State Key Laboratory of Chemical Engineering

Surface resistance to nonspecific protein adsorption, cell/bacterial adhesion, and biofilm formation is critical for the development and performance of biomedical and analytical devices. Significant needs and efforts have been made in the development of biocompatible and bioactive materials for antifouling surfaces, but much of the work retains an empirical flavor due to the complexity of experiments and the lack of robust theoretical models. In this review, two major classes of nonfouling materials (i.e. hydrophilic and zwitterionic materials) and associated basic nonfouling mechanisms and practical examples are discussed. Highly hydrated chemical groups with optimized physical properties of the surface, along with appropriate surface coating methods, are the keys to developing effective and stable nonfouling materials for long-term biomedical applications. The zwitterionic polymers are promising nonfouling biomaterials due to the simplicity of synthesis, ease of applicability, abundance of raw materials, and availability of functional groups.

Free-standing and flexible sandwich-like MXene/carbon nanotube (CNT) paper, composed of alternating MXene and CNT layers, is fabricated using a simple filtration method. These sandwich-like papers exhibit high volumetric capacitances, good rate performances, and excellent cycling stability when employed as electrodes in supercapacitors.

Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers with highly tuneable structures and functionalities. COFs have been proposed as ideal materials for applications in the energy-intensive field of molecular separation due to their notable intrinsic features such as low density, exceptional stability, high surface area, and readily adjustable pore size and chemical environment. This review attempts to highlight the key advancements made in the synthesis of COFs for diverse separation applications such as water treatment or the separation of gas mixtures and organic molecules, including chiral and isomeric compounds. Methods proposed for the fabrication of COF-based columns and continuous membranes for practical applications are also discussed in detail. Finally, a perspective regarding the remaining challenges and future directions for COF research in the field of separation has also been presented.

Dynamic covalent polymer networks (DCPN) have historically attracted attention for their unique roles in chemical recycling and self-healing, which are both relevant for sustainable societal development. Efforts in these directions have intensified in the past decade with notable progress in newly discovered dynamic covalent chemistry, fundamental material concepts, and extension toward emerging applications including energy and electronic devices. Beyond that, the values of DCPN in discovering/designing functional properties not offered by classical thermoplastic and thermoset polymers have recently gained traction. In particular, the dynamic bond exchangeability of DCPN has shown unparalleled design versatility in various areas including shape-shifting materials/devices, artificial muscles, and microfabrication. Going beyond this basic bond exchangeability, various molecular mechanisms to manipulate network topologies (topological transformation) have led to opportunities to program polymers, with notable concepts such as living networks and topological isomerization. In this review, we provide an overview of the above progress with particular focuses on molecular design strategies for the exploitation of functional material properties. Based on this, we point out the remaining issues and offer perspectives on how this class of materials can shape the future in ways that are complementary with classical thermoplastic and thermoset polymers.

Longer and stronger; stiff but not brittle Hydrogels are highly water-swollen, cross-linked polymers. Although they can be highly deformed, they tend to be weak, and methods to strengthen or toughen them tend to reduce stretchability. Two papers now report strategies to create tough but deformable hydrogels (see the Perspective by Bosnjak and Silberstein). Wang et al . introduced a toughening mechanism by storing releasable extra chain length in the stiff part of a double-network hydrogel. A high applied force triggered the opening of cycling strands that were only activated at high chain extension. Kim et al . synthesized acrylamide gels in which dense entanglements could be achieved by using unusually low amounts of water, cross-linker, and initiator during the synthesis. This approach improves the mechanical strength in solid form while also improving the wear resistance once swollen as a hydrogel. —MSL

