Crosslinking ionic oligomers as conformable precursors to calcium carbonate.

Inorganic materials have essential roles in society, including in building construction, optical devices, mechanical engineering and as biomaterials1-4. However, the manufacture of inorganic materials is limited by classical crystallization5, which often produces powders rather than monoliths with continuous structures. Several precursors that enable non-classical crystallization-such as pre-nucleation clusters6-8, dense liquid droplets9,10, polymer-induced liquid precursor phases11-13 and nanoparticles14-have been proposed to improve the construction of inorganic materials, but the large-scale application of these precursors in monolith preparations is limited by availability and by practical considerations. Inspired by the processability of polymeric materials that can be manufactured by crosslinking monomers or oligomers15, here we demonstrate the construction of continuously structured inorganic materials by crosslinking ionic oligomers. Using calcium carbonate as a model, we obtain a large quantity of its oligomers (CaCO3)n with controllable molecular weights, in which triethylamine acts as a capping agent to stabilize the oligomers. The removal of triethylamine initiates crosslinking of the (CaCO3)n oligomers, and thus the rapid construction of pure monolithic calcium carbonate and even single crystals with a continuous internal structure. The fluid-like behaviour of the oligomer precursor enables it to be readily processed or moulded into shapes, even for materials with structural complexity and variable morphologies. The material construction strategy that we introduce here arises from a fusion of classic inorganic and polymer chemistry, and uses the same cross-linking process for the manufacture the materials.

Precise Control of Metal Active Sites of Metal-Organic Framework Nanozymes for Achieving Excellent Enzyme-Like Activity and Efficient Pancreatitis Therapy.

Acute pancreatitis (AP) is a potentially life-threatening inflammatory disease that can lead to the development of systemic inflammatory response syndrome and its progression to severe acute pancreatitis. Hence, there is an urgent need for the rational design of highly efficient antioxidants to treat AP. Herein, an optimized Cu-based metal-organic framework (MOF) nanozyme with exceptional antioxidant activity is introduced, designed to effectively alleviate AP, by engineering the metal coordination centers in MN2Cl2 (M = Co, Ni, Cu). Specifically, the Cu MOF, which benefits from a Cu active center similar to that of natural superoxide dismutase (SOD), exhibited at least four times higher SOD-like activity than the Ni/Co MOF. Theoretical analyses further demonstrate that the CuN2Cl2 site not only has a moderate adsorption effect on the substrate molecule •OOH but also reduces the dissociation energy of the product H2 O2 . Additionally, the Cu MOF nanozyme possesses the excellent catalase-like activity and •OH removal ability. Consequently, the Cu MOF with broad-spectrum antioxidant activity can efficiently scavenge reactive oxygen species to alleviate arginine-induced AP. More importantly, it can also mitigate apoptosis and necrosis of acinar cells by activating the PINK1/PARK2-mediated mitophagy pathway. This study highlights the distinctive functions of tunable MOF nanozymes and their potential bio-applications.

Modular Design for Proteins Assembling into Antifouling Coatings: Case of Gold Surfaces.

We analyze modularity for a B-M-E triblock protein designed to self-assemble into antifouling coatings. Previously, we have shown that the design performs well on silica surfaces when B is taken to be a silica-binding peptide, M is a thermostable trimer domain, and E is the uncharged elastin-like polypeptide (ELP), E = (GSGVP)40. Here, we demonstrate that we can modulate the nature of the substrate on which the coatings form by choosing different solid-binding peptides as binding domain B and that we can modulate antifouling properties by choosing a different hydrophilic block E. Specifically, to arrive at antifouling coatings for gold surfaces, as binding block B we use the gold-binding peptide GBP1 (with the sequence MHGKTQATSGTIQS), while we replace the antifouling blocks E by zwitterionic ELPs of different lengths, EZn = (GDGVP-GKGVP)n/2, with n = 20, 40, or 80. We find that even the B-M-E proteins with the shortest E blocks make coatings on gold surfaces with excellent antifouling against 1% human serum (HS) and reasonable antifouling against 10% HS. This suggests that the B-M-E triblock protein can be easily adapted to form antifouling coatings on any substrate for which solid-binding peptide sequences are available.

