Double Stimuli‐Responsive Isoporous Membranes via Post‐Modification of pH‐Sensitive Self‐Assembled Diblock Copolymer Membranes

Double stimuli‐responsive membranes are prepared by modification of pH‐sensitive integral asymmetric polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes with temperature‐responsive poly(N‐isopropylacrylamide) (pNIPAM) by a surface linking reaction. PS‐b‐P4VP membranes are first functionalized with a mild mussel‐inspired polydopamine coating and then reacted via Michael addition with an amine‐terminated pNIPAM‐NH₂ under slightly basic conditions. The membranes are thoroughly characterized by nuclear magnetic resonance (¹H‐NMR), Fourier transform infrared spectroscopy and X‐ray‐induced photoelectron spectroscopy. Additionally dynamic contact angle measurements are performed comparing the sinking rate of water droplets at different temperatures. The pH‐ and thermo‐double sensitivities of the modified membranes are proven by determining the water flux under different temperature and pH conditions.     

Self‐Assembled SERS Substrates with Tunable Surface Plasmon Resonances

The fabrication of surface‐enhanced Raman spectroscopy (SERS) substrates that are optimized for use with specific laser wavelength–analyte combinations is addressed. In order to achieve large signal enhancement, temporal stability, and reproducibility over large substrate areas at low cost, only self‐assembly and templating processes are employed. The resulting substrates consist of arrays of gold nanospheres with controlled diameter and spacing, properties that dictate the optical response of the structure. Tunability of the extended surface plasmon resonance is observed in the range of 520–1000 nm. It is demonstrated that the enhancement factor is maximized when the surface plasmon resonance is red‐shifted with respect to the SERS instrument laser line. Despite relying on self‐organization, site‐to‐site enhancement factor variations smaller than 10% are obtained.     

Functional Coating of Porous Silica Microparticles with Native Biomembranes towards Portable Flow‐Through Biochemical Microreactors

In biological cells, various transmembrane enzymes function as highly effective chemical reactors confined in space with characteristic length scales of tens of nanometers to micrometer. However, it is still challenging to quantitatively confine membranes in compact reactor platforms without losing their biochemical functions. Here, a simple and straightforward strategy towards the fabrication of a new flow‐through reactor by the functional coating of porous silica microparticles with sarcoplasmic reticulum membranes is described. After a short incubation, the membranes achieve the homogeneous, full coverage of the particle surface, spanning across pores with the diameter of about 100 nm. By using the underlying pores as cavity reservoirs, transmembrane enzyme (Ca²⁺‐ATPase) in the membrane retains their capability of ATP hydrolysis. This enables us to confine 1.1 m² of native membranes containing a large amount of Ca²⁺‐ATPase (approx. 10 nmol) in a column‐packaged, flow‐through reactor with merely 1.8 mL volume, which cannot be achieved by the reconstitution of proteins in artificial lipid membranes or condensation of membranes in suspensions. The distinct functional levels corresponding to different reaction buffers can be reproduced even after many buffer exchanges over 14 days, confirming the stability and reproducibility of the membrane‐particle hybrid reactors.     

Novel PEGylated Nanoassemblies Made of Self‐Assembled Squalenoyl Nucleoside Analogues

This study describes a new simple method to obtain high loading of anticancer or antiviral nucleoside analogues into “stealth” poly(ethylene glycol) (PEG)‐coated nanoassemblies. These nanodevices are obtained by co‐nanoprecipitation in water of (i) squalenoyl prodrugs obtained by the bioconjugation of the natural lipid squalene with either the anticancer drug gemcitabine (Gem‐Sq) or the antiviral drug deoxycytidine (ddC‐Sq) with (ii) a PEG derivative of either cholesterol (Chol‐PEG) or squalene (Sq‐PEG). It was found that both PEG derivatives (Chol‐PEG or Sq‐PEG) were efficiently incorporated in the resulting composite nanoassemblies (CNAs), as shown by radioactivity studies, Zeta potential determination, and size measurements. Optimal compositions were defined for each PEG derivative to ensure the best stability in water and in buffer solutions. X‐ray diffraction and electron microscopy investigations revealed that depending on the structure of the squalenoyl nucleoside analogue used (Gem‐Sq or ddC‐Sq), these nanoassemblies might be toroids or cubosomes. Following PEGylation, the Gem‐Sq nanoassemblies displayed superior in vitro anticancer activity on gemcitabine‐resistant leukemia L1210 10K cells than either their non‐PEGylated counterparts or gemcitabine alone.     

