Superstrong Ionogel Enabled by Coacervation-Induced Nanofibril Assembly for Sustainable Moisture Energy Harvesting.

Ionogels have grabbed significant interest in various applications, from sensors and actuators to wearable electronics and energy storage devices. However, current ionogels suffer from low strength and poor ionic conductivity, limiting their performance in practical applications. Here, inspired by the mechanical reinforcement of natural biomacromolecules through noncovalent aggregates, a strategy is proposed to construct nanofibril-based ionogels through complex coacervation-induced assembly. Cellulose nanofibrils (CNFs) can bundle together with poly(ionic liquid) (PIL) to form a superstrong nanofibrous network, in which the ionic liquid (IL) can be retained to form ionogels with high liquid inclusion and ionic conductivity. The strength of the CNF-PIL-IL ionogels can be tuned by the IL content over a wide range of up to 78 MPa. The optical transparency, high strength, and hygroscopicity enabled them to be promising candidates in moist-electricity generation and applications such as energy harvesting windows and wearable power generators. In addition, the ionogels are degradable and the ionogel-based generators can be recycled through dehydration. Our strategy suggests perspectives for the fabrication of high-strength and multifunctional ionogels for sustainable applications.

Simultaneous Realization of Superoleophobicity and Strong Substrate Adhesion in Water via a Unique Segment Orientation Mechanism.

The underwater superoleophobicity of a coating is often caused by its preferential water affinity, which, however, normally weakens the substrate adhesion property. In this work, a new strategy is reported for achieving strong underwater adhesion between a well-designed amphiphilic polyurethane coating and a diverse range of substrates while also rendering the coating surface's superoleophobicity. When the coating, which is a mixture of an amphiphilic polyurethane and a water miscible solvent, is immersed in water, the hydrophobic segments aggregate to orientate and pile along the surface of substrates via a segment orientation mechanism triggered by solvent exchange with water penetration to exert strong adhesion. At the same time, the hydrophilic segments will physically crosslink to form a hydrogel coating, endowing the substrate with underwater superoleophobicity. This work provides a facile, versatile, and scalable approach for the future design of superoleophobic coatings in a water environment.

A Surface-Confined Gradient Conductive Network Strategy for Transparent Strain Sensors toward Full-Range Monitoring.

The development of transparent and flexible sensors suitable for the full-range monitoring of human activities is highly desirable, yet presents a daunting challenge due to the need for a combination of properties such as high stretchability, high sensitivity, and good linearity. Gradient structures are commonly found in many biological systems and exhibit excellent mechanical properties. Here, we report a novel surface-confined gradient conductive network (SGN) strategy to construct conductive polymer hydrogel-based stain sensors (CHSS). This CHSS showed an ultrahigh stretchability of 4000% strain, transparency above 90% at a wavelength of 600 nm, as well as skin-like Young's modulus of 40 kPa. Impressively, the sensitivity was improved to 3.0 and outstanding linear sensing performance was achieved simultaneously in the ultrawide range of 0% to 4000% strain with a high R-square value of 0.994. With the help of SGN strategy, this CHSS was able to monitor both large-scale and small-scale human motions and activities. This SGN strategy can open a new avenue for the development of novel flexible strain sensors with excellent mechanical, transparent, and sensing performance for full-range monitoring of human activities.

Topological cyclodextrin nanoparticles as crosslinkers for self-healing tough hydrogels as strain sensors.

Hydrogels have been widely used for various applications, and thus addressing the challenges associated with the design of sustainable hydrogels has become an important issue. However, little attention has been devoted toward the design of crosslinkers which are often toxic, lack self-healing capabilities, and derived from petrochemicals. Herein, novel cyclodextrin topological nanoparticles (TNPs) have been constructed. These TNPs were found to possess crosslinking capabilities and the corresponding TNPs-crosslinked hydrogels showed excellent mechanical performances with a high stretchability of 1860 % and stress of 180 kPa and good anti-fatigue abilities. These hydrogels could be readily recycled and used for modular assembly and disassembly in various shapes and could serve as flexible strain sensors to monitor human activities with a sensing range of 0-1800 %, controllable sensitivity, and good fatigue resistance. These topological nanoparticles can inspire the design of novel physical crosslinkers for novel flexible strain sensors, tough and self-healing hydrogels, and soft robotics.

Molecular Understanding and Design of Porous Polyurethane Hydrogels with Ultralow-Oil-Adhesion for Oil-Water Separation.