Selective Chiral Recognition between Amino Acids and Growing Gypsum Crystals.

In nature, selective chiral interactions between biomolecules and minerals provide insight into the mysterious origin of homochirality. Here, we show growing gypsum crystals in a nonequilibrium state can recognize chiral enantiomers of amino acids. The chiral selection for amino acids with different functional groups by growing minerals are distinct. For 11 amino acids, the d-isomer slows dynamic gypsum growth more than the l-isomer, whereas for another 7 amino acids, the opposite was observed. These differences in chiral recognition are attributed to the different stereochemical matching between the chiral amino acids and the dynamic steps of growing gypsum. These stereoselective interactions between amino acid enantiomers and dynamic growing crystals can be applied toward the fabrication of gypsum cements to regulate their structure and mechanical properties. These findings provide insight into understanding the mechanism of the origin of homochirality in nature and suggest a pathway for constructing advanced functional materials.

Thermal conductivity of fivefold twinned silicon-germanium heteronanowires.

The thermal transport properties of five-fold twinned (5FT) germanium-silicon (Ge-Si) heteronanowires (h-NWs) with varying cross-sectional areas, germanium (Ge) domain ratios and heterostructural patterns are investigated using homogeneous nonequilibrium molecular dynamics (HNEMD) simulations. The results demonstrate a distinctive behavior in the thermal conductivity (κ) of 5FT-NWs, characterized by a "flipped" trend at a critical cross-sectional area. This behavior is attributed to the hydrodynamic phonon flow, arising from the normal three-phonon scattering process in the low-frequency region. In addition, the composition ratio of 5FT-NWs has a significant impact on reducing the κ of 5FT-NWs and suppressing the hydrodynamic effect. Intriguingly, as the homogeneous element domains are separated, stronger phonon hydrodynamic flows are observed in comparison to the adjacent homogeneous element domains. By analyzing various phonon properties, including phonon dispersion, three-phonon scattering rate, and phonon mean free path, critical insights into the origin of the differential κ in different 5FT-NW structures are provided. The findings deepen the understanding of the thermal transport properties of nanomaterials and hold implications for the design and development of nanoelectronics and thermoelectric devices.

Shape-preserving amorphous-to-crystalline transformation of CaCO3 revealed by in situ TEM.

Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape-preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals.

Consistency and Discrepancy between Visibility and PM2.5 Measurements: Potential Application of Visibility Observation to Air Quality Study.

High-quality measurements of air quality are the highest priority for understanding widespread air pollution. Visibility has been widely suggested to be a good alternative to PM2.5 concentration as a measure. In this study, the similarities and differences between visibility and PM2.5 measurements in China are checked and the results reveal the potential application of visibility observation to the study of air quality. Based on the quality-controlled PM2.5 and visibility data from 2016 to 2018, the nonparametric Spearman correlation coefficient (ρ) values between stations for PM2.5 and visibility-derived surface extinction coefficient (bext) decrease as the station distance (R) increases. Some relatively low ρ values (<0.4) occur in regions characterized by the lowest (background) levels of PM2.5 and bext values, for example, the Tibetan and Yungui Plateau. The relatively lower ρ for bext compared to PM2.5 is probably caused by the predefined maximum threshold of visibility measurements (generally 30 km). A significant correlation between PM2.5 and bext is derived in most stations and relatively larger ρ values are evident in eastern China (Northeast China excluded) and in winter (the national median ρ is 0.67). The abrupt changes in specific mass extinction efficiency (αext) imply a potentially large influence of alternation of visibility sensors or recalibrations on visibility measurements. The bext data are thereafter corrected by comparison to the reference measurements at the adjacent stations, which leads to a three-year quality assured of visibility and bext datasets.

Role of mechanical deformation in the thermal transport of sI-type methane hydrate.

