A Near-Infrared Photothermal-Responsive Underwater Adhesive with Tough Adhesion and Antibacterial Properties.

Developing tunable underwater adhesives that possess tough adhesion in service and easy detachment when required remains challenging. Herein, a strategy is proposed to design a near infrared (NIR) photothermal-responsive underwater adhesive by incorporating MXene (Ti3C2Tx)-based nanoparticles within isocyanate-modified polydimethylsiloxane (PDMS) polymer chains. The developed adhesive exhibits long-term and tough adhesion with an underwater adhesion strength reaching 5.478 MPa. Such strong adhesion is mainly attributed to the covalent bonds and hydrogen bonds at the adhesive-substrate interface. By making use of the photothermal-response of MXene-based nanoparticles and the thermal response of PDMS-based chains, the adhesive possesses photothermal-responsive performance, exhibiting sharply diminished adhesion under NIR irradiation. Such NIR-triggered tunable adhesion allows for easy and active detachment of the adhesive when needed. Moreover, the underwater adhesive exhibits photothermal antibacterial property, making it highly desirable for underwater applications. This work enhances the understanding of photothermal-responsive underwater adhesion, enabling the design of tunable underwater adhesives for biomedical and engineering applications.

Self-Polymerized Tough and High-Entanglement Zwitterionic Functional Hydrogels.

Zwitterionic hydrogels exhibit great potential in biomedical applications due to their antifouling properties and biocompatibility. However, the single-network structure of pure zwitterionic hydrogels leads to a low toughness and strength, limiting their application in biomedical fields. In this work, a high entanglement sulfobetaine methacrylate-dopamine hydrogel (SBMA-DA-PE) with low cross-linker content and high monomer concentration is prepared by using a dopamine oxidative radical polymerization method. Compared to a regular zwitterionic hydrogel, the SBMA-DA-PE hydrogel exhibits a 5-fold increase in tensile fracture stress and a 10-fold increase in compressive fracture stress. The SBMA-DA-PE hydrogel possesses excellent mechanical properties (the maximum compressive stress ≥4.85 MPa, the maximum compressive strain ≥90%). Besides, the non-covalent interactions between catechol or ortho-quinones within the SBMA-DA-PE hydrogel, combined with strong intermolecular electrostatic interactions, endow the SBMA-DA-PE hydrogel with great self-healing capabilities and fatigue resistance. The SBMA-DA-PE hydrogel demonstrates low swellability and possesses good antifouling properties. Furthermore, the good printability and conductivity of the tough SBMA-DA-PE hydrogel endows it with new possibilities for developing biological 3D scaffolds and electronic devices. Overall, this work provides new insights into the preparation of zwitterionic hydrogels with high mechanical strength and multi-functionality for biomedical applications.

The Effect of Solvents on the Crystal Morphology of Isosorbide Mononitrate and Its Molecular Mechanisms.

In this work, the modified attachment energy model was used to predict the crystal morphology of isosorbide mononitrate (ISMN) in the dichloromethane (CH2Cl2) solvent system and dichloromethane-n-hexane (CH2Cl2-C6H14) mixed solvent system. The solvent effect can significantly affect the crystal morphology, which can profoundly impact both the drug's physicochemical properties and the subsequent technological treatment process. In addition, the interactions between solvent molecules and crystal faces were investigated using molecular dynamics simulation, and radial distribution function (RDF) analysis was performed to determine the types of interactions. The structural parameter S was introduced to characterize the roughness of each crystal surface; the change in the CH2Cl2 diffusion coefficient before and after the addition of C6H14 was analyzed using mean square displacement (MSD). The calculation results of the modified attachment energy from the two solvent systems revealed that C6H14 could accelerate crystal growth, while the crystal morphology was not greatly affected, which is of some significance as a guide for the industrial crystallization process.

Simulation Study for the Adsorption of Carbon Disulfide on Hydroxyl Modified Activated Carbon.

In this study, grand canonical Monte Carlo simulations (GCMC) and molecular dynamics simulations (MD) were used to construct models of activated carbon with hydroxyl-modified hexachlorobenzene basic unit contents of 0%, 12.5%, 25%, 35% and 50%. The mechanism of adsorption of carbon disulfide (CS2) by hydroxyl-modified activated carbon was then studied. It is found that the introduction of hydroxyl functional groups will improve the adsorption capacity of activated carbon for carbon disulfide. As far as the simulation results are concerned, the activated carbon model containing 25% hydroxyl modified activated carbon basic units has the best adsorption performance for carbon disulfide molecules at 318 K and atmospheric pressure. At the same time, the changes in the porosity, accessible surface area of the solvent, ultimate diameter and maximum pore diameter of the activated carbon model also led to great differences in the diffusion coefficient of carbon disulfide molecules in different hydroxyl-modified activated carbons. However, the same adsorption heat and temperature had little effect on the adsorption of carbon disulfide molecules.

