Alginate‐Boronic Acid: pH‐Triggered Bioinspired Glue for Hydrogel Assembly

The development of bioadhesives has become an emerging research field for tissue sealants, wound dressings, and hemostatic agents. However, assembling hydrogels using bioadhesive‐mediated attachment remains a challenging task. Significantly high water content (>90%) in hydrogels compared to that of biological tissues is the main cause of failure. Considering that hydrogels are primary testing scaffolds mimicking in vivo environments, developing strategies to assemble hydrogels that exhibit diverse properties is important. Self‐healing gels have been reported, but such gels often lack biocompatibility, and two gel pieces should be identical in chemistry for assembly, thus not allowing co‐existence of diverse biological environments. Herein, a mussel‐mimetic cis‐diol‐based adhesive, alginate‐boronic acid, that exhibits pH‐responsive curing from a viscoelastic solution to soft gels is developed. Associated mechanisms are that 1) polymeric diffusion occurs at interfaces utilizing intrinsic high water content; 2) the conjugated cis‐diols strongly interact/entangle with hydrogel chains; 3) curing processes begin by a slight increase in pH, resulting in robust attachment of diverse types of hydrogel building blocks for assembly. The findings obtained with alginate‐boronic acid glues suggest a rational design principle to attach diverse hydrogel building blocks to provide platforms mimicking in vivo environments.     

Diffused Phase Transition Boosts Thermal Stability of High‐Performance Lead‐Free Piezoelectrics

High piezoelectricity of (K,Na)NbO₃ (KNN) lead‐free materials benefits from a polymorphic phase transition (PPT) around room temperature, but its temperature sensitivity has been a bottleneck impeding their applications. It is found that good thermal stability can be achieved in CaZrO₃‐modified KNN lead‐free piezoceramics, in which the normalized strain d ₃₃* almost keeps constant from room temperature up to 140 °C. In situ synchrotron X‐ray diffraction experiments combined with permitivity measurements disclose the occurrence of a new phase transformation under an electrical field, which extends the transition range between tetragonal and orthorhombic phases. It is revealed that such an electrically enhanced diffused PPT contributed to the boosted thermal stability of KNN‐based lead‐free piezoceramics with high piezoelectricity. The present approach based on phase engineering should also be effective in endowing other lead‐free piezoelectrics with high piezoelectricity and good temperature stability.     

Insights into the In Vitro Formation of Apatite from Mg-Stabilized Amorphous Calcium Carbonate

A protein-free formation of bone-like apatite from amorphous precursors through ball-milling is reported. Mg²⁺ ions are crucial to achieve full amorphization of CaCO₃. Mg²⁺ incorporation generates defects which strongly retard a recrystallization of ball-milled Mg-doped amorphous calcium carbonate (BM-aMCC), which promotes the growth of osteoblastic and endothelial cells in simulated body fluid and has no effect on endothelial cell gene expression. Ex situ snapshots of the processes revealed the reaction mechanisms. For low Mg contents (<30%) a two phase system consisting of Mg-doped amorphous calcium carbonate (ACC) and calcite “impurities” was formed. For high (>40%) Mg²⁺ contents, BM-aMCC follows a different crystallization path via magnesian calcite and monohydrocalcite to aragonite. While pure ACC crystallizes rapidly to calcite in aqueous media, Mg-doped ACC forms in the presence of phosphate ions bone-like hydroxycarbonate apatite (dahllite), a carbonate apatite with carbonate substitution in both type A (OH⁻) and type B (PO₄³⁻) sites, which grows on calcite “impurities” via heterogeneous nucleation. This process produces an endotoxin-free material and makes BM-aMCC an excellent “ion storage buffer” that promotes cell growth by stimulating cell viability and metabolism with promising applications in the treatment of bone defects and bone degenerative diseases.     

New Insights into Tunable Volatility of Ionic Materials through Counter‐Ion Control

Recent development in the field of small molecular materials has led to great advances in the performance of vacuum‐evaporated organic light‐emitting diodes. However, as a significant class of phosphorescent emitters, ionic transition metal complexes are seldom sublimable due to the inherent ionic nature and low vapor pressure, restricting their applications in state‐of‐the‐art devices fabricated by vacuum evaporation deposition. Here a facile, feasible and versatile strategy is shown to tune the volatility of ionic transition metal complexes through counter‐ion control. By introducing counter‐ions with large steric hindrance and well‐dispersed charges, a series of evaporable ionic iridium complexes are developed, and efficient vapor‐processed devices with a high brightness, small efficiency roll‐off, and polychromic emission ranging from deep‐blue to red‐orange are achieved. Our findings unlock the utilization of ionic functional materials in vacuum‐evaporated devices, and may open new doors for modern electronic materials technology.     