Natural gas hydrates (NGHs) are rising as an unconventional energy resource. The fundamental thermal characteristics of NGHs are of importance for natural gas exploitation from permafrost and oceanic sediments that are geomechanically deformed. Here, utilizing classic molecular dynamics simulations with all-atom (AA) and coarse-grained (CG) models of the methane guest molecule, the effects of mechanical strain on the thermal conductivity of sI-type methane hydrate are for the first time examined. Upon triaxial tension and compression, methane hydrate exhibits strong asymmetry in the stress responses. As the triaxial loads go from compression to tension, a reduction trend in the thermal conductivity is revealed for methane hydrate with both AA and CG models of methane, within a maximum reduction of over 44%. This reduction is because triaxial strain from compression to tension softens the phonon modes. Interestingly, there is a sudden rise in thermal conductivity at critical triaxial strain of 0.06, originating from that, at which, the phonon modes are hardened and the peaks of radial distribution functions are shifted back. This study provides important information on the thermal conductivity of methane hydrate, which is helpful for the practical production of natural gas from geo-deformed NGH-bearing sediments via a heating technique as well as evaluating their stability.

Spontaneous Adsorption of Graphene Oxide on Multiple Polymeric Surfaces.

The controllable integration of low-dimensional nanomaterials on solid surfaces is pivotal for the fabrication of next-generation miniaturized electronic and optoelectronic devices. For instance, organization of two-dimensional (2D) nanomaterials on polymeric surfaces paves the way for the development of flexible electronics for applications in wearable devices. Nevertheless, the understanding of the molecular interactions between these nanomaterials and the polymeric surfaces remains limited, which impedes the rational design of 2D nanomaterial-based functional coatings. In the current work, we report that graphene oxide (GO) nanosheets, in their dispersion phase, can be adsorbed on multiple polymeric surfaces in a spontaneous manner. Both experimental findings and simulational results indicate that the main driving force is hydrogen bonding interactions, although other molecular interactions such as polarity and dispersion ones contribute to the adsorption as well. The relatively high hydrogen bonding interactions cause not only increased GO surface coverage but also enhanced GO adsorption kinetics on polymeric surfaces. The adsorbed GO layers are robust, which can be explained by the large aspect ratios of GO nanosheets and the presence of multiple spots for molecular interactions. As a proof of concept, GO-covered polymethyl methacrylate effectively decreases surface static charges when compared with its pristine counterpart. The integration of the GO constituents turns many inert polymeric substrates into multifunctional hybrids, and the functional groups on GO can be used further to bridge with additional functional materials for the development of high-performance electronic devices.

Mechanical ductile detwinning in CH3NH3PbI3 perovskite.

Twin boundaries (TBs) were identified to show conflicting positive/negative effects on the physical properties of CH3NH3PbI3 perovskites, but their effects on the mechanical properties are still unclear. Herein, the tensile characteristics of a variety of TB-dominated bicrystalline CH3NH3PbI3 perovskites are explored using molecular simulations. The results show that TB-containing CH3NH3PbI3 perovskites can be classified into four types based on their tensile ductile detwinning characteristics. Type I is characterized by smooth loading flow stress-strain responses, originating from relatively uniform stress distribution induced gradual amorphization in the TB region. Types II and III are represented by a sudden drop in loading stresses but then distinct ductile flow stress-strain curves, resulting from limited and large-area amorphizations of TB-involved structures, respectively. However, Type IV is highlighted by double apparent peaks in the loading curve, followed by a ductile flow response, originating from the stress-concentration of localization-to-globalization in the TB region, as well as amorphization. This study provides critical insights into the mechanical characteristics of CH3NH3PbI3 perovskites and indicates that TB engineering is a promising strategy to design mechanically robust hybrid organic-inorganic perovskite-based device systems.

Classical nucleation theory of ice nucleation: Second-order corrections to thermodynamic parameters.