Abstract Secondary batteries based on metal anodes (e.g., Li, Na, Mg, Zn, and Al) are among the most sought‐after candidates for next‐generation mobile and stationary storage systems because they are able to store a larger amount of energy per unit mass or volume. However, unstable electrodeposition and uncontrolled interfacial reactions occuring in liquid electrolytes cause unsatisfying cell performance and potential safety concerns for the commercial application of these metal anodes. Solid‐state electrolytes (SSEs) having a higher modulus are considered capable of inhibiting difficulties associated with the anodes and may enable building of safe all‐solid‐state metal batteries, yet several challenges, such as insufficient room‐temperature ionic conductivity and poor interfacial stability between the electrode and the electrolyte, hinder the large‐scale development of such batteries. Here, research and development of SSEs including inorganic ceramics, organic solid polymers, and organic–inorganic hybrid/composite materials for metal‐based batteries are reviewed. The comparison of different types of electrolytes is discussed in detail, in the context of electrochemical energy storage applications. Then, the focus of this study is on recent advances in a range of attractive and innovative battery chemistries and technologies that are enabled by SSEs. Finally, the challenges and future perspectives are outlined to foresee the development of SSEs.

Recently, carbon dioxide capture and conversion, along with hydrogen from renewable resources, provide an alternative approach to synthesis of useful fuels and chemicals. People are increasingly interested in developing innovative carbon dioxide hydrogenation catalysts, and the pace of progress in this area is accelerating. Accordingly, this perspective presents current state of the art and outlook in synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols through two leading hydrogenation mechanisms: methanol reaction and Fischer-Tropsch based carbon dioxide hydrogenation. The future research directions for developing new heterogeneous catalysts with transformational technologies, including 3D printing and artificial intelligence, are provided.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTADDITION / CORRECTIONThis article has been corrected. View the notice.Supramolecular Amphiphiles Based on Host–Guest Molecular Recognition MotifsGuocan Yu, Kecheng Jie, and Feihe Huang*View Author Information State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China*E-mail: [email protected]. Fax and phone: +86-571-8795-3189.Cite this: Chem. Rev. 2015, 115, 15, 7240–7303Publication Date (Web):February 26, 2015Publication History Received19 September 2014Published online26 February 2015Published inissue 12 August 2015https://pubs.acs.org/doi/10.1021/cr5005315https://doi.org/10.1021/cr5005315review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views31579Altmetric-Citations871LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Amphiphiles,Hydrophobicity,Micelles,Self organization,Vesicles Get e-Alerts

Self-assembling systems play a significant role in physiological functions and have therefore attracted tremendous attention due to their great potential for applications in energy, biomedicine and nanotechnology. Peptides, consisting of amino acids, are among the most popular building blocks and programmable molecular motifs. Nanostructures and materials assembled using peptides exhibit important potential for green-life new technology and biomedical applications mostly because of their bio-friendliness and reversibility. The formation of these ordered nanostructures pertains to the synergistic effect of various intermolecular non-covalent interactions, including hydrogen-bonding, π-π stacking, electrostatic, hydrophobic, and van der Waals interactions. Therefore, the self-assembly process is mainly driven by thermodynamics; however, kinetics is also a critical factor in structural modulation and function integration. In this review, we focus on the influence of thermodynamic and kinetic factors on structural assembly and regulation based on different types of peptide building blocks, including aromatic dipeptides, amphiphilic peptides, polypeptides, and amyloid-relevant peptides.

Dynamic covalent polymer networks have long been recognized. With the initial focus on the unintended impact of dynamic covalent linkages on the viscoelasticity of commercial rubbers, efforts in modern times have transitioned into designing dynamic covalent polymer networks with unique adaptive properties. Whereas self-healing and thermoset reprocessing have been the primary motivations for studying dynamic covalent polymer networks, the recent discovery of the vitrimeric rheological behavior and solid-state plasticity for this type of material have opened up new opportunities in material innovations. This, coupled with the revelation of the dynamic characteristics of commercially relevant polymer building blocks such as esters and urethanes, suggests a promising future for this class of materials.

Self-assembled peptide and protein amyloid nanostructures have traditionally been considered only as pathological aggregates implicated in human neurodegenerative diseases. In more recent times, these nanostructures have found interesting applications as advanced materials in biomedicine, tissue engineering, renewable energy, environmental science, nanotechnology and material science, to name only a few fields. In all these applications, the final function depends on: (i) the specific mechanisms of protein aggregation, (ii) the hierarchical structure of the protein and peptide amyloids from the atomistic to mesoscopic length scales and (iii) the physical properties of the amyloids in the context of their surrounding environment (biological or artificial). In this review, we will discuss recent progress made in the field of functional and artificial amyloids and highlight connections between protein/peptide folding, unfolding and aggregation mechanisms, with the resulting amyloid structure and functionality. We also highlight current advances in the design and synthesis of amyloid-based biological and functional materials and identify new potential fields in which amyloid-based structures promise new breakthroughs.

