Coordination-Driven Hierarchical Assembly of Hybrid Nanostructures Based on 2D Materials.

2D materials have received tremendous scientific and engineering interests due to their remarkable properties and broad-ranging applications such as energy storage and conversion, catalysis, biomedicine, electronics, and so forth. To further enhance their performance and endow them with new functions, 2D materials are proposed to hybridize with other nanostructured building blocks, resulting in hybrid nanostructures with various morphologies and structures. The properties and functions of these hybrid nanostructures depend strongly on the interfacial interactions between 2D materials and other building blocks. Covalent and coordination bonds are two strong interactions that hold high potential in constructing these robust hybrid nanostructures based on 2D materials. However, most 2D materials are chemically inert, posing problems for the covalent assembly with other building blocks. There are usually coordination atoms in most of 2D materials and their derivatives, thus coordination interaction as a strong interfacial interaction has attracted much attention. In this review, recent progress on the coordination-driven hierarchical assembly based on 2D materials is summarized, focusing on the synthesis approaches, various architectures, and structure-property relationship. Furthermore, insights into the present challenges and future research directions are also presented.

How can multi-bond network hydrogels dissipate energy more effectively: an investigation on the relationship between network structure and properties.

Constructing a multi-bond network (MBN), which involves hierarchical dynamic bonds with different bond association energies, is an effective method for achieving super tough hydrogels. In this work, a small amount of poly(vinyl alcohol) (PVA) is introduced into a loosely chemically crosslinked poly(acrylic acid) (PAA) network. The hydrophilic PVA chains can physically interact and form hydrogen bonds with the PAA chains. After a freeze-thaw process, PVA could partially crystallize and the generated microcrystals could become new crosslinking points of the hydrogels. Meanwhile, the hydrogen bonds between PAA and PVA, which connect to the microcrystal "core" through PVA chains, could also become new crosslinking points of the hydrogels. The obtained ternary-crosslinked hydrogels (T-gel 10%) exhibit toughness as high as 8 times that in pure PAA hydrogels. When the PVA content exceeds 15 wt%, PVA chains will run through the whole PAA network. Thus the PVA chains will be crosslinked by microcrystals through freeze-thaw treatment, leading to a double network structure, resulting in a brittle hydrogel. The step-increased modulus of the hydrogels with different PVA contents clearly demonstrates the change in the network structure of the hydrogels. Successively, Fe3+ is introduced into the MBN hydrogels as a third cross-linking point. The obtained quaternary-crosslinked hydrogels (Q-gel 10%-Fe5) (50 wt% water content) exhibit significantly improved mechanical properties: tensile strength as high as 6.83 MPa with a fracture energy of 29.9 MJ m-3. This work provides clear insight into the relationship between network structure and mechanical properties in super tough MBN hydrogels.

Structural reorganization and crack-healing properties of hydrogels based on dynamic diselenide linkages.

We report the dynamic behavior of diselenide-containing hydrophilic polyurethanes and hydrogels based on diselenide exchange reactions in an aqueous media. Diselenide-containing linear and cross-linked polyurethanes were synthesized via polyaddition reactions using diselenide-containing diol in combination with pyridinium diol that enhances the hydrophilicity of the polymer chains. The obtained linear polyurethanes underwent photo-induced diselenide exchange reactions with small diselenide compounds and degraded to smaller fragments, confirming the dynamicity of the obtained hydrophilic polyurethanes. The prepared hydrogels displayed characteristic large swelling behavior based on the structural reorganization through diselenide exchange either under photo-irradiation at 365 nm or even in the dark at room temperature. The diselenide-containing hydrogels also showed crack-healing behavior under the same exchanging conditions, presenting the utility of diselenide linkages as simple and useful units to offer high dynamicity to hydrogels.

Ultrathin MXene Nanosheets Decorated with TiO2 Quantum Dots as an Efficient Sulfur Host toward Fast and Stable Li-S Batteries.