Accurately estimating the nucleation rate is crucial in studying ice nucleation and ice-promoting and anti-freeze strategies. In classical nucleation theory, estimates of the ice nucleation rate are very sensitive to thermodynamic parameters, such as the chemical potential difference between water and ice Δµ and the ice-water interfacial free energy γ. However, even today, there are still many contradictions and approximations when estimating these thermodynamic parameters, introducing a large uncertainty in any estimate of the ice nucleation rate. Starting from basic concepts for a general solid-liquid crystallization system, we expand the Gibbs-Thomson equation to second order and derive second-order analytical formulas for Δµ, γ, and the nucleation barrier ΔG*, which are used in molecular dynamics simulations. These formulas describe well the temperature dependence of these thermodynamic parameters. This may be a new method of estimating Δµ, γ, and ΔG*.

Control of ice nucleation: freezing and antifreeze strategies.

Water freezing remains a perennial topic of great relevance to many important aspects of our lives; from the climate to human society and from economics to medicine, frozen water profoundly influences our living environment and life activities. There have been numerous publications on water freezing; however, confusion regarding the process of freezing remains. In this review, we mainly focused on the nucleation aspects of water freezing; in particular, we focused on the effect of the surface morphology and nanostructure of foreign bodies. This review covers the recent progress in ice nucleation and anti-freezing strategies within the framework of nucleation principles. In this regard, we first summarize the crystal nucleation theories. Due to high interfacial energy, ice crystallization is primarily controlled by heterogeneous nucleation events, because the homogeneous nucleation barrier of ice is extremely high. In addition to the interfacial energy, the interfacial morphology or nanostructure of foreign bodies plays a diverse role under different supercooling regimes due to the Gibbs-Thomson effect. This effect gives rise to the inverse homogeneous-like nucleation phenomenon, in which foreign bodies have little influence on the nucleation barrier. This ensures the accurate measurement of the nucleation barrier, critical size, and water-ice interfacial energy, in agreement with the latest studies based on a microemulsions approach, metadynamics, the mW model, etc. As a consequence, anti-freezing strategies can be implemented by reducing the nucleation rate through restriction of the contact area of the water/substrate interface, by increasing the heterogeneous nucleation barrier through modification of the interfacial properties of foreign particles, including the interfacial structure and the interaction between the water and foreign particles and by kink kinetics. Within this context, the anti-freezing mechanism of superhydrophobic substrates was reviewed. Therefore, it follows that by significantly reducing the contact area between the water and substrate, superhydrophobic materials can effectively reduce the heterogeneous nucleation rate. We hope that this review will provide a unified picture and guidance for future work on water freezing.

Grain-Size-Controlled Mechanical Properties of Polycrystalline Monolayer MoS2.

Pristine monocrystalline molybdenum disulfide (MoS2) possesses high mechanical strength comparable to that of stainless steel. Large-area chemical-vapor-deposited monolayer MoS2 tends to be polycrystalline with intrinsic grain boundaries (GBs). Topological defects and grain size skillfully alter its physical properties in a variety of materials; however, the polycrystallinity and its role played in the mechanical performance of the emerging single-layer MoS2 remain largely unknown. Here, using large-scale atomistic simulations, GB structures and mechanical characteristics of realistic single-layered polycrystalline MoS2 of varying grain size prepared by confinement-quenched method are investigated. Depending on misorientation angle, structural energetics of polar-GBs in polycrystals favor diverse dislocation cores, consistent with experimental observations. Polycrystals exhibit grain-size-dependent thermally induced global out-of-plane deformation, although defective GBs in MoS2 show planar structures that are in contrast to the graphene. Tensile tests show that presence of cohesive GBs pronouncedly deteriorates the in-plane mechanical properties of MoS2. Both stiffness and strength follow an inverse pseudo Hall-Petch relation to grain size, which is shown to be governed by the weakest link mechanism. Under uniaxial tension, transgranular crack propagates with small deflection, whereas upon biaxial stretching, the crack grows in a kinked manner with large deflection. These findings shed new light in GB-based engineering and control of mechanical properties of MoS2 crystals toward real-world applications in flexible electronics and nanoelectromechanical systems.

Switchable Chiral Selection of Aspartic Acids by Dynamic States of Brushite.