Molecular Simulation to Explore the Dissolution Behavior of Sulfur in Carbon Disulfide.

Soluble sulfur (S8) and insoluble sulfur (IS) have different application fields, and molecular dynamics simulation can reveal their differences in solubility in solvents. It is found that in the simulated carbon disulfide (CS2) solvent, soluble sulfur in the form of clusters mainly promotes the dissolution of clusters through van der Waals interaction between solvent molecules (CS2) and S8, and the solubility gradually increases with the increase in temperature. However, the strong interaction between polymer chains of insoluble sulfur in the form of polymer hinders the diffusion of IS into CS2 solvent, which is not conducive to high-temperature dissolution. The simulated solubility parameter shows that the solubility parameter of soluble sulfur is closer to that of the solvent, which is consistent with the above explanation that soluble sulfur is easy to dissolve.

Oxidations of Benzhydrazide and Phenylacetic Hydrazide by Hexachloroiridate(IV): Reaction Mechanism and Structure-Reactivity Relationship.

Benz(o)hydrazide (BH) is the basic aryl hydrazide; aryl hydrazides have been pursued in the course of drug discovery. Oxidations of BH and phenylacetic hydrazide (PAH) by hexachloroiridate(IV) ([IrCl6]2-) were investigated by use of stopped-flow spectral, rapid spectral scan, RP-HPLC and NMR spectroscopic techniques. The oxidation reactions followed well-defined second-order kinetics and the observed second-order rate constant k' versus pH profiles were established over a wide pH range. Product analysis revealed that BH and PAH were cleanly oxidized to benzoic acid and phenylacetic acid, respectively. A reaction mechanism was proposed, resembling those suggested previously for the oxidations of isoniazid (INH) and nicotinic hydrazide (NH) by [IrCl6]2-. Rate constants of the rate-determining steps were evaluated, confirming a huge reactivity span of the protolysis species observed previously. The enolate species of BH is extremely reactive towards reduction of [IrCl6]2-. The determined middle-ranged negative values of activation entropies together with rapid scan spectra manifest that an outer-sphere electron transfer is probably taking place in the rate-determining steps. The reactivity of neutral species of hydrazides is clearly not correlated to the corresponding pKa values of the hydrazides. On the other hand, a linear correlation, logkenolate = (0.16 ± 0.07)pKenol + (6.1 ± 0.8), is found for the aryl hydrazides studied so far. The big intercept and the small slope of this correlation may pave a way for a rational design of new antioxidants based on aryl hydrazides. The present work also provides the pKa values for BH and PAH at 25.0 °C and 1.0 M ionic strength which were not reported before.

Simultaneous enrichment and speciation of lead and mercury by magnetic solid-phase extraction coupled to HPLC-ICP-MS based on magnetic hydrazine-linked covalent organic frameworks.

BACKGROUND: Trace levels of organic and inorganic lead and mercury species in the environment, including divalent lead (Pb2+), trimethyllead (TML), divalent mercury (Hg2+), monomethylmercury (MeHg), and ethylmercury (EtHg), are highly toxic to humans and ecology. It is of great importance for speciation of lead and mercury to evaluate the toxicity of lead and mercury and their biogeochemistry in the environment. However, simultaneous multi-elemental enrichment and speciation at trace level remains a challenge. There are few reports of simultaneous magnetic solid-phase extraction (MSPE) of organic and inorganic lead and mercury species at trace level in the real water. RESULTS: In this work, a novel core-shell magnetic hydrazine-linked covalent organic frameworks (Fe3O4@COF-TCH) was prepared for the first time by grafting hydrazine-linked COFs on the Fe3O4 nanoparticles. Fe3O4@COF-TCH with abundant thione and imino groups has strong adsorption for lead and mercury species. Based on it, a simple and practical magnetic solid-phase extraction high-performance liquid chromatography-inductively coupled plasma mass spectrometry (MSPE-HPLC-ICP-MS) method was developed for extraction and determination of trace lead and mercury species, including Hg2+, MeHg, EtHg, Pb2+ and TML. The limits of detection (3δ) of the developed method were 0.08, 0.81, 0.90, 0.56 and 0.88 ng L-1 with the enrichment factors (EFs) of 384, 376, 379, 389 and 360-fold for Pb2+, TML, Hg2+, MeHg and EtHg, respectively. The high accuracy and reproducibility have been proved by the spiked recoveries (94.4-103 %) in real samples. SIGNIFICANCE: The proposed method with simple operation and high sensitivity has been successfully applied to simultaneous speciation of lead and mercury at trace levels in the water samples with complicated matrices, including underground water, surface water, sea water. Meanwhile, it has the advantages of cost-saving, labor-saving and time-saving and is suitable for the investigation and risk assessment in water. The development of MSPE-HPLC-ICP-MS method provides ideas and guidance for the simultaneous multi-elemental enrichment and speciation.

