Ultralow‐Fouling,Functionalizable, and Hydrolyzable Zwitterionic Materials and Their Derivatives for Biological Applications

In recent years, zwitterionic materials such as poly(carboxybetaine) (pCB) and poly(sulfobetaine) (pSB) have been applied to a broad range of biomedical and engineering materials. Due to electrostatically induced hydration, surfaces coated with zwitterionic groups are highly resistant to nonspecific protein adsorption, bacterial adhesion, and biofilm formation. Among zwitterionic materials, pCB is unique due to its abundant functional groups for the convenient immobilization of biomolecules. pCB can also be prepared in a hydrolyzable form as cationic pCB esters, which can kill bacteria or condense DNA. The hydrolysis of cationic pCB esters into nonfouling zwitterionic groups will lead to the release of killed microbes or the irreversible unpackaging of DNA. Furthermore, mixed‐charge materials have been shown to be equivalent to zwitterionic materials in resisting nonspecific protein adsorption when they are uniformly mixed at the molecular scale.     

Hierarchical Assembly of Nanocellulose‐Based Filaments by Interfacial Complexation

In the present study, interfacial complexation spinning of oppositely charged cellulose‐materials is applied to fabricate hierarchical and continuous nanocellulose based filaments under aqueous conditions by using cationic cellulose nanocrystals with different anionic celluloses including soluble sodium carboxymethyl cellulose and insoluble 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy radical‐oxidized cellulose nanofibers and dicarboxylated cellulose nanocrystals (DC‐CNC). The morphologies of the wet and dry nanocellulose based filaments are further investigated by optical and electron microscopy. All fabricated continuous nanocellulose based filaments display a hierarchical structure similar to the natural cellulose fibers in plant cells. As far as it is known, this is not only the first report about the fabrication of nanocellulose based filaments by interfacial complexation of cationic CNCs with anionic celluloses but also the first demonstration of fabricating continuous fibers directly from oppositely charged nanoparticles by interfacial nanoparticle complexation (INC). This INC approach may provide a new route to design continuous filaments from many other oppositely charged nanoparticles with tailored characteristics.     

水性聚氨酯的发展、分类、合成及应用

水性聚氨酯是一种环境友好型高分子材料。在概述水性聚氨酯发展历程的基础上，详细阐述了阴离子型、阳离子型、两性离子型、非离子型水性聚氨酯的合成工艺路线、制备方法的优缺点，以及水性聚氨酯的主要应用领域，并指出水性聚氨酯的发展方向。     

Simultaneous separation of cationic and anionic proteins using zwitterionic surfactants in capillary electrophoresis

The zwitterionic surfactant Rewoteric AM CAS U forms a dynamic wall coating that prevents the adsorption of cationic proteins as well as suppresses the electroosmotic flow (EOF). Addition of polarizable anions to buffers containing this zwitterionic surfactant increases the once suppressed EOF to values nearing +3 x 10(-4) cm2/(V s). The retention of the EOF allows for the separation of analytes of widely different mobilities and is demonstrated by the simultaneous separation of cationic and anionic proteins. Using a buffer containing optimal amounts of the polarizable anion perchlorate and surfactant CAS U, the proteins lysozyme, ribonuclease A, alpha-chymotrypsinogen A, and myoglobin are separated in less than 15 min. Efficiencies as high as 1.5 million plates/m and recoveries greater than 91% are observed for proteins injected in distilled water. Migration time reproducibility is approximately 1% RSD within 1 day and approximately 3% RSD from day to day. The anionic and cationic proteins can be separated over a pH range of 5.5-9, all yielding good efficiencies.     

高分子科学中的计算机模拟

综述了计算机模拟在高分子科学中的发展和现状,介绍了它的研究方法及研究领域,并指出了它的发展方向。     

基于分子尺度的沥青材料设计

基于分子尺度的沥青材料设计是指利用多尺度分子模拟预测沥青材料的性能,指导制备符合高性能要求的沥青材料。分子尺度的设计方法主要有量子力学方法、蒙特卡洛方法和分子动力学方法。总结了沥青质模型、沥青模型、量子力学和分子模拟在沥青材料性能预测和设计中的应用,重点介绍了改性沥青材料常用物理力学性质的模拟计算方法及相关研究成果。     

Effect of molecular architecture of polycarboxylate ethers on plasticizing performance in alkali-activated slag paste

A range of anionic and cationic polycarboxylate ether (PCE) plasticizers with different molecular architectures (molecular weights, side chain lengths, and ratios of side chain density to backbone charge) are synthesized and tested to determine their effects on the rheological properties of fresh alkali-activated slag (AAS) pastes. A higher density of long side chains in the lower molecular weight polymers can provide a noticeable yield stress reduction, indicating a mild increase in workability compared to that of an unmodified AAS paste. It is hypothesized that side chains may have two important roles, i.e., providing steric hindrance to disperse particles after PCE adsorption on a particle surface, and also providing partial protection of the backbone charges against attachment of one PCE molecule to two or more slag particles, which is called bridging. This enhances the likelihood of adsorption on single particles, and thus increases the plasticizing action. A very similar plasticizing mechanism is observed for PCEs with similar structures but differing charge signs (cationic/anionic), which indicates that both anionic and cationic adsorption sites are available on AAS particle surfaces. The measured flow curves of all pastes are well described by the Herschel–Bulkley model with shear thinning behavior.     