Elucidating Mechanisms of Diffusion‐Based Calcium Carbonate Synthesis Leads to Controlled Mesocrystal Formation

Aggregation‐based crystal growth often gives rise to crystals with complex morphologies which cannot be generated via classical growth processes. Despite this, understanding of the mechanism is rather poor, particularly when organic additives or amorphous precursor phases are present. In this work, advantage is taken of the observation that aggregation‐based growth of calcium carbonate, and indeed many other minerals, is most often observed using diffusion‐based synthetic methods. By fully characterizing the widely used ammonia diffusion method (ADM)–which is currently used as a “black box”–the solution and supersaturation conditions which accompany CaCO₃ precipitation using this method are identified and insight is gained into the nucleation and growth processes which generate calcite mesocrystals. This reveals that the distinguishing feature of the ADM is that the initial nucleation burst consumes only a small quantity of the available ions, and the supersaturation then remains relatively constant, and well above the solubility of amorphous calcium carbonate (ACC), until the reaction is almost complete. New material is thus generated over the entire course of the precipitation, a feature which appears to be fundamental to the formation of complex, aggregation‐based morphologies. Finally, the importance of this understanding is demonstrated using the identified carbonate and supersaturation profiles to perfectly replicate CaCO₃ mesocrystals through slow addition of reagents to a bulk solution. This approach overcomes many of the inherent problems of the ADM by offering excellent reproducibility, enabling the synthesis of such CaCO₃ structures in large‐scale and continuous‐flow systems, and ultimately facilitating in situ studies of assembly‐based crystallization mechanisms.     

Insights into Nanoscale Electrochemical Reduction in a Memristive Oxide: the Role of Three‐Phase Boundaries

The nanoscale electro‐reduction in a memristive oxide is a highly relevant field for future non‐volatile memory materials. Photoemission electron microscopy is used to identify the conducting filaments and correlate them to structural features of the top electrode that indicate a critical role of the three phase boundary (electrode‐oxide‐ambient) for the electro‐chemical reduction. Based on simulated temperature profiles, the essential role of Joule heating through localized currents for electro‐reduction and morphology changes is demonstrated.     

Time‐Resolved Evolution of Short‐ and Long‐Range Order During the Transformation of Amorphous Calcium Carbonate to Calcite in the Sea Urchin Embryo

Use of amorphous precursors is a widespread strategy in biomineralization. In sea urchin embryos, controlled transformation of amorphous calcium carbonate (ACC) to calcite results in smoothly curving and branching single crystals. However, the mechanism of the disorder‐to‐order transformation remains poorly understood. Here, the use of strontium as a probe in X‐ray absorption spectroscopy (XAS) greatly facilitates investigation of the evolution of order. In pulse‐chase experiments, embryos incorporate Sr²⁺ from Sr‐enriched seawater into small volumes of the growing endoskeleton. During the chase, the Sr‐labeled mineral matures under physiological conditions. Based on Sr K‐edge spectra of cryo‐frozen whole embryos, it is proposed that the transformation occurs in three stages. The initially deposited calcium carbonate has short‐range order resembling synthetic hydrated ACC. Within 3 h, the short‐range order of calcite is established. Between 3 h and 24 h, the short‐range order does not change, while long‐range order increases. These results refute the notion that organisms imprint the local order of the final crystal on ACC. Furthermore, it is proposed that the intermediate is more similar to disordered calcite than to anhydrous ACC. Pulse‐chase experiments in conjunction with heavy element labeling have great potential to improve understanding of phase transformations during biomineralization.     

A Matter of Size and Stress: Understanding the First‐Order Transition in Materials for Solid‐State Refrigeration

Solid‐state magnetic refrigeration is a high‐potential, resource‐efficient cooling technology. However, many challenges involving materials science and engineering need to be overcome to achieve an industry‐ready technology. Caloric materials with a first‐order transition—associated with a large volume expansion or contraction—appear to be the most promising because of their large adiabatic temperature and isothermal entropy changes. In this study, using experiment and simulation, it is demonstrated with the most promising magnetocaloric candidate materials, La–Fe–Si, Mn–Fe–P–Si, and Ni–Mn–In–Co, that the characteristics of the first‐order transition are fundamentally determined by the evolution of mechanical stresses. This phenomenon is referred to as the stress‐coupling mechanism. Furthermore, its applicability goes beyond magnetocaloric materials, since it describes the first‐order transitions in multicaloric materials as well.     