Nanoarchitectonics of Injectable Biomimetic Conjugates for Cartilage Protection and Therapy Based on Degenerative Osteoarthritis Progression.

Osteoarthritis (OA) is a common age-related degenerative disease characterized by changes in the local tissue environment as inflammation progresses. Inspired by the wind-dispersal mechanism of dandelion seeds, this study develops responsive biomimetic microsphere-drug conjugate for OA therapy and protection. The conjugate integrates dibenzaldehyde polyethylene glycol (DFPEG) with chitosan and polyethylene glycol diacrylate (PEGDA) through dynamic covalent bonds to form a dual-network hydrogel microsphere. Based on the progression of OA, the conjugate with the surface-anchored cyclic peptide cortistatin-14 (CST-14) achieves targeted drug therapy and a self-regulating hydrogel network. In cases of progressing inflammation (pH < 5), CST-14 dissociates from the microsphere surface (viz. the drug release rate increased) and inhibits TNF-α signaling to suppress OA. Concurrently, the monomer DFPEG responsively detaches from the hydrogel network and scavenges reactive oxygen species (ROS) to protect the cartilage tissue. The ROS scavenging of DFPEG is comparable to that of coenzyme Q10 and vitamin C. The degraded PEGDA microspheres provide tissue lubrication through reused conjugates. The rat OA model successfully achieved a synergistic therapeutic effect greater than the additive effect (1 + 1 > 2). This strategy offers an approach for anchoring amine-containing drugs and has marked potential for OA treatment and protection.

An underwater stable and durable gelatin composite hydrogel coating for biomedical applications.

Developing underwater stable and durable hydrogel coatings with drag-reducing, drug release, and antibacterial properties is essential for lots of biomedical applications. However, most hydrogel coatings cannot meet the requirement of underwater stability and versatility, which severely limits their widespread use. In this work, an underwater stable, durable and substrate-independent gelatin composite hydrogel (GMP) coating is developed through covalent crosslinks, where a silane coupling agent with an unsaturated double bond is grafted onto a substrate of co-deposited polydopamine and polyethylenimine. GMP coating can be easily coated onto various medical device surfaces, such as artificial joints, catheters, tracheal tubes and titanium alloys, showing excellent structural stability and mechanical tunability under extreme conditions of ultrasonic treatment for 1 h (400 W of ultrasonic power) or underwater shearing for 14 days (400 rpm). Besides, friction experiment reveals that GMP coating exhibits good lubrication properties (coefficient of friction < 0.003). The drug-loading and bacterial inhibition ring tests show that the GMP coating has a tunable drug release ability with the final releasing ratios of 70-95% by changing the content of poly (ethylene glycol) diacrylate. This work offers a scalable approach of fabricating bio-functional and stable hydrogel coatings, which can be potentially used in biomedical applications.

Biphase synthesis of a one-dimensional coordination polymer based on a dinuclear Cd(II) secondary building unit and a novel semi-rigid dicarboxylate.

A one-dimensional coordination polymer, namely catena-poly[[aquapyridinecadmium(II)]-µ(3)-{4,4'-[(2,4,6-trimethyl-1,3-phenylene)bis(methylene)]dibenzoato}], [Cd(C(25)H(22)O(4))(C(5)H(5)N)(H(2)O)](n), has been synthesized by a biphasic solvothermal reaction. The Cd(II) cation is located in a CdO(5)N six-coordinated environment. The trans 4,4'-[(2,4,6-trimethyl-1,3-phenylene)bis(methylene)]dibenzoate ligand connects the Cd(II) cations to form a one-dimensional ribbon incorporating centrosymmetric [Cd(2)(COO)(2)] secondary building units. Inter-ribbon O-H...O hydrogen bonds extend the one-dimensional ribbons into a two-dimensional sheet. No π-π interactions are observed. Comparing products synthesized using a different method, it was found that biphasic solvothermal conditions play a crucial role in obtaining large well-shaped single crystals; only intractable precipitates were obtained by the traditional single-phase solvothermal method.

Manufacturing and post-engineering strategies of hydrogel actuators and sensors: From materials to interfaces.