Abstract Nanocrystalline cellulose (NCC) is an emerging renewable nanomaterial that holds promise in many different applications, such as in personal care, chemicals, foods, pharmaceuticals, etc. By appropriate modification of NCC, various functional nanomaterials with outstanding properties, or significantly improved physical, chemical, biological, as well as electronic properties can be developed. The nanoparticles are stabilised in aqueous suspension by negative charges on the surface, which are produced during the acid hydrolysis process. NCC suspensions can form a chiral nematic ordered phase beyond a critical concentration, i.e. NCC suspensions transform from an isotropic to an anisotropic chiral nematic liquid crystalline phase. Due to its nanoscale dimension and intrinsic physicochemical properties, NCC is a promising renewable biomaterial that can be used as a reinforcing component in high performance nanocomposites. Many new nanocomposite materials with attractive properties were obtained by the physical incorporation of NCC into a natural or synthetic polymeric matrix. Simple chemical modification on NCC surface can improve its dispersability in different solvents and expand its utilisation in nano‐related applications, such as drug delivery, protein immobilisation, and inorganic reaction template. This review paper provides an overview on this emerging nanomaterial, focusing on the surface modification, properties and applications of NCC.

Fabricating active materials into specific macrostructures is critical in the pursuit of high electro-catalytic activity. Herein we demonstrate that a three-dimensional (3D) architecture of NiFe layered double hydroxide (NiFe-LDH) significantly reduced the onset potential, yielded high current density at small overpotentials, and showed outstanding stability in electrochemical oxygen evolution reaction.

Soft robots driven by stimuli-responsive materials have unique advantages over conventional rigid robots, especially in their high adaptability for field exploration and seamless interaction with humans. The grand challenge lies in achieving self-powered soft robots with high mobility, environmental tolerance, and long endurance. We are able to advance a soft electronic fish with a fully integrated onboard system for power and remote control. Without any motor, the fish is driven solely by a soft electroactive structure made of dielectric elastomer and ionically conductive hydrogel. The electronic fish can swim at a speed of 6.4 cm/s (0.69 body length per second), which is much faster than previously reported untethered soft robotic fish driven by soft responsive materials. The fish shows consistent performance in a wide temperature range and permits stealth sailing due to its nearly transparent nature. Furthermore, the fish is robust, as it uses the surrounding water as the electric ground and can operate for 3 hours with one single charge. The design principle can be potentially extended to a variety of flexible devices and soft robots.

Graphdiyne (GDY), a new two-dimensional (2D) carbon allotrope, has been receiving increased attention. Its unique sp-sp2 carbon atoms, uniform pores, and highly π-conjugated structure provide promising potential in practical applications, such as gas separation, catalysis, water remediation, humidity sensor, and energy-related fields. In the recent years, considerable efforts have been expended toward the development of well-defined GDY. However, GDY materials still face numerous challenges, including the need for a more thorough understanding of the growth mechanism, strategies for synthesizing one- or few-layer single-crystalline GDY films, characterization of basic physicochemical properties, and achievement of promising applications. This review aims at providing a comprehensive update on the synthesis of GDY and GDY-based materials, as well as their properties, including structural, electronic, mechanical, and spectral properties, and their applications in nanotechnology.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTDevelopment of Pseudorotaxanes and Rotaxanes: From Synthesis to Stimuli-Responsive Motions to ApplicationsMin Xue†, Yong Yang‡, Xiaodong Chi†, Xuzhou Yan†, and Feihe Huang*†View Author Information† State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China‡ Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 15, 7398–7501Publication Date (Web):March 3, 2015Publication History Received10 October 2014Published online3 March 2015Published inissue 12 August 2015https://pubs.acs.org/doi/10.1021/cr5005869https://doi.org/10.1021/cr5005869review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views24378Altmetric-Citations718LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Macrocycles,Polymers,Reaction products,Rotaxanes,Supramolecular chemistry Get e-Alerts