Carboxybetaine-modified succinylated chitosan-based beads encourage pancreatic β-cells (Min-6) to form islet-like spheroids under in vitro conditions

In vitro, pancreatic β-cells tend to reduce their ability to aggregate into islets and lose insulin-producing ability, likely due to insufficient cell–cell and cell–matrix interactions that are essential for β-cell retention, viability and functionality. In response to these needs, surfaces of succinylated chitosan-based beads (NSC) were modified with zwitterionic carboxy-betaine (CB) moieties, a compatible osmolyte known to regulate cellular hydration state, and used to promote the formation of β-cell spheroids using a conventional 2D cell culture technique. The NSC were synthesised by ionic gelation and surface-functionalised with CB using carbodiimide chemistry. Scanning electron microscopy (SEM), dynamic laser scattering (DLS) and Fourier transform infrared spectroscopy (FTIR) were employed as characterisation tools to confirm the successful modification of the succinylated chitosan material into spherical beads with rough surfaces and a diameter of 0.4?µm. NSC with and without CB were re-suspended at concentrations of 0.1, 0.3 and 0.6?mg/mL in saline medium and tested in vitro with MIN6 murine pancreatic β-cell line. Results showed that a concentration of 0.3?mg/mL, NSC-CB encouraged pancreatic MIN6 cells to proliferate and form spheroids via E-cadherin and Pdx-1 activation within 48?h in culture. These spheroids, with a size of approximately 80?µm, exhibited high cell viability and enhanced insulin protein expression and secretion when compared to cells organised by the non-modified beads.     

Chemomechanics of complex materials: challenges and opportunities in predictive kinetic timescales

What do nanoscopic biomolecular complexes between the cells that line our blood vessels have in common with the microscopic silicate glass fiber optics that line our communication highways, or with the macroscopic steel rails that line our bridges? To be sure, these are diverse materials which have been developed and studied for years by distinct experimental and computational research communities. However, the macroscopic functional properties of each of these structurally complex materials pivots on a strong yet poorly understood interplay between applied mechanical states and local chemical reaction kinetics. As is the case for many multiscale material phenomena, this chemomechanical coupling can be abstracted through computational modeling and simulation to identify key unit processes of mechanically altered chemical reactions. In the modeling community, challenges in predicting the kinetics of such structurally complex materials are often attributed to the so-called rough energy landscape, though rigorous connection between this simple picture and observable properties is possible for only the simplest of structures and transition states. By recognizing the common effects of mechanical force on rare atomistic events ranging from molecular unbinding to hydrolytic atomic bond rupture, we can develop perspectives and tools to address the challenges of predicting macroscopic kinetic consequences in complex materials characterized by rough energy landscapes. Here, we discuss the effects of mechanical force on chemical reactivity for specific complex materials of interest, and indicate how such validated computational analysis can enable predictive design of complex materials in reactive environments.     

电子陶瓷材料的数字模拟与建模

电子陶瓷材料正由经验研究和实物展示向虚拟设计和测试转变，从材料到器件性能的计算机数字模拟和建模也应运而生。本文介绍了电子陶瓷材料领域技术数字模拟与建模的理论背景，着重讨论了有限元方法(FEM)在压电及其相关陶瓷及换能器建模中的应用，以及分子动力学模拟在电子陶瓷材料电子结构、点缺陷和晶界特性等电子陶瓷材料中的研究进展和发展趋势。     

Elasticity, strength and resilience: A comparative study on mechanical signatures of α-Helix, β-sheet and tropocollagen domains

In biology, structural design and materials engineering is unified through formation of hierarchical features with atomic resolution, from nano to macro. Three molecular building blocks are particularly prevalent in all structural protein materials: alpha helices (AHs), beta-sheets (BSs) and tropocollagen (TC). In this article we present a comparative study of these three key building blocks by focusing on their mechanical signatures, based on results from full-atomistic simulation studies. We find that each of the basic structures is associated with a characteristic material behavior: AH protein domains provide resilience at large deformation through energy dissipation at low force levels, BS protein domains provide great strength under shear loading, and tropocollagen molecules provide large elasticity for deformation recovery. This suggests that AHs, BSs, and TC molecules have mutually exclusive mechanical signatures. We correlate each of these basic properties with the molecule’s structure and the associated fundamental rupture mechanisms. Our study may enable the use of abundant protein building blocks in nanoengineered materials, and may provide critical insight into basic biological mechanisms for bio-inspired nanotechnologies. The transfer towards the design of novel nanostructures could lead to new multifunctional and mechanically active, tunable, and changeable materials.     