Being conductive and flexible, 2D transition metal nitrides and carbides (MXenes) can serve in Li-S batteries as sulfur hosts to increase the conductivity and alleviate the volume expansion. However, the surface functional groups, such as OH and F, weaken the ability of bare MXenes in the chemisorption of polysulfides. Besides, they create numerous hydrogen bonds which make MXenes liable to restack, resulting in substantial loss of active area and, thus, inaccessibility of ions and electrolyte. Herein, a facile, one-step strategy is developed for the growth of TiO2 quantum dots (QDs) on ultrathin MXene (Ti3 C2 Tx ) nanosheets by cetyltrimethylammonium bromide-assisted solvothermal synthesis. These QDs act as spacers to isolate the MXene nanosheets from restacking, and preserve their 2D geometry which guarantees larger electrode-electrolyte contact area and higher sulfur loading. The stronger adsorption energy of polysulfides with TiO2 (than with Ti3 C2 Tx ), as proven by density functional theory calculations, is essential for better on-site polysulfide retention. The ultrathin nature and protected conductivity ensure rapid ion and electron diffusion, and the excellent flexibility maintains high mechanical integrity. In result, the TiO2 QDs@MXene/S cathode exhibits significantly improved long-term cyclability and rate capability, disclosing a new opportunity toward fast and stable Li-S batteries.

An Intrinsically Stretchable and Compressible Supercapacitor Containing a Polyacrylamide Hydrogel Electrolyte.

Stretchability and compressibility of supercapacitors is an essential element of modern electronics, such as flexible, wearable devices. Widely used polyvinyl alcohol-based electrolytes are neither very stretchable nor compressible, which fundamentally limits the realization of supercapacitors with high stretchability and compressibility. A new electrolyte that is intrinsically super-stretchable and compressible is presented. Vinyl hybrid silica nanoparticle cross-linkers were introduced into polyacrylamide hydrogel backbones to promote dynamic cross-linking of the polymer networks. These cross-linkers serve as stress buffers to dissipate energy when strain is applied, providing a solution to the intrinsically low stretchability and compressibility shortcomings of conventional supercapacitors. The newly developed supercapacitor and electrolyte can be stretched up to an unprecedented 1000 % strain with enhanced performance, and compressed to 50 % strain with good retention of the initial performance.

Facile and Green Production of Impurity-Free Aqueous Solutions of WS2 Nanosheets by Direct Exfoliation in Water.

To obtain 2D materials with large quantity, low cost, and little pollution, liquid-phase exfoliation of their bulk form in water is a particularly fascinating concept. However, the current strategies for water-borne exfoliation exclusively employ stabilizers, such as surfactants, polymers, or inorganic salts, to minimize the extremely high surface energy of these nanosheets and stabilize them by steric repulsion. It is worth noting, however, that the remaining impurities inevitably bring about adverse effects to the ultimate performances of 2D materials. Here, a facile and green route to large-scale production of impurity-free aqueous solutions of WS2 nanosheets is reported by direct exfoliation in water. Crucial parameters such as initial concentration, sonication time, centrifugation speed, and centrifugation time are systematically evaluated to screen out an optimized condition for scaling up. Statistics based on morphological characterization prove that substantial fraction (66%) of the obtained WS2 nanosheets are one to five layers. X-ray diffraction and Raman characterizations reveal a high quality with few, if any, structural distortions. The water-borne exfoliation route opens up new opportunities for easy, clean processing of WS2 -based film devices that may shine in the fields of, e.g., energy storage and functional nanocomposites owing to their excellent electrochemical, mechanical, and thermal properties.

Dually cross-linked single network poly(acrylic acid) hydrogels with superior mechanical properties and water absorbency.