Lithium‐metal batteries are of particular interest for next‐generation electrical energy storage because of their high energy density on both volumetric and gravimetric bases. Effective strategies to stabilize the Li‐metal anode are the prerequisite for the progress of these exceptional storage technologies, such as Li–S and Li–O 2 batteries. Various challenges, such as uneven Li electrodeposition, anode volume expansion, and dendrite‐induced short‐circuit have hindered the practical application of rechargeable Li‐metal batteries. Herein, a one‐step facile and cost‐effective strategy for stabilizing lithium‐metal batteries via 3D porous Cu current collector/Li‐metal composite anode is reported. The porous structure of the composite electrode provides a “cage” for the redeposition of “hostless” lithium and accommodates the anode volume expansion during cycling. Compared with planar Cu foil, its high specific surface area favors the electrochemical reaction kinetics and lowers the local current density along the anode. It leads to low interfacial resistance and stabilizes the Li electrodeposition. On this basis, galvanostatic measurements are performed on both symmetric cells and Li/Li 4 Ti 5 O 12 cells and it is found that the electrodes exhibit exceptional abilities of promoting cell lifetime and stabilizing the cycling behavior. Although this work focuses on lithium metal, this novel tactic is easy to generalize to other metal electrodes.

Phototheranostics represents a promising direction for modern precision medicine, which has recently attracted great research interest from multidisciplinary research areas. Organic optical agents including small molecular fluorophores, semiconducting/conjugated polymers, aggregation-induced emission luminogens, etc. with tuneable photophysical properties, high biosafety and biocompatibility, facile processability and ease of functionalization have delivered encouraging performance in disease phototheranostics. This review summarizes the recent progress of organic phototheranostic agents with an emphasis on the main strategies to manipulate the three excitation energy dissipation pathways, namely, radiative decay, thermal deactivation, and intersystem crossing, with the assistance of a Jablonski diagram, which particularly showcases how the Jablonski diagram has been guiding the design of organic agents from molecule to aggregate levels to promote the disease phototheranostic outcomes. Molecular design and nanoengineering strategies to modulate photophysical processes of organic optical agents to convert the absorbed photons into fluorescent/phosphorescent/photoacoustic signals and/or photodynamic/photothermal curing effects for improved disease phototheranostics are elaborated. Noteworthily, adaptive phototheranostics with activatable and transformable functions on demand, and regulation of excitation such as chemiexcitation to promote the phototheranostic efficacies are also included. A brief summary with the discussion of current challenges and future perspectives in this research field is further presented.

product generation is discussed. We aim to provide a detailed review of the state-of-the-art C─C coupling strategies to the community for further development and inspiration in both fundamental understanding and technological applications.

Nitrogen-doped graphene sheets were prepared through a hydrothermal reduction of colloidal dispersions of graphite oxide in the presence of hydrazine and ammonia at pH of 10. The effect of hydrothermal temperature on the structure, morphology, and surface chemistry of as-prepared graphene sheets were investigated though XRD, N(2) adsorption, solid-state (13)C NMR, SEM, TEM, and XPS characterizations. Oxygen reduction and nitrogen doping were achieved simultaneously under the hydrothermal reaction. Up to 5% nitrogen-doped graphene sheets with slightly wrinkled and folded feature were obtained at the relative low hydrothermal temperature. With the increase of hydrothermal temperature, the nitrogen content decreased slightly and more pyridinic N incorporated into the graphene network. Meanwhile, a jellyfish-like graphene structure was formed by self-organization of graphene sheets at the hydrothermal temperature of 160 °C. Further increase of the temperature to 200 °C, graphene sheets could self-aggregate into agglomerate particles but still contained doping level of 4 wt % N. The unique hydrothermal environment should play an important role in the nitrogen doping and the jellyfish-like graphene formation. This simple hydrothermal method could provide the synthesis of nitrogen-doped graphene sheets in large scale for various practical applications.