In this work, we present a versatile surface engineering strategy by the combination of mussel adhesive peptide mimicking and bioorthogonal click chemistry. The main idea reflected in this work derived from a novel mussel-inspired peptide mimic with a bioclickable azide group (i.e., DOPA₄-azide). Similar to the adhesion mechanism of the mussel foot protein (i.e., covalent/noncovalent comediated surface adhesion), the bioinspired and bioclickable peptide mimic DOPA₄-azide enables stable binding on a broad range of materials, such as metallic, inorganic, and organic polymer substrates. In addition to the material universality, the azide residues of DOPA₄-azide are also capable of a specific conjugation of dibenzylcyclooctyne- (DBCO-) modified bioactive ligands through bioorthogonal click reaction in a second step. To demonstrate the applicability of this strategy for diversified biofunctionalization, we bioorthogonally conjugated several typical bioactive molecules with DBCO functionalization on different substrates to fabricate functional surfaces which fulfil essential requirements of biomedically used implants. For instance, antibiofouling, antibacterial, and antithrombogenic properties could be easily applied to the relevant biomaterial surfaces, by grafting antifouling polymer, antibacterial peptide, and NO-generating catalyst, respectively. Overall, the novel surface bioengineering strategy has shown broad applicability for both the types of substrate materials and the expected biofunctionalities. Conceivably, the “clean” molecular modification of bioorthogonal chemistry and the universality of mussel-inspired surface adhesion may synergically provide a versatile surface bioengineering strategy for a wide range of biomedical materials.

The mechanical properties of tissues are pivotal for morphogenesis and disease progression. Recent approaches have enabled measurements of the spatial distributions of viscoelastic properties among embryonic and pathological model systems and facilitated the generation of important hypotheses such as durotaxis and tissue-scale phase transition. There likely are many unexpected aspects of embryo biomechanics we have yet to discover which will change our views of mechanisms that govern development and disease. One area in the blind spot of even the most recent approaches to measuring tissue stiffness is the potentially anisotropic nature of that parameter. Here, we report a magnetic micromanipulation device that generates a uniform magnetic field gradient within a large workspace and permits measurement of the variation of tissue stiffness along three orthogonal axes. By applying the device to the organ-stage mouse embryo, we identify spatially heterogenous and directionally anisotropic stiffness within the mandibular arch. Those properties correspond to the domain of expression and the angular distribution of fibronectin and have potential implications for mechanisms that orient collective cell movements and shape tissues during development. Assessment of anisotropic properties extends the repertoire of current methods and will enable the generation and testing of hypotheses.

Surface-enhanced Raman spectroscopy (SERS) is a powerful sensing technique capable of capturing ultrasensitive fingerprint signal of analytes with extremely low concentration. However, conventional SERS probes are passive nanoparticles which are usually massively applied for biochemical sensing, lacking controllability and adaptability for precise and targeted sensing at a small scale. Herein, we report a “rod-like” magnetic nanomotor-based SERS probe (MNM-SP) that integrates a mobile and controllable platform of micro-/nanomotors with a SERS sensing technique. The “rod-like” structure is prepared by coating a thin layer of silica onto the self-assembled magnetic nanoparticles. Afterwards, SERS hotspots of silver nanoparticles (AgNPs) are decorated as detecting nanoprobes. The MNM-SPs can be navigated on-demand to avoid obstacles and target sensing sites by the guidance of an external gradient magnetic field. Through applying a rotating magnetic field, the MNM-SPs can actively rotate to efficiently stir and mix surrounding fluid and thus contact with analytes quickly for SERS sensing. Innovatively, we demonstrate the self-cleaning capability of the MNM-SPs which can be used to overcome the contamination problem of traditional single-use SERS probes. Furthermore, the MNM-SPs could precisely approach the targeted single cell and then enter into the cell by endocytosis. It is worth mentioning that by the effective mixing of intracellular biocomponents, much more informative Raman signals with improved signal-to-noise ratio can be captured after active rotation. Therefore, the demonstrated magnetically activated MNM-SPs that are endowed with SERS sensing capability pave way to the future development of smart sensing probes with maneuverability for biochemical analysis at the micro-/nanoscale.