Poly(acrylic acid) (PAA) hydrogels with superior mechanical properties, based on a single network structure with dual cross-linking, are prepared by one-pot free radical polymerization. The network structure of the PAA hydrogels is composed of dual cross-linking: a dynamic and reversible ionic cross-linking among the PAA chains enabled by Fe(3+) ions, and a sparse covalent cross-linking enabled by a covalent cross-linker (Bis). Under deformation, the covalently cross-linked PAA chains remain intact to maintain their original configuration, while the Fe(3+)-enabled ionic cross-linking among the PAA chains is broken to dissipate energy and then recombined. It is found that the mechanical properties of the PAA hydrogels are significantly influenced by the contents of covalent cross-linkers, Fe(3+) ions and water, which can be adjusted within a substantial range and thus broaden the applications of the hydrogels. Meanwhile, the PAA hydrogels have excellent recoverability based on the dynamic and reversible ionic cross-linking enabled by Fe(3+) ions. Moreover, the swelling capacity of the PAA hydrogels is as high as 1800 times in deionized water due to the synergistic effects of ionic and covalent cross-linkings. The combination of balanced mechanical properties, efficient recoverability, high swelling capacity and facile preparation provides a new method to obtain high-performance hydrogels.

Self-healable, tough and highly stretchable ionic nanocomposite physical hydrogels.

We present a facile strategy to synthesize self-healable tough and highly stretchable hydrogels. Our design rationale for the creation of ionic cross-linked hydrogels is to graft an acrylic acid monomer on the surface of vinyl hybrid silica nanoparticles (VSNPs) for the growth of poly(acrylic) acid (PAA), and the obtained VSNP-PAA nanobrush can be used as a gelator. Physical cross-linking through hydrogen bonding and ferric ion-mediated ionic interactions between PAA polymer chains of the gelators yielded ionic nanocomposite physical hydrogels with excellent and balanced mechanical properties (tensile strength 860 kPa, elongation at break ∼2300%), and the ability to self-repair (tensile strength ∼560 kPa, elongation at break ∼1800%). The toughness and stretchability arise from the reversible cross-linking interactions between the polymer chains that help dissipate energy through stress (deformation) triggered dynamic processes. These unique properties will enable greater application of these hydrogel materials, especially in tissue engineering.

The Effect of Colloidal Nanoparticles on Phase Separation of Block and Heteroarm Star Copolymers Confined between Polymer Brushes.

The effect of colloidal nanoparticles on the phase changes of the amphiphilic AB linear diblock, A1A2B, and A2B heteroarm star copolymers confined between two polymer brush substrates was investigated by using a real-space self-consistent field theory. By changing the concentrations of nanoparticles and polymer brushes, the phase structure of the amphiphilic AB copolymer transforms from lamellar to core-shell hexagonal phase to cylinder phase. The pattern of A2B heteroarm star copolymer changes from core-shell hexagonal phases to lamellar phases and the layer decreases when increasing the density of the polymer brushes. The results showed that the phase behavior of the system is strongly influenced by the polymer brush architecture and the colloidal nanoparticle numbers. The colloidal nanoparticles and the soft confined surface of polymer brushes make amphiphilic AB copolymers easier to form ordered structures. The dispersion of the nanoparticles was also investigated in detail. The soft surfaces of polymer brushes and the conformation of the block copolymers work together to force the nanoparticles to disperse evenly. It will give helpful guidance for making some new functional materials by nano etching technology, nano photoresist, and nanoprinting.

Steady solution and its stability of a mathematical model of diabetic atherosclerosis.

Atherosclerosis is a leading cause of death worldwide. Making matters worse, nearly 463 million people have diabetes, which increases atherosclerosis-related inflammation. Diabetic patients are twice as likely to have a heart attack or stroke. In this paper, we consider a simplified mathematical model for diabetic atherosclerosis involving LDL, HDL, glucose, insulin, free radicals (ROS), ß cells, macrophages and foam cells, which satisfy a system of partial differential equations with a free boundary, the interface between the blood flow and the plaque. We establish the existence of small radially symmetric stationary solutions to the model and study their stability. Our analysis shows that the plague will persist due to hyperglycemia even when LDL and HDL are in normal range, hence confirms that diabetes increase the risk of atherosclerosis.