Materials with opposite affinities toward oil and water have been extensively used to coat porous substrates for oil-water separation, but the applications of these materials have been limited by the need for complex coating processes as well as the short-term adherence of these materials onto different substrates under extreme conditions. As reported herein, the robust porous polyurethane hydrogel has been theoretically and structurally designed with ultralow-oil-adhesion properties which is free stand without depending on additional substrates. The combination of superhydrophilic properties along with the underwater superoleophobic behavior of this porous hydrogel allows gravity driven separations of oil-water mixtures, and its antiadhesion performance toward oil prevents undesirable oily fouling. The underwater superoleophobic properties were also illustrated by molecular dynamics simulation to understand the resisting effect of hydrated layers. The as-prepared porous hydrogel shows ultrahigh oil-water separation efficiencies of 99.9% for various oil-water mixtures, ranging from those containing viscous oils (pump oil and peanut oil) to organic solvents (n-hexane, n-hexadecane, and toluene). In addition, this hydrogel is durable even with exposure to various harsh conditions including acidic and basic media (pH 0-14) as well as exposure to mechanical abrasion. We believe that the combination of facile preparation, substrate independence, gravity driven separation, antifouling properties, high durability, as well as the outstanding separation flux and efficiency of this robust porous hydrogel will help to advance the design and application of materials in oil-water separation fields.

A polysaccharide-based micelle-hydrogel synergistic therapy system for diabetes and vascular diabetes complications treatment.

Various glucose-sensitive drug delivery platforms have been developed recently to treat diabetes. However, there is much less work has been reported on treatment of diabetes and vascular diabetes complications simultaneously. In this work, a novel polysaccharide-based micelle-hydrogel synergistic therapy system was fabricated to address this limitation. Zwitterionic dialdehyde starch-based micelles (SB-DAS-VPBA) were synthesized via single electron transfer-living radical polymerization (SET-LRP). Hydrophilic segment sulfobetaine (SB) and hydrophobic segment 4­vinylphenylboronic acid (VPBA) were grafted to the dialdehyde starch (DAS) backbones. Then, chitosan/dialdehyde starch derivatives (CS/SB-DAS-VPBA) micelle-hydrogel was synthesized by Schiff-base bonds. Insulin and nattokinase were loaded to obtain the micelle-hydrogel synergistic therapy system. In vitro drug delivery and blood clots dissolution behaviors were determined. Results suggest that the micelle-hydrogel synergistic therapy system not only possesses glucose-responsive insulin delivery property, but also provides good thrombolytic capacity. Thus, this micelle-hydrogel synergistic therapy system can be used as a platform for diabetes and vascular diabetes complications treatment.

Coexistence of Antiadhesion Performance, Intrinsic Stretchability, and Transparency.

Antiadhesion performance, stretchability, and transparency are highly desirable properties for materials and devices in numerous applications. However, the existing strategies for imparting materials with antiadhesion performance generally induce rigidity and opacity, and principle is yet to be provided for designing materials that combine these important parameters. Here, we show that four factors including a low surface energy, appropriate cross-linking, availability of a homogeneous and amorphous composite, and a smooth material surface can be used to design an intrinsically stretchable and transparent polymer film with antiadhesion performance against various liquids including water, diiodomethane, hexadecane, cooking oil, and pump oil. The film can be obtained via simply molding a waterborne polymer network at ambient temperature. Furthermore, the film can retain its antiadhesion performance and outstanding transparency even when it is subjected to large mechanical deformations reaching up to 1800%, and its maximal fracture strain exceeds 3000%. These design concepts offer a general platform for achieving multiple material functionalities, and may open new avenues for the surface functionalization of stretchable materials and devices.

Hydrogel bowls for cleaning oil spills on water.

We demonstrate a hydrogel bowl capable of selectively and rapidly collecting spilled oil while floating on water. The bowl has macroscopic openings in its sidewall, and its surface is first coated with octadecyltrichlorosilane (OTS) and then with diffusion pump oil, which imparts exceptional hydrophobic, oleophilic, and high oil wettability properties. The use of a hydrogel makes it possible to obtain surface hydrophobicity and oleophilicity, while also being inexpensive, eco-friendly, and easy to fabricate. Using a prototype of the bowl and a small pump system, we demonstrate that oils with a broad range of viscosities (2.7-2000.0 cSt at 20-40 °C) are more rapidly and efficiently collected from the surface of both pure water and seawater than with any other reported technique. The hydrogel bowl can collect oil for more than one month without losing its efficiency and can be stored in oil for reuse. Therefore, such hydrogel bowls represent a new alternative to conventional oil spill remediation techniques.

Construction of polylysine dendrimer nanocomposites carrying nattokinase and their application in thrombolysis.

Thrombotic disease has become one of the leading causes of mortality among humans globally. Nattokinase (NK), a novel thrombolytic agent, has attracted the attention of researchers. However, NK is a serine protease that is vulnerable to environmental effects resulting in its inactivation. In this study, polylysine dendrimer (PLLD) was synthesized through divergence-convergence method, and a series of NK/PLLD nanocomposites with different molar ratio was prepared. In addition, NK was successfully incorporated into the cores of PLLD G4 through hydrogen bonds and van der Waals forces. In NK/PLLD nanocomposites, when the molar ratio of NK to PLLD is 1:30, a high relative enzyme activity level (up to 117%) was achieved and was more stable at different temperatures and pH than free NK. In in vitro thrombolysis experiment, compared with free NK, NK/PLLD nanocomposites could control the release of NK. The thrombolysis rate of NK/PLLD nanocomposites reached 50% at 12 h, which can effectively avoid other complications such as hemorrhage. Interestingly, NK/PLLD nanocomposites with positive charge can penetrate into the negatively charged thrombus through electrostatic interaction, thus providing a good thrombolytic effect. Hemolysis and MTT experiments show that PLLD nanomaterials can serve as ideal carriers of protein drugs. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 440-449, 2018.