Phase‐Engineered Synthesis of Ultrathin Hexagonal and Monoclinic GaTe Flakes and Phase Transition Study

GaTe is an important III–VI semiconductor with direct bandgap; thus, it holds great potential in the field of optoelectronics. Although it is known that GaTe can exist both in monoclinic and hexagonal phases, current studies are still exclusively restricted to the monoclinic phase of two dimensional (2D) GaTe owing to the difficulty in the fabrication of 2D hexagonal GaTe. Both monoclinic and hexagonal GaTe are demonstrated in this work, which can be selectively synthesized via a physical vapor deposition method, under precisely controlled growth temperatures. The pristine Raman and non‐linear optical properties of hexagonal GaTe has been systematically explored for the first time; moreover, a novel selected‐area phase transition from hexagonal to monoclinic of GeTe has been achieved via fs‐laser irradiation. This work may pave the way for widely use of 2D GaTe in various fields in future.     

Dual Phase‐Controlled Synthesis of Uniform Lanthanide‐Doped NaGdF4 Upconversion Nanocrystals Via an OA/Ionic Liquid Two‐Phase System for In Vivo Dual‐Modality Imaging

A novel OA/ionic liquid two‐phase system combining the merits of thermal decomposition method, the IL‐based strategy, and the two‐phase approach is introduced to synthesize high‐quality lanthanide‐doped NaGdF₄ upconversion nanocrystals with different crystal‐phases in OA‐phase and IL‐phase through a one‐step controllable reaction. Oil‐dispersible cubic‐phase NaGdF₄:Yb, Er (Ho, Tm) nanocrystals with ultra‐small size (～5 nm) and monodispersity are obtained in the OA phase of the two‐phase system via an IL‐based reaction. More importantly, water‐soluble hexagonal‐phase NaGdF₄:Yb, Er nanocrystals are obtained in the same system simply by adopting an extremely facile method to complete the dual phase‐transition (crystal‐phase transition and OA‐phase to IL‐phase transition) simultaneously. The synthesized lanthanide‐doped NaGdF₄ upconversion nanocrystals are effective for dual‐mode UCL imaging and CT imaging in vivo.     

Theoretical Insights into the Mechanism of Selective Nitrate-to-Ammonia Electroreduction on Single-Atom Catalysts

Selective nitrate-to-ammonia electrochemical conversion is an efficient pathway to solve the pollution of nitrate and an attractive strategy for low-temperature ammonia synthesis. However, current studies for nitrate electroreduction (NO₃RR) mainly focus on metal-based catalysts, which remains challenging because of the poor understanding of the catalytic mechanism. Herein, taking single transition metal atom supported on graphitic carbon nitrides (g-CN) as an example, the NO₃RR feasibility of single-atom catalysts (SACs) is first demonstrated by using density functional theory calculations. The results reveal that highly efficient NO₃RR toward NH₃ can be achieved on Ti/g-CN and Zr/g-CN with low limiting potentials of −0.39 and −0.41 V, respectively. Furthermore, the considerable energy barriers are observed during the formation of byproducts NO₂, NO, N₂O, and N₂ on Ti/g-CN and Zr/g-CN, guaranteeing their high selectivity. This work provides a new route for the application of SACs and paves the way to the development of NO₃RR.     

Novel Designed MnS-MoS2 Heterostructure for Fast and Stable Li/Na Storage:Insights into the Advanced Mechanism Attributed to Phase Engineering

Combining 2D MoS₂ with other transition metal sulfide is a promising strategy to elevate its electrochemical performances. Herein, heterostructures constructed using MnS nanoparticles embedded in MoS₂ nanosheets (denoted as MnS-MoS₂) are designed and synthesized as anode materials for lithium/sodium-ion batteries via a facile one-step hydrothermal method. Phase transition and built-in electric field brought by the heterostructure enhance the Li/Na ion intercalation kinetics, elevate the charge transport, and accommodate the volume expansion. The sequential phase transitions from 2H to 3R of MoS₂ and α to γ of MnS are revealed for the first time. As a result, the MnS-MoS₂ electrode delivers outstanding specific capacity (1246.2 mAh g⁻¹ at 1 A g⁻¹), excellent rate, and stable long-term cycling stability (397.2 mAh g⁻¹ maintained after 3000 cycles at 20 A g⁻¹) in Li-ion half-cells. Superior cycling and rate performance are also presented in sodium half-cells and Li/Na full cells, demonstrating a promising practical application of the MnS-MoS₂ electrode. This work is anticipated to afford an in-depth comprehension of the heterostructure contribution in energy storage and illuminate a new perspective to construct binary transition metal sulfide anodes.     