One-Step in Situ Synthesis of Tough and Highly Conductive Ionohydrogels with Water-Retentive and Antifreezing Properties.

Flexible and conductive gels are promising materials as intelligent and wearable electronics. Herein, through a facile one-step in situ free-radical polymerization, tough VSNPs-PAA-Zr4+ ionohydrogels with integrated multiple functionalities are prepared, which are dually cross-linked by multivalent vinyl-functionalized silica nanoparticles (VSNPs) and metal coordination between Zr4+ and the carboxyl groups in PAA chains. The incorporation of Zr4+ with stable valency during polymerization enables the direct formation of a large number of metal coordination cross-links for adequate energy dissipation, overcoming the inhibition of unstable metal ions on the polymerization process. Meanwhile, VSNPs serve as multivalent cross-linkers and effective stress transfer centers. The obtained VSNPs-PAA-Zr4+ ionohydrogels show high toughness of up to 25 MJ m-3 with a high tensile strength of 3010 kPa and a large elongation at break of 1360%, along with reliable adhesive performance. Attributed to use of an IL/water binary solvent, the ionohydrogels possess excellent water-retentive and antifreezing abilities. Moreover, the existence of large quantities of mobile ions endows the VSNPs-PAA-Zr4+ ionohydrogels with a superior conductivity of 4.77 S m-1 and a high strain sensitivity with a gauge factor (GF) of 9.04, which are promising materials as intelligent and wearable strain sensors.

Highly Conductive Polysiloxane Elastomers with Excellent Transparency, Resilience, and Stretchability.

Flexible transparent conductive materials show great potential in wearable electronics, flexible sensors, and so on. But the most used flexible conductive materials like hydrogels and ionogels suffer from evaporation and solvent leakage. For the application in these fields, integrated performances of preeminent resilience, transparency, stability, and conductivity that do not change with deformation are prerequisites. It is still challenging to handle the trade-off among these performances. Herein, a facile approach is established to balance these properties into one elastomer. Through the thiol-ene click reaction, mercaptopropyl-modified polydimethylsiloxane (mPDMS) is cross-linked and grafted by PEG-based macromonomers to prepare conductive elastomers. By anchoring with mPDMS through carbon-sulfur bonds, PEG can be evenly dispersed, resulting in ultratransparency (97%) and stable conductivity of as high as 1.68 × 10-2 S m-1, comparable to pure PEG/lithium salt conductivity. It also has a wide electrochemical stability window with a high voltage of 4.8 V. Moreover, the multibond network strategy is employed through grafting ligand 1-vinylimidazole to mPDMS to construct dynamic cross-links between Zn(II) and 1-vinylimidazol, bestowing excellent properties to the elastomers. Overall, elastomers with a well-balanced performance of high resilience, good conductivity, and ultratransparency are obtained, providing promising applications for soft electronics, lithium battery electrolytes, and flexible devices.

WELL-POSEDNESS OF A MATHEMATICAL MODEL OF DIABETIC ATHEROSCLEROSIS WITH ADVANCED GLYCATION END-PRODUCTS.

Atherosclerosis is a leading cause of death worldwide; it emerges as a result of multiple dynamical cell processes including hemodynamics, endothelial damage, innate immunity and sterol biochemistry. Making matters worse, nearly 463 million people have diabetes, which increases atherosclerosis-related inflammation, diabetic patients are twice as likely to have a heart attack or stroke. The pathophysiology of diabetic vascular disease is generally understood. Dyslipidemia with increased levels of atherogenic LDL, hyperglycemia, oxidative stress and increased inflammation are factors that increase the risk and accelerate development of atherosclerosis. In a recent paper [53], we have developed mathematical model that includes the effect of hyperglycemia and insulin resistance on plaque growth. In this paper, we propose a more comprehensive mathematical model for diabetic atherosclerosis which include more variables; in particular it includes the variable for Advanced Glycation End-Products (AGEs)concentration. Hyperglycemia trigger vascular damage by forming AGEs, which are not easily metabolized and may accelerate the progression of vascular disease in diabetic patients. The model is given by a system of partial differential equations with a free boundary. We also establish local existence and uniqueness of solution to the model. The methodology is to use Hanzawa transformation to reduce the free boundary to a fixed boundary and reduce the system of partial differential equations to an abstract evolution equation in Banach spaces, and apply the theory of analytic semigroup.