Electronic materials process modeling

Summary This report focuses on current needs in the process modeling of materials used in electronic and optoelectronic device fabrication and provides specific recommendations in addressing these needs. The establishment of relationships between materials structure and processing is identified as the critical modeling need in the electronics industry. A hierarchical modeling approach is suggested aiming at the development of efficient and robust process simulators with predictive capabilities and, thus, providing modeling tools for development of optimal materials processing strategies. This approach is based on linking a variety of existing theoretical and computational methods which include: ab initio, semi-empirical, and empirical atomic-scale simulation methods for accurate calculation of materials properties and mechanistic physical understanding; microstructural-scale thermodynamic, transport, and kinetic modeling; and macroscopic process-specific process simulation. Issues of interdisciplinary communication and collaboration and exploratory research for new materials are also addressed.Providing a standard list of literature references is beyond the scope of this report. A general overview of industrial needs and technical goals is provided by Ref. 1.     

Towards High‐Performance Bioinspired Composites

Biological composites have evolved elaborate hierarchical structures to achieve outstanding mechanical properties using weak but readily available building blocks. Combining the underlying design principles of such biological materials with the rich chemistry accessible in synthetic systems may enable the creation of artificial composites with unprecedented properties and functionalities. This bioinspired approach requires identification, understanding, and quantification of natural design principles and their replication in synthetic materials, taking into account the intrinsic properties of the stronger artificial building blocks and the boundary conditions of engineering applications. In this progress report, the scientific and technological questions that have to be addressed to achieve this goal are highlighted, and examples of recent research efforts to tackle them are presented. These include the local characterization of the heterogeneous architecture of biological materials, the investigation of structure–function relationships to help unveil natural design principles, and the development of synthetic processing routes that can potentially be used to implement some of these principles in synthetic materials. The importance of replicating the design principles of biological materials rather than their structure per se is highlighted, and possible directions for further progress in this fascinating, interdisciplinary field are discussed.     

Supramolecular Chiral 2D Materials and Emerging Functions

Chiral materials are widely applied in various fields such as enantiomeric separation, asymmetric catalysis, and chiroptical effects, providing stereospecific conditions and environments. Supramolecular concepts to create the chiral materials can provide an insight for emerging chiro-optical properties due to their well-defined scaffolds and the precise functionalization of the surfaces or skeletons. Among the various supramolecular chiral structures, 2D chiral sheet structures are particularly interesting materials because of their extremely high surface area coupled with many unique chemical and physical properties, thereby offering potential for the next generation of functional materials for optically active systems and optoelectronic devices. Nevertheless, relatively limited examples for 2D chiral materials exhibiting specific functionality have been reported because incorporation of molecular chirality into 2D architectures is difficult at the present stage. Here, a brief overview of the recent advances is provided on the construction of chiral supramolecular 2D materials and their functions. The design principles toward 2D chirality and their potential applications are also discussed.     

The zwitterion effect in high-conductivity polyelectrolyte materials

The future of lithium metal batteries as a widespread, safe and reliable form of high-energy-density rechargeable battery depends on a significant advancement in the electrolyte material used in these devices. Molecular solvent-based electrolytes have been superceded by polymer electrolytes in some prototype devices, primarily in a drive to overcome leakage and flammability problems, but these often exhibit low ionic conductivity and prohibitively poor lithium-ion transport. To overcome this, it is necessary to encourage dissociation of the lithium ion from the anionic polymer backbone, ideally without the introduction of competing, mobile ionic species. Here we demonstrate the effect of zwitterionic compounds, where the cationic and anionic charges are immobilized on the same molecule, as extremely effective lithium ion 'dissociation enhancers'. The zwitterion produces electrolyte materials with conductivities up to seven times larger than the pure polyelectrolyte gels, a phenomenon that appears to be common to a number of different copolymer and solvent systems.     