Living bodies are made of numerous bio-sensors and actuators for perceiving external stimuli and making movement. Hydrogels have been considered as ideal candidates for manufacturing bio-sensors and actuators because of their excellent biocompatibility, similar mechanical and electrical properties to that of living organs. The key point of manufacturing hydrogel sensors/actuators is that the materials should not only possess excellent mechanical and electrical properties but also form effective interfacial connections with various substrates. Traditional hydrogel normally shows high electrical resistance (~ MΩ•cm) with limited mechanical strength (<1 MPa), and it is prone to fatigue fracture during continuous loading-unloading cycles. Just like iron should be toughened and hardened into steel, manufacturing and post-treatment processes are necessary for modifying hydrogels. Besides, advanced design and manufacturing strategies can build effective interfaces between sensors/actuators and other substrates, thus enhancing the desired mechanical and electrical performances. Although various literatures have reviewed the manufacture or modification of hydrogels, the summary regarding the post-treatment strategies and the creation of effective electrical and mechanically sustainable interfaces are still lacking. This paper aims at providing an overview of the following topics: (i) the manufacturing and post-engineering treatment of hydrogel sensors and actuators; (ii) the processes of creating sensor(actuator)-substrate interfaces; (iii) the development and innovation of hydrogel manufacturing and interface creation. In the first section, the manufacturing processes and the principles for post-engineering treatments are discussed, and some typical examples are also presented. In the second section, the studies of interfaces between hydrogels and various substrates are reviewed. Lastly, we summarize the current manufacturing processes of hydrogels, and provide potential perspectives for hydrogel manufacturing and post-treatment methods.

Magnetic solid-phase extraction for speciation of mercury based on thiol and thioether-functionalized magnetic covalent organic frameworks nanocomposite synthesized at room temperature.

A simple and practical magnetic solid-phase extraction high-performance liquid chromatography-inductively coupled plasma mass spectrometry (MSPE-HPLC-ICP-MS) method for extraction and determination of trace mercury species, including inorganic mercury (IHg), monomethylmercury (MeHg) and ethylmercury (EtHg), was developed. The MSPE adsorbent, urchin-like thiol and thioether-functionalized magnetic covalent organic frameworks (Fe3O4@COF-S-SH), was synthesized by coating covalent organic frameworks (COFs) on the surface of Fe3O4 nanoparticles at room temperature and then easily grafting 1,2-Ethanedithiol on the COFs. The as-prepared Fe3O4@COF-S-SH has strong adsorption capacity for IHg, MeHg and EtHg, with excellent static adsorption capacity: 571, 559 and 564 mg g-1, respectively. The parameters influencing the extraction and enrichment had been optimized, including pH, adsorption and desorption time, composition and amount of the eluent, co-existing ions and dissolved organic materials etc. Under the optimized condition, the limit of detection (3δ) of the proposed method were 0.96, 0.17 and 0.47 ng L-1 for IHg, MeHg and EtHg, and the developed method has high actual enrichment factors of 370, 395, 365-fold for IHg, MeHg and EtHg based on 200 mL samples, respectively. The high accuracy and reproducibility has been proved by the spiked recoveries (96.0‒108 %) in real water samples and determination of the certified reference material. Both the adsorption and desorption process can be completed within 5 min. The proposed method with simple operation, short pre-concentration time and high sensitivity has been successfully applied to mercury speciation at trace levels in the samples with complicated matrices, including underground water, surface water, sea water and fish samples.

Environmentally stable, photochromic and thermotropic organohydrogels for low cost on-demand optical devices.

HYPOTHESIS: The color-changing ability of creatures widely existed in nature has inspired the development of adaptive allochroic materials, which can respond to various external stimuli. Integrating multi-stimuli responsiveness and long-term stability in allochroic system are urgent for practical applications under complex circumstances. EXPERIMENTS: The photochromic/thermotropic organohydrogels (PTOs) comprised polyacrylamide and cationic cellulose (JR400) were prepared by facile free-radical polymerization and glycerol displacement. The coexisting covalent bonds and noncovalent interactions collaboratively reinforce the networks, endowing the PTOs with boosted stretchability and toughness. FINDINGS: The photochromic ammonium molybdate (Mo7) and thermo-sensitive poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (EPE) were made into networks. In these cooperative networks, each constituent performed their own function without disruption, including fast photochromism (10 s) and durable thermo-responsiveness. Importantly, the glycerol-water solvent bestowed the distinct anti-freezing (-30 °C) and anti-dehydration performances on the PTOs. Accordingly, the materials could serve as promising rewritable devices for high-resolution and long-term data storage/encryption. Moreover, on-demand PTO windows integrating UV-prevention and solar energy regulation with Tlum (92.96%) and ΔTsol (46.02%) could create comfortable and healthy environments for occupants. This work offers a new design strategy for low-cost, environmentally stable smart optical devices.