Reinforcement of Shear Thinning Protein Hydrogels by Responsive Block Copolymer Self‐Assembly

Shear thinning hydrogels are promising materials that exhibit rapid self‐healing following the cessation of shear, making them attractive for applications including injectable biomaterials. Here, self‐assembly is demonstrated as a strategy to introduce a reinforcing network within shear thinning artificially engineered protein gels, enabling a responsive transition from an injectable state at low temperatures with a low yield stress to a stiffened state at physiological temperatures with resistance to shear thinning, higher toughness, and reduced erosion rates and creep compliance. Protein‐polymer triblock copolymers capable of the responsive self‐assembly of two orthogonal networks are synthesized. Midblock association forms a shear‐thinning network, while endblock aggregation at elevated temperatures introduces a second, independent physical network into the protein hydrogel. These reversible crosslinks introduce extremely long relaxation times and lead to a five‐fold increase in the elastic modulus, significantly larger than is expected from transient network theory. Thermoresponsive reinforcement reduces the high temperature creep compliance by over four orders of magnitude, decreases the erosion rate by at least a factor of five, and increases the yield stress by up to a factor of seven. Combined with the demonstrated potential of shear thinning artificial protein hydrogels for various uses, this reinforcement mechanism broadens the range of applications that can be addressed with shear‐thinning physical gels.     

Electrochemically Triggered Selective Adsorption of Biotemplated Nanoparticles on Self‐Assembled Organometallic Diblock Copolymer Thin Films

The controlled adsorption of the iron‐containing cage protein ferritin at the nanoscale using stimuli‐responsive self‐assembled diblock copolymer thin‐film templates is reported. The diblock copolymer used study consists of a cylinder‐forming polystyrene‐block‐polyferrocenylsilane (PS‐b‐PFS), with PFS as the minor block, and shows reversible redox properties. To prevent any spontaneous protein adsorption on either block, the electrolyte pH is selected to leave the ferritin negatively charged, and the protein concentration and solution ionic strength are carefully tuned. Selective adsorption of ferritin on the PFS domains of the self‐assembled thin films is then triggered in situ by applying a positive potential, simultaneously oxidizing the PFS and attracting the ferritin electrostatically.     

Modification of the Gallium‐Doped Zinc Oxide Surface with Self‐Assembled Monolayers of Phosphonic Acids: A Joint Theoretical and Experimental Study

Gallium‐doped zinc oxide (GZO) surfaces, both bare and modified with chemisorbed phosphonic acid (PA) molecules, are studied using a combination of density functional theory calculations and ultraviolet and X‐ray photoelectron spectroscopy measurements. Excellent agreement between theory and experiment is obtained, which leads to an understanding of: i) the core‐level binding energy shifts of the various oxygen atoms belonging to different surface sites and to the phosphonic acid molecules; ii) the GZO work‐function change upon surface modification, and; iii) the energy level alignments of the frontier molecular orbitals of the PA molecules with respect to the valence band edge and Fermi level of the GZO surface. Importantly, both density of states calculations and experimental measurements of the valence band features demonstrate an increase in the density of states and changes in the characteristics of the valence band edge of GZO upon deposition of the phosphonic acid molecules. The new valence band features are associated with contributions from surface oxygen atoms near a defect site on the oxide surface and from the highest occupied molecular orbitals of the phosphonic acid molecules.     

Solid‐State NMR Investigations of the Unusual Effects Resulting from the Nanoconfinement of Water within Amphiphilic Crosslinked Polymer Networks

Two types of solid‐state ¹⁹F NMR spectroscopy experiments are used to characterize phase‐separated hyperbranched fluoropolymer–poly(ethylene glycol) (HBFP–PEG) crosslinked networks. Mobile (soft) domains are detected in the HBFP phase by a rotor‐synchronized Hahn echo under magic‐angle spinning conditions, and rigid (hard) domains by a solid echo with no magic‐angle spinning. The mobility of chains is detected in the PEG phase by ¹H → ¹³C cross‐polarization transfers with ¹H spin‐lock filters with and without magic‐angle spinning. The interface between HBFP and PEG phases is detected by a third experiment, which utilized a ¹⁹F → ¹H–(spin diffusion)–¹H → ¹³C double transfer with ¹³C solid‐echo detection. The results of these experiments show that composition‐dependent PEG inclusions in the HBFP glass rigidify on hydration, consistent with an increase in macroscopic tensile strength.     

A New Type of Efficient CO2 Adsorbent with Improved Thermal Stability: Self‐Assembled Nanohybrids with Optimized Microporosity and Gas Adsorption Functions

A new type of efficient CO₂ absorbent with improved thermal stability is synthesized via self‐assembly between 2D inorganic nanosheets and two kinds of 0D inorganic nanoclusters. In these self‐assembled nanohybrids, the nanoclusters of CdO and Cr₂O₃ are commonly interstratified with layered titanate nanosheets, leading to the formation of highly microporous pillared structure with increased basicity of pore wall. The co‐pillaring of basic CdO with Cr₂O₃ is fairly effective at increasing a proportion of micropores and reactivity for CO₂ molecules and at improving the thermal stability of the resulting porous structure. Of prime importance is that the present inorganic‐pillared nanohybrids show highly efficient CO₂ adsorption capacity, which is much superior to those of many other absorbents and compatible to those of CO₂ adsorbing metal?organic framework (MOF) compounds. Taking into account an excellent thermal stability of the present nanohybrids, these materials are very promising CO₂ adsorbents usable at elevated temperature. This is the first example of efficient CO₂ adsorbent from pillared materials. The co‐pillaring of basic metal oxide nanoclusters employed in this study can provide a very powerful way of developing thermally stable CO₂ adsorbents from many known pillared systems.     