Multifunctional Environmental Smart Fertilizer Based on l-Aspartic Acid for Sustained Nutrient Release.

Fertilizer is one of the most important elements of modern agriculture. However, conventional fertilizer, when applied to crops, is vulnerable to losses through volatilization, leaching, nitrification, or other means. Such a loss limits crop yields and pollutes the environment. In an effort to enhance nutrient use efficiency and reduce environmental pollution, an environmental smart fertilizer was reported in the current study. Poly(aspartic acid) and a degradable macro-cross-linker based on l-aspartic acid were synthesized and introduced into the fertilizer as a superabsorbent to improve the fertilizer degradability and soil moisture-retention capacity. Sustained release behavior of the fertilizer was achieved in soil. Cumulative release of nitrogen and phosphorus was 79.8% and 64.4% after 30 days, respectively. The water-holding and water-retention capacities of soil with the superabsorbent are obviously higher than those of the control soil without superabsorbent. For the sample of 200 g of soil with 1.5 g of superabsorbent, the water-holding capacity is 81.8%, and the water-retention capacity remains 22.6% after 23 days. All of the current results in this study indicated that the as-prepared fertilizer has a promising application in sustainable modern agriculture.

Injectable and Self-Healing Carbohydrate-Based Hydrogel for Cell Encapsulation.

With the fast development of cell therapy, there has been a shift toward the development of injectable hydrogels as cell carriers that can overcome current limitations in cell therapy. However, the hydrogels are prone to damage during use, inducing cell apoptosis. Therefore, this study was carried out to develop an injectable and self-healing hydrogel based on chondroitin sulfate multiple aldehyde (CSMA) and N-succinyl-chitosan (SC). By varying the CSMA to SC ratio, the hydrogel stiffness, water content, and kinetics of gelation could be controlled. Gelation readily occurred at physiological conditions, predominantly due to a Schiff base reaction between the aldehyde groups on CSMA and amino groups on SC. Meanwhile, because of the dynamic equilibrium of Schiff base linkage, the hydrogel was found to be self-healing. Cells encapsulated in the hydrogel remained viable and metabolically active. In addition, the hydrogel produced minimal inflammatory response when injected subcutaneously in a rat model and showed biodegradability in vivo. This work establishes an injectable and self-healing hydrogel derived from carbohydrates with potential applications as a cell carrier and in tissue engineering.

Universal perceptron and DNA-like learning algorithm for binary neural networks: non-LSBF implementation.

Implementing linearly nonseparable Boolean functions (non-LSBF) has been an important and yet challenging task due to the extremely high complexity of this kind of functions and the exponentially increasing percentage of the number of non-LSBF in the entire set of Boolean functions as the number of input variables increases. In this paper, an algorithm named DNA-like learning and decomposing algorithm (DNA-like LDA) is proposed, which is capable of effectively implementing non-LSBF. The novel algorithm first trains the DNA-like offset sequence and decomposes non-LSBF into logic XOR operations of a sequence of LSBF, and then determines the weight-threshold values of the multilayer perceptron (MLP) that perform both the decompositions of LSBF and the function mapping the hidden neurons to the output neuron. The algorithm is validated by two typical examples about the problem of approximating the circular region and the well-known n-bit parity Boolean function (PBF).

Universal perceptron and DNA-like learning algorithm for binary neural networks: LSBF and PBF implementations.

Universal perceptron (UP), a generalization of Rosenblatt's perceptron, is considered in this paper, which is capable of implementing all Boolean functions (BFs). In the classification of BFs, there are: 1) linearly separable Boolean function (LSBF) class, 2) parity Boolean function (PBF) class, and 3) non-LSBF and non-PBF class. To implement these functions, UP takes different kinds of simple topological structures in which each contains at most one hidden layer along with the smallest possible number of hidden neurons. Inspired by the concept of DNA sequences in biological systems, a novel learning algorithm named DNA-like learning is developed, which is able to quickly train a network with any prescribed BF. The focus is on performing LSBF and PBF by a single-layer perceptron (SLP) with the new algorithm. Two criteria for LSBF and PBF are proposed, respectively, and a new measure for a BF, named nonlinearly separable degree (NLSD), is introduced. In the sense of this measure, the PBF is the most complex one. The new algorithm has many advantages including, in particular, fast running speed, good robustness, and no need of considering the convergence property. For example, the number of iterations and computations in implementing the basic 2-bit logic operations such as AND, OR, and XOR by using the new algorithm is far smaller than the ones needed by using other existing algorithms such as error-correction (EC) and backpropagation (BP) algorithms. Moreover, the synaptic weights and threshold values derived from UP can be directly used in designing of the template of cellular neural networks (CNNs), which has been considered as a new spatial-temporal sensory computing paradigm.