WELL-POSEDNESS OF A MATHEMATICAL MODEL OF DIABETIC ATHEROSCLEROSIS.

Atherosclerosis is a leading cause of death in the United States and worldwide; it emerges as a result of multiple dynamical cell processes including hemodynamics, endothelial damage, innate immunity and sterol biochemistry. Making matters worse, nearly 21 million Americans have diabetes, a disease where patients' cells cannot efficiently take in dietary sugar, causing it to build up in the blood. In part because diabetes increases atherosclerosis-related inflammation, diabetic patients are twice as likely to have a heart attack or stroke. Past work has shown that hyperglycemia and insulin resistance alter function of multiple cell types, including endothelium, smooth muscle cells and platelets, indicating the extent of vascular disarray in this disease. Although the pathophysiology of diabetic vascular disease is generally understood, there is no mathematical model to date that includes the effect of diabetes on plaque growth. In this paper, we propose a mathematical model for diabetic atherosclerosis; the model is given by a system of partial differential equations with a free boundary. We establish local existence and uniqueness of solution to the model. The methodology is to use Hanzawa transformation to reduce the free boundary to a fixed boundary and reduce the system of partial differential equations to an abstract evolution equation in Banach spaces, and apply the theory of analytic semigroup.

Super Tough and Intelligent Multibond Network Physical Hydrogels Facilitated by Ti3C2Tx MXene Nanosheets.

Stretchable and conductive hydrogels have emerged as promising candidates for intelligent and flexible electronic devices. Herein, based on a multibond network (MBN) design rationale, super tough and highly stretchable nanocomposite physical hydrogels are prepared, where 2D Ti3C2Tx MXene nanosheets serve as multifunctional cross-linkers and effective stress transfer centers. Further MXene-poly(acrylic acid) (PAA)-Fe3+ MBN physical hydrogels fabricated through controlled permeation of Fe3+ exhibit prominent and well-balanced mechanical properties (e.g., the tensile strength can reach 10.4 MPa and elongation at break can be as high as 3080%), attributed to the dual cross-linking network with dense Fe3+-mediated coordination cross-links between MXene nanosheets and PAA chains and sparse carboxy-Fe3+ cross-links between PAA chains. Moreover, both conductive MXene nanosheets and numerous ions endow the hydrogels with superior conductivity (up to 3.8 S m-1), strain sensitivity (high gauge factor of 10.09), and self-healing performance, showing great prospect as intelligent flexible electronics.

Biomimetic Gradient Hydrogel Actuators with Ultrafast Thermo-Responsiveness and High Strength.

Most current hydrogel actuators suffer from either poor mechanical properties or limited responsiveness. Also, the widely used thermo-responsive poly-(N-isopropylacrylamide) (PNIPAM) homopolymer hydrogels have a slow response rate. Thus, it remains a challenge to fabricate thermo-responsive hydrogel actuators with both excellent mechanical and responsive properties. Herein, ultrafast thermo-responsive VSNPs-P(NIPAM-co-AA) hydrogels containing multivalent vinyl functionalized silica nanoparticles (VSNPs) are fabricated. The ultrafast thermo-responsiveness is due to the mobile polymer chains grafted from the surfaces of the VSNPs, which can facilitate hydrophobic aggregation, inducing the phase transition and generating water transport channels for quick water expulsion. In addition, the copolymerization of NIPAM with acrylic acid (AA) decreases the transition temperature of the thermo-responsive PNIPAM-based hydrogels, contributing to ultrafast thermo-responsive shrinking behavior with a large volume change of as high as 72.5%. Moreover, inspired by nature, intelligent hydrogel actuators with gradient structure can be facilely prepared through self-healing between the ultrafast thermo-responsive VSNPs-P(NIPAM-co-AA) hydrogel layers and high-strength VSNPs-PAA-Fe3+ multibond network (MBN) hydrogel layers. The obtained well-integrated gradient hydrogel actuators show ultrafast thermo-responsive performance within only 9 s in 60 °C water, as well as high strength, and can be used for more practical applications as intelligent soft actuators or artificial robots.

