to collocate a collective data starting from the historical perspective of cellulose discovery to modern cellulosic chemistry and its renovation as nanocellulose with recent technological hype for broad spanning applications.

Nanosuspension as an Efficient Carrier for Improved Ocular Permeation of Voriconazole.

BACKGROUND: The present limitations related to the ocular administration of antifungal drugs for the treatment of fungal keratitis include poor ocular bioavailability, limited retention time, and low ocular tissue penetration. METHODS: This study aimed to prepare a novel ophthalmic voriconazole-loaded nanosuspension based on Eudragit RS 100. Pharmasolve® was explored as a corneal permeation enhancer in voriconazole ophthalmic formulation using in vitro and in vivo experiments. Briefly, 1% voriconazole-loaded nanosuspension was prepared using the quasi-emulsion solvent evaporation process. RESULTS: Characterizations of the voriconazole-loaded nanosuspension by Zetasizer Nano ZS and Transmission Electron Microscope (TEM) showed a uniform spherical shape without any agglomeration. The well-discreted nanoparticle with a size of 138 ± 1.3 nm was achieved with high entrapment efficiency (98.6 ± 2.5%) and positive zeta potential in the range of 22.5-31.2mV, indicating excellent physical stability. DISCUSSION: Voriconazole-loaded nanosuspension containing the penetration enhancer displayed good permeability both in vitro and in vivo compared with the commercial voriconazole injection. The voriconazole-loaded nanosuspension exhibited good antifungal activity, significantly inhibiting the growth of Candida albicans at a lower concentration of voriconazole (2.5µg/mL, p < 0.05). CONCLUSION: In conclusion, the voriconazole-loaded nanosuspension containing Pharmasolve® can be used as an effective ophthalmic formulation for the topical ocular delivery of voriconazole.