The Coral Protein CARP3 Acts from a Disordered Mineral Surface Film to Divert Aragonite Crystallization in Favor of Mg‐Calcite

Stony corals construct their aragonite skeleton by calcium carbonate precipitation, in a process recently suggested to be biologically controlled. Amorphous calcium carbonate and small amounts of calcite are also reported recently, however, their functional role is unknown. Coral acid‐rich proteins (CARPs) are extracted from the coral skeleton and are shown to be active in calcium carbonate precipitation in vitro. However, individual function of these proteins in coral mineralization is not known. Here, the regulatory activity of the aspartate‐rich CARP3 protein is examined. The whole protein and two peptides representing its acidic domain and its variable domain are used in CaCO₃ precipitation reactions from Mg‐rich solutions. The biomolecules alter crystallization pathways, promoting Mg‐calcite in place of aragonite, with the acidic peptide capable of eradicating aragonite formation. The activity of CARP3 and its representative peptides is exerted from disordered CaCO₃ mineral phases, coating the crystals formed, as shown by 2D ¹H–¹³C heteronuclear correlation nuclear magnetic resonance (NMR) measurements, localizing organic protons in atomic proximity to disordered carbonate carbons. The structures of the protein and individual domains as derived from NMR measurements and folding calculations and their amino acid compositions are discussed in the context of their observed activity and its implication to mineralization in hard corals.     

Polymorph Selectivity of Coccolith‐Associated Polysaccharides from Gephyrocapsa Oceanica on Calcium Carbonate Formation In Vitro

Coccolith‐associated polysaccharides (CAPs) are thought to be a key part of the biomineralization process in coccolithophores; however, their role is not fully understood. Two different systems that promote different polymorphs of calcium carbonate are used to show the effect of CAPs on nucleation and polymorph selection in vitro. Using a combination of time‐resolved cryo‐transmission electron microscopy and scanning electron microscopy, the mechanisms of calcite nucleation and growth in the presence of the intracrystalline fraction are examined containing CAPs extracted from coccoliths from Gephyrocapsa oceanica and Emiliania huxleyi, two closely related coccolithophore species. The CAPs extracted from G. oceanica are shown to promote calcite nucleation in vitro, even under conditions favoring the kinetic products of calcium carbonate, vaterite, and aragonite. This is not the case with CAPs extracted from E. huxleyi, suggesting that the functional role of CAPs in vivo may be different between the two species. Additionally, high‐resolution synchrotron powder X‐ray diffraction has revealed that the polysaccharide is located between grain boundaries of both calcite produced in the presence of the CAPs in vitro and biogenic calcite, rather than within the crystal lattice.     

Room‐Temperature Phase Demixing in Bulk Heterojunction Layers of Solution‐Processed Organic Photodetectors: the Effect of Active Layer Ageing on the Device Electro‐optical Properties

Herein, we address the reduction in the external quantum efficiency (EQE) of solution‐processed organic photodetectors caused by the room temperature phase demixing of components in the composite material of the photoactive layer. The reduction takes place under ambient conditions and after the completion of device fabrication. As a model system, we study photoactive blend films that consist of the electron acceptor N,N’‐bis(alkyl)‐3,4,9,10‐perylene tetracarboxylic diimide) (PDI) and the electron donor polymer poly(9,9’‐dioctylfluorene‐co‐benzothiadiazole) (F8BT). The ambient ageing of these photo­active layers is a consequence of the PDI component segregation; however, the final PDI domain size remains smaller than the resolution limit of optical microscopy. We find that the photophysical properties of the aged F8BT:PDI layer and the EQE of the aged device are significantly altered. The fabrication of F8BT:PDI layers from solvents of increasing boiling point allows for the spectroscopic monitoring of the ageing‐induced phase segregation (a‐PSG) process. For each solvent used, the extent of a‐PSG is correlated with the PDI dispersion in the F8BT matrix as received immediately after layer deposition. The tendency for room temperature phase demixing becomes stronger as PDI is more finely dispersed in the freshly spun F8BT:PDI layer. The evolution of the room temperature phase segregation of PDI has a negative impact on the photophysical processes that are essential for charge photogeneration in the F8BT:PDI photoactive layer.     