Concentric ring pattern formation in a competing crystallization and phase separation process.

Spherulitic patterns usually form in the single process of crystallization in polymer blends. But when phase separation intervenes under deep quench, the radial growth of the initial spherulitic patterns tends to invert into concentric alternating crystalline-/amorphous-rich ring structures. Within crystalline-rich regions, lateral lamellae orient in the tangential direction rather than in the usual radial direction. We demonstrate the determining factor for this first observed phenomenon is the concentration deviation enhanced phase separation dynamics at the growth interface of crystals.

Quantum algorithm for MMNG-based DBSCAN.

DBSCAN is a famous density-based clustering algorithm that can discover clusters with arbitrary shapes without the minimal requirements of domain knowledge to determine the input parameters. However, DBSCAN is not suitable for databases with different local-density clusters and is also a very time-consuming clustering algorithm. In this paper, we present a quantum mutual MinPts-nearest neighbor graph (MMNG)-based DBSCAN algorithm. The proposed algorithm performs better on databases with different local-density clusters. Furthermore, the proposed algorithm has a dramatic increase in speed compared to its classic counterpart.

Cellulose-based dual graft molecular brushes as potential drug nanocarriers: stimulus-responsive micelles, self-assembled phase transition behavior, and tunable crystalline morphologies.

Well-defined cellulose-based dual graft molecular brushes, composed of ethyl cellulose-graft-poly(N,N-dimethylaminoethyl methacrylate)-graft-poly(epsilon-caprolactone) (EC-g-PDMAEMA-g-PCL), have been prepared by ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Unlike other brush copolymers, the new molecular brushes show some unique physicochemical properties and multifunction due to their unique topological structures. These biocompatible copolymers self-assembled to micelles in aqueous solution. Upon pH change, the single micelles further assembled into micellar aggregates. As a result, the micelles in aqueous media could act as excellent drug nanocarriers for controlled drug release. The crystallinity and crystal morphology of the copolymers can be controlled to a certain extent by varying the length of the side chains, which may exert strong spacial restriction and, hence, affect the crystal structures.

Homogeneous and Real Super Tough Multi-Bond Network Hydrogels Created through a Controllable Metal Ion Permeation Strategy.

Poly(acrylic acid) (PAA) hydrogels with a multi-bond network composed of sparse chemical cross-links and carboxyl-Fe3+ coordination are prepared through a controllable permeation strategy utilizing ferric citrate (FeCA). The existing strategies that directly soak PAA hydrogels in Fe3+ solutions usually induce an inhomogeneous network with densely cross-linked shells and uncertain water content of the hydrogels, which brings about ambiguity when investigating strengthening mechanisms because water content significantly affects the mechanical properties of hydrogels. Herein, the controllable permeation of Fe3+ into PAA networks based on the competition between citric acid (CA)-Fe3+ chelation and PAA-Fe3+ coordination guarantees sustained release of Fe3+, facilitating homogeneous distribution of ionic cross-links and a certain water content. The obtained hydrogels exhibit excellent and balanced mechanical properties (high tensile strength of 3.28 to 6.95 MPa with large elongations at break of 1400 to 780% when water content decreases from 80 to 50 wt %). The real robust tensile strength of this hydrogel originates from the effective energy dissipation of the homogeneous PAA-Fe3+ cross-links, and the high water content ensures a large elongation at break. Furthermore, the hydrogel also has pH-responsive and shape-memory properties.