Investigation of charge effects on drug release behavior for ionic thermosensitive hydrogels

The influence of various drugs with different charges on the drug release behavior in porous ionic thermosensitive hydrogels was investigated. The present hydrogels were prepared from N-isopropylacrylamide (NIPAAm) and cationic monomer, trimethyl (acrylamido propyl) ammonium iodide (TMAAI), or anionic monomer, acrylic acid (AA), or zwitterionic monomer, N′,N′-dimethyl (acrylamido propyl) ammonium propane sulfonate (DMAAPS), or nonionic monomer, poly(ethylene glycol) methylether acrylate (PEGMEA), and pore-forming agent, poly(ethylene glycol) (PEG) with different molecular weights. Caffeine as a nonionic drug, crystal violet (CV) as a cationic drug solute, and phenol red as an anionic drug solute were chosen as model drugs to perform the drug release experiment. Results show that the release ratio of caffeine in the hydrogels is not affected by the ionicity of hydrogels. The CV strongly interacted with the anionic hydrogel; thus, the CV release ratio is very low. CV is only adsorbed on the skin layer of the cationic hydrogel due to charge repulsion and is released rapidly. The result of phenol red (anionic solute) release in the hydrogels is contrary to CV. In addition, the partition coefficients (K_d) and the drug delivery behavior of the present gels were also investigated.     

Precise Molecular Design for High-Performance Luminogens with Aggregation-Induced Emission

Precise design of fluorescent molecules with desired properties has enabled the rapid development of many research fields. Among the different types of optically active materials, luminogens with aggregation-induced emission (AIEgens) have attracted significant interest over the past two decades. The negligible luminescence of AIEgens as a molecular species and high brightness in aggregate states distinguish them from conventional fluorescent dyes, which has galvanized efforts to bring AIEgens to a wide array of multidisciplinary applications. Herein, the useful principles and emerging structure–property relationships for precise molecular design toward AIEgens with desirable properties using concrete examples are revealed. The cutting-edge applications of AIEgens and their excellent performance in enabling new research directions in biomedical theranostics, optoelectronic devices, stimuli-responsive smart materials, and visualization of physical processes are also highlighted.     

Recent Progress in Ionic Iridium(III) Complexes for Organic Electronic Devices

Ionic iridium(III) complexes are emerging with great promise for organic electronic devices, owing to their unique features such as ease of molecular design and synthesis, excellent photophysical properties, superior redox stability, and highly efficient emissions of virtually all colors. Here, recent progress on new material design, regarding photo‐ and electroluminescence is highlighted, including several interesting topics such as: i) color‐tuning strategies of cationic iridium(III) complexes, ii) widespread utilization in phosphorescent light‐emitting devices fabricated by not only solution processes but also vacuum evaporation deposition, and iii) potential applications in data record, storage, and sercurity. Results on anionic iridium(III) complexes and “soft salts” are also discussed, indicating a new related subject. Finally, a brief outlook is suggested, pointing out that ionic iridium(III) complexes should play a more significant role in future organic electronic materials technology.     

Application of Fracture Mechanics Concepts to Hierarchical Biomechanics of Bone and Bone-like Materials

Fracture mechanics concepts are applied to gain some understanding of the hierarchical nanocomposite structures of hard biological tissues such as bone, tooth and shells. At the most elementary level of structural hierarchy, bone and bone-like materials exhibit a generic structure on the nanometer length scale consisting of hard mineral platelets arranged in a parallel staggered pattern in a soft protein matrix. The discussions in this paper are organized around the following questions: (1) The length scale question: why is nanoscale important to biological materials? (2) The stiffness question: how does nature create a stiff composite containing a high volume fraction of a soft material? (3) The toughness question: how does nature build a tough composite containing a high volume fraction of a brittle material? (4) The strength question: how does nature balance the widely different strengths of protein and mineral? (5) The optimization question: Can the generic nanostructure of bone and bone-like materials be understood from a structural optimization point of view? If so, what is being optimized? What is the objective function? (6) The buckling question: how does nature prevent the slender mineral platelets in bone from buckling under compression? (7) The hierarchy question: why does nature always design hierarchical structures? What is the role of structural hierarchy? A complete analysis of these questions taking into account the full biological complexities is far beyond the scope of this paper. The intention here is only to illustrate some of the basic mechanical design principles of bone-like materials using simple analytical and numerical models. With this objective in mind, the length scale question is addressed based on the principle of flaw tolerance which, in analogy with related concepts in fracture mechanics, indicates that the nanometer size makes the normally brittle mineral crystals insensitive to cracks-like flaws. Below a critical size on the nanometer length scale, the mineral crystals fail no longer by propagation of pre-existing cracks, but by uniform rupture near their limiting strength. The robust design of bone-like materials against brittle fracture provides an interesting analogy between Darwinian competition for survivability and engineering design for notch insensitivity. The follow-up analysis with respect to the questions on stiffness, strength, toughness, stability and optimization of the biological nanostructure provides further insights into the basic design principles of bone and bone-like materials. The staggered nanostructure is shown to be an optimized structure with the hard mineral crystals providing structural rigidity and the soft protein matrix dissipating fracture energy. Finally, the question on structural hierarchy is discussed via a model hierarchical material consisting of multiple levels of self-similar composite structures mimicking the nanostructure of bone. We show that the resulting “fractal bone”, a model hierarchical material with different properties at different length scales, can be designed to tolerate crack-like flaws of multiple length scales.