Elevation of operational temperatures of polymer electrolyte membrane fuel cells (PEMFCs) has been demonstrated with phosphoric acid-doped polybenzimidazole (PA/PBI) membranes. The technical perspective of the technology is simplified construction and operation with possible integration with, e.g., methanol reformers. Toward this target, significant efforts have been made to develop acid-base polymer membranes, inorganic proton conductors, and organic-inorganic composite materials. This report is devoted to updating the recent progress of the development particularly of acid-doped PBI, phosphate-based solid inorganic proton conductors, and their composite electrolytes. Long-term stability of PBI membranes has been well documented, however, at typical temperatures of 160°C. Inorganic proton-conducting materials, e.g., alkali metal dihydrogen phosphates, heteropolyacids, tetravalent metal pyrophosphates, and phosphosilicates, exhibit significant proton conductivity at temperatures of up to 300°C but have so far found limited applications in the form of thin films. Composite membranes of PBI and phosphates, particularly in situ formed phosphosilicates in the polymer matrix, showed exceptionally stable conductivity at temperatures well above 200°C. Fuel cell tests at up to 260°C are reported operational with good tolerance of up to 16% CO in hydrogen, fast kinetics for direct methanol oxidation, and feasibility of nonprecious metal catalysts. The prospect and future exploration of new proton conductors based on phosphate immobilization and fuel cell technologies at temperatures above 200°C are discussed.

Metal-organic frameworks are an emerging and fascinating category of porous solids that can be self-assembled with metal-based cations linked by organic molecules. The unique features of MOFs in porosity (or surface areas), together with their diversity for chemical components and architectures, make MOFs attractive candidates in many applications. MOF membranes represent a long-term endeavor to convert MOF crystals in the lab to potentially industry-available commodities, which, as a promising alternative to distillation, provide a bright future for energy-efficient separation technologies closely related with chemicals, the environment, and energy. The membrane reactor shows a typical intensified process strategy by combining the catalytic reaction with the membrane separation in one unit. This review highlights the recent process of MOF-based membranes and the importance of MOF-based membrane reactors in relative intensified chemical processes.

Microneedles have attracted increasing interest among various medical fields due to their painless, noninvasive, and efficient way of drug delivery. However, practical applications of these microneedles in different epidermal locations and environments are still restricted by their low adhesion and poor antimicrobial activity. Here, inspired by the antibacterial strategy of Paenibacillus polymyxa and adhesion mechanisms of mussel byssi and octopus tentacles, we develop hierarchical microneedles with multifunctional adhesive and antibacterial abilities. With polydopamine hydrogel as the microneedle base and a loop of suction-cup-structured concave chambers encircling each microneedle, the generated microneedles can fit the skin well; keep strong adhesion in dry, moist, and wet environments; and realize self-repair after being split into two parts. Besides, as polymyxin is loaded into both the hydrogel tips and the polydopamine base, the microneedles are endowed with excellent ability to resist common bacteria during storage and usage. We have demonstrated that these microneedles not only showed excellent adhesion when applied to knuckles and ideal antibacterial activity but also performed well in drug-sustained release and treatment for the osteoarthritis rat model. These results indicate that bioinspired multifunctional microneedles will break through the limitation of traditional methods and be ideal candidates for versatile transdermal drug delivery systems.