Supramolecular Surface Chemistry: Substrate‐Independent,Phosphate‐Driven Growth of Polyamine‐Based Multifunctional Thin Films

The ability to engineer surfaces at the supramolecular level by controlled integration of specific chemical units through substrate‐independent methodologies represents one of the new paradigms of contemporary materials science. Here, a method is reported to form multifunctional supramolecular coatings through simple dip‐coating of substrates in an aqueous solution of polyamine in the presence of phosphate anions. The chemical richness and versatility of polyamines are exploited as phosphate receptors to form thin functional films on a broad variety of substrates, ranging from metal to carbonaceous surfaces. It is shown that the simple derivatization of pendant amino groups of polyallylamine precursors with different chemical groups can endow films with predefined responsiveness or multiple functions—this translates into one‐pot and one‐step preparation of substrate‐adherent films displaying built‐in functions. It is believed that the flexibility, speed, and versatility with which this method provides such robust functional films make it very attractive for preparing samples of fundamental and technological interest.     

Strongly‐Coupled Freestanding Hybrid Films of Graphene and Layered Titanate Nanosheets: An Effective Way to Tailor the Physicochemical and Antibacterial Properties of Graphene Film

An effective way to tailor the physicochemical properties of graphene film is developed by combining colloidal suspensions of reduced graphene oxide (rG‐O) nanosheets and exfoliated layered titanate nanosheets for the fabrication of freestanding hybrid films comprised of stacked and overlapped nanosheets. A flow‐directed filtration of such mixed colloidal suspensions yields freestanding hybrid films comprised of strongly‐coupled rG‐O and titanate nanosheets with tunable chemical composition. This is the first example of highly flexible hybrid films composed of graphene and metal oxide nanosheets. The intimate incorporation of layered titanate nanosheets into the graphene film gives rise not only to an increase of mechanical strength but also to increased surface roughness, chemical stability, and hydrophilicity; thus, the physicochemical properties of the graphene film can be tuned by hybridization with inorganic nanosheets. These freestanding hybrid films of rG‐O‐layered titanate show unprecedentedly high antibacterial property, resulting in the complete sterilization of Escherichia coli O157:H7 (≈100%) in the very short time of 15 min. The antibacterial activity of the hybrid film is far superior to that of the pure graphene film, underscoring the beneficial effect of the layered metal oxide nanosheets in improving the functionality of the graphene film.     

Chain Extension of Stimuli‐Responsive Polymer Brushes: A General Strategy to Overcome the Drawbacks of the “Grafting‐To” Approach

Stimuli‐responsive polymer brushes are smart materials for the design of bio‐interactive and responsive interfaces. The “grafting‐to” approach is a convenient preparation procedure that allows the modification of surfaces with preformed and most notably well‐defined functionalized macromolecules. However, the shortcoming of this approach is an intrinsic limitation of the grafting density, which in turn affects the stimuli‐responsive properties of the brush system. Here, a general strategy to overcome this limitation and to simultaneously improve the switching behavior of a temperature‐responsive poly(N‐isopropylacrylamide) (PNiPAAm) brush is reported. A technically simple processing step is used in combination with the thermal azide–alkyne cycloaddition to perform the chain extension of alkyne‐functionalized PNiPAAm brushes with azide‐functionalized PNiPAAm molecules.     

Novel,Robust, and Versatile Bijels of Nitromethane,Ethanediol, and Colloidal Silica: Capsules,Sub‐Ten‐Micrometer Domains,and Mechanical Properties

Bicontinuous, interfacially jammed emulsion gels (bijels) are a class of soft solid materials in which interpenetrating domains of two immiscible fluids are stabilized by an interfacial colloidal monolayer. Such structures form through the arrest of the spinodal decomposition of an initially single‐phase liquid mixture containing a colloidal suspension. With the use of hexalmethyldisilazane, the wetting character of silica colloids, ranging in size and dye content, can be modified for fabricating a novel bijel system comprising the binary liquid ethanediol–nitromethane. Unlike the preceding water‐lutidine based system, this bijel is stable at room temperature and its fabrication and resultant manipulation are comparatively straightforward. The new system has facilitated three advancements: firstly, we use sub 100 nm silica particles to stabilize the first bijel made from low molecular weight liquids that has domains smaller than ten micrometers. Secondly, our new and robust bijel permits qualitative rheological work which reveals the bijel to be significantly elastic and self healing whilst its domains are able to break, reform and locally rearrange. Thirdly, we encapsulate the ethanediol–nitromethane bijel in Pickering drops to form novel particle‐stabilized bicontinuous multiple emulsions that we christen bijel capsules. These emulsions are stimuli responsive – they liberate their contained materials in response to changes in temperature and solvency, and hence they show potential for controlled release applications.