Structure and Properties of Nanocomposites Formed by the Occlusion of Block Copolymer Worms and Vesicles Within Calcite Crystals

This article describes an experimentally versatile strategy for producing inorganic/organic nanocomposites, with control over the microstructure at the nano‐ and mesoscales. Taking inspiration from biominerals, CaCO₃ is coprecipitated with anionic diblock copolymer worms or vesicles to produce single crystals of calcite occluding a high density of the organic component. This approach can also be extended to generate complex structures in which the crystals are internally patterned with nano‐objects of differing morphologies. Extensive characterization of the nanocomposite crystals using high resolution synchrotron powder X‐ray diffraction and vibrational spectroscopy demonstrates how the occlusions affect the short and long‐range order of the crystal lattice. By comparison with nanocomposite crystals containing latex particles and copolymer micelles, it is shown that the effect of these occlusions on the crystal lattice is dominated by the interface between the inorganic crystal and the organic nano‐objects, rather than the occlusion size. This is supported by in situ atomic force microscopy studies of worm occlusion in calcite, which reveal flattening of the copolymer worms on the crystal surface, followed by burial and void formation. Finally, the mechanical properties of the nanocomposite crystals are determined using nanoindentation techniques, which reveal that they have hardnesses approaching those of biogenic calcites.     

Size‐Dependent Staging and Phase Transition in LiFePO4/FePO4

The LiFePO₄/FePO₄ phase transition process is remarkable in terms of its excellent reversibility, making this redox system extremely promising for high rate lithium storage. The recent observation of ordering effects (Li_0.5FePO₄) during the phase transition challenges the traditional two phase models. In this work, the phenomenon of staging for LiFePO₄ for different sizes (70 nm and 50 nm) by high resolution aberration corrected annular bright electron microscopy is detected, investigated, and discussed along with previous results on larger crystals. In the small crystals, staging is found throughout with a decrease of order from center to the surface. For the larger crystal, a staging phase occurs constituting the interfacial zone (width around 15 nm) between LiFePO₄ and FePO₄. A comparison is made to recent experiments on even larger crystals showing such an interphase of smaller extent (around 2 nm). Thus it appears that these zones narrow with increasing size. These findings are discussed in the light of phase transition thermodynamics and kinetics. In particular, the possibility is discussed that the staging interphase may constitute a low energy solution to the LiFePO₄/FePO₄ contact.     

Suppressed light-induced phase transition of CsPbBr2I:Strategies,progress and applications in the photovoltaic field

The rapid rise in the power conversion efficiency (PCE) of CsPbBr2I-based perovskite solar cells (PSCs),from 4.7％ in 2016 to 11.08％ in 2020,render it a promising material for use in photovoltaic devices.However,the phase stability and cur-rent hysteresis caused by photo-induced phase segregation in CsPbBr2I represent major obstacles to further improvements in the PCE for such devices.In this review,we describe the basic structure and optical properties of CsPbBr2I,and systematically elaborate on the mechanism of the phase transition.We then discuss the strategies in progress to suppress phase transition in CsPbBr2I,and their potential application in the photovoltaic field.Finally,challenges and application prospects for CsPbBr2I PSCs are summarized in the final section of this article.     

Wavelength‐Emission Tuning of ZnO Nanowire‐Based Light‐Emitting Diodes by Cu Doping: Experimental and Computational Insights

The band‐gap engineering of doped ZnO nanowires is of the utmost importance for tunable light‐emitting‐diode (LED) applications. A combined experimental and density‐functional theory (DFT) study of ZnO doping by copper (Zn²⁺ substitution by Cu²⁺) is presented. ZnO:Cu nanowires are epitaxially grown on magnesium‐doped p‐GaN by electrochemical deposition. The heterojunction is integrated into a LED structure. Efficient charge injection and radiative recombination in the Cu‐doped ZnO nanowires are demonstrated. In the devices, the nanowires act as the light emitters. At room temperature, Cu‐doped ZnO LEDs exhibit low‐threshold emission voltage and electroluminescence emission shifted from the ultraviolet to violet–blue spectral region compared to pure ZnO LEDs. The emission wavelength can be tuned by changing the copper content in the ZnO nanoemitters. The shift is explained by DFT calculations with the appearance of copper d states in the ZnO band‐gap and subsequent gap reduction upon doping. The presented data demonstrate the possibility to tune the band‐gap of ZnO nanowire emitters by copper doping for nano‐LEDs.