Solar-driven N₂ fixation using a photocatalyst in water presents a promising alternative to the traditional Haber-Bosch process in terms of both energy efficiency and environmental concern. At present, the product of solar N₂ fixation is either NH₄⁺ or NO₃^-. Few reports described the simultaneous formation of ammonia (NH₄⁺) and nitrate (NO₃^-) by a photocatalytic reaction and the related mechanism. In this work, we report a strategy to photocatalytically fix nitrogen through simultaneous reduction and oxidation to produce NH₄⁺ and NO₃^- by W₁₈O₄₉ nanowires in pure water. The underlying mechanism of wavelength-dependent N₂ fixation in the presence of surface defects is proposed, with an emphasis on oxygen vacancies that not only facilitate the activation and dissociation of N₂ but also improve light absorption and the separation of the photoexcited carriers. Both NH₄⁺ and NO₃^- can be produced in pure water under a simulated solar light and even till the wavelength reaching 730 nm. The maximum quantum efficiency reaches 9% at 365 nm. Theoretical calculation reveals that disproportionation reaction of the N₂ molecule is more energetically favorable than either reduction or oxidation alone. It is worth noting that the molar fraction of NH₄⁺ in the total product (NH₄⁺ plus NO₃^-) shows an inverted volcano shape from 365 nm to 730 nm. The increased fraction of NO₃^- from 365 nm to around 427 nm results from the competition between the oxygen evolution reaction (OER) at W sites without oxygen vacancies and the N₂ oxidation reaction (NOR) at oxygen vacancy sites, which is driven by the intrinsically delocalized photoexcited holes. From 427 nm to 730 nm, NOR is energetically restricted due to its higher equilibrium potential than that of OER, accompanied by the localized photoexcited holes on oxygen vacancies. Full disproportionation of N₂ is achieved within a range of wavelength from ~427 nm to ~515 nm. This work presents a rational strategy to efficiently utilize the photoexcited carriers and optimize the photocatalyst for practical nitrogen fixation.

A high-performance anion exchange membrane (AEM) is critical for the development of alkaline fuel cell. In this work, AEMs with an interpenetrating polymer network (IPN) are synthesized. An electron microscope clearly reveals a highly efficient “ion channel” network, which is constructed with a small amount of cation exchange groups. This specially designed ion channel leads to extraordinary hydroxide conductivity (e.g., 257.8 mS cm^-1 at 80 °C) of IPN AEMs at moderate ion exchange capacity (\text{IEC}=1.75\text{mmol}{\text{g}}^{-1}), as well as excellent long-term alkaline stability at harsh condition which showed that 81% of original conductivity can be retained after a long time for 1248 hours. Moreover, a remarkable peak power density of 1.20 W cm^-2 (0.1 MPa backpressure) with nonprecious metal (FeNx-CNTs) as oxygen reduction reaction (ORR) catalyst in a fuel cell test was achieved. This work offers a general strategy to prepare high-performance AEMs based on IPN structure design.

We develop a unified view of topological phase transitions (TPTs) in solids by revising the classical band theory with the inclusion of topology. Reevaluating the band evolution from an “atomic crystal” (a normal insulator (NI)) to a solid crystal, such as a semiconductor, we demonstrate that there exists ubiquitously an intermediate phase of topological insulator (TI), whose critical transition point displays a linear scaling between electron hopping potential and average bond length, underlined by deformation-potential theory. The validity of the scaling relation is verified in various two-dimensional (2D) lattices regardless of lattice symmetry, periodicity, and form of electron hoppings, based on a generic tight-binding model. Significantly, this linear scaling is shown to set an upper bound for the degree of structural disorder to destroy the topological order in a crystalline solid, as exemplified by formation of vacancies and thermal disorder. Our work formulates a simple framework for understanding the physical nature of TPTs with significant implications in practical applications of topological materials.

Three-dimensional laser writing inside silicon remains today inaccessible with the shortest infrared light pulses unless complex schemes are used to circumvent screening propagation nonlinearities. Here, we explore a new approach irradiating silicon with trains of femtosecond laser pulses at repetition rates up to 5.6 THz that is order of magnitude higher than any source used for laser processing so far. This extremely high repetition rate is faster than laser energy dissipation from microvolume inside silicon, thus enabling unique capabilities for pulse-to-pulse accumulation of free carriers generated by nonlinear ionization, as well as progressive thermal bandgap closure before any diffusion process comes into play. By space-resolved measurements of energy delivery inside silicon, we evidence changes in the interplay between detrimental nonlinearities and accumulation-based effects. This leads to a net increase on the level of space-time energy localization. The improvement is also supported by experiments demonstrating high performance for 3D laser writing inside silicon. In comparison to repeated single pulses, irradiation with trains of only four-picosecond pulses with the same total energy leads to an apparent decrease of the energy threshold for modification and drastic improvements on the repeatability, uniformity, and symmetricity of the produced features. The unique benefits of THz bursts can provide a new route to meet the challenge of 3D inscription inside narrow bandgap materials.