We herein show the chiral recognition and separation of aspartic acid (Asp) enantiomers by achiral brushite due to the asymmetries of their dynamical steps in its nonequilibrium states. Growing brushite has a higher adsorption affinity to d-Asp, while l-Asp is predominant on the dissolving brushite surface. Microstructural characterization reveals that chiral selection is mainly attributed to brushite [101] steps, which exhibit two different configurations during crystal growth and dissolution, respectively, with each preferring a distinct enantiomer due to this asymmetry. Because these transition step configurations have different stabilities, they subsequently result in asymmetric adsorption. By varying free energy barriers through solution thermodynamic driving force (i.e., supersaturation), the dominant nonequilibrium intermediate states can be switched and chiral selection regulated. This finding highlights that the dynamic steps can be vital for chiral selection, which may provide a potential pathway for chirality generation through the dynamic nature.

Mechanical properties of monocrystalline and polycrystalline monolayer black phosphorus.

The mechanical properties of monocrystalline and polycrystalline monolayer black phosphorus (MBP) are systematically investigated using classic molecular dynamic simulations. For monocrystalline MBP, it is found that the shear strain rate, sample dimensions, temperature, atomic vacancies and applied statistical ensemble affect the shear behaviour. The wrinkled morphology is closely connected with the direction of the in-plane shear, dimensions of the samples, and applied ensembles. Particularly, small samples subjected to loading/unloading of the shear deformation along the armchair direction demonstrate a clear mechanical hysteresis loop. For polycrystalline MBP, the maximum shear stress as a function of the average grain size follows an inverse pseudo Hall-Petch type relationship under an isothermal-isobaric (NPT) ensemble, whereas under a canonical (NVT) ensemble, the maximum shear stress of polycrystalline MBP exhibits a 'flipped' behaviour. Furthermore, polycrystalline MBP subjected to uniaxial tension also exhibits a strongly grain size-dependent mechanical response, and it can fail by brittle intergranular and transgranular fractures because of its weaker grain boundary structures and the direction-dependent edge energy, respectively. These findings provide useful insight into the mechanical design of BP for nanoelectronic devices.

Carbon nanotubes kirigami mechanical metamaterials.

Imparting elasticity and functionality to materials is one of the key objects of materials science research. Here, inspired by the art of kirigami, mechanical metamaterials comprising carbon nanotubes (CNTs) are hypothetically constructed. Using classical molecular dynamics (MD) simulations, a systematic study of the elastic limit, extensibility and yield stress of as-generated CNTs kirigami (CNT-k) is performed. Three designated kirigami patterns are employed to achieve high stretchability of CNTs. It is shown that CNT-k typically exhibits three distinct deformation stages, of which the first stage, which is referred to as geometric deformation, contributes quite a high proportion of the ductility. Various geometric parameters of CNT-k that influence the key mechanical properties of interest are respectively discussed. Three types of CNT-k with specifically identical geometric parameters exhibit distinct mechanical characteristics. This study provides an interesting example of interplay between the geometry, ductility, and mechanical characteristics of tubular materials.

Computer simulation of water desalination through boron nitride nanotubes.

Development of high-efficiency and low-cost seawater desalination technologies is critical to solving the global water crisis. Herein we report a fast water filtering method with high salt rejection by boron nitride nanotubes (BNNTs). The effect of the radius of BNNTs on water filtering and salt rejection was investigated by molecular dynamics (MD) simulation. Our simulation results demonstrate that fast water permeation and high salt rejection could be achieved by BNNT(7,7) under both high pressure and low pressure. The potential of mean force (PMF) of Na+ ion and water molecule through BNNT(7,7) further revealed the mechanism of seawater desalination by BNNT(7,7). Using BNNT(7,7) array, a 10 cm2 nanotube membrane with 1.5 × 1013 pores per cm2 will produce freshwater with a flow rate of 98 L per day per MPa under 100 MPa. Our study shows the potential application of BNNTs membrane for fast and efficient desalination.

Targeting Hippo pathway by specific interruption of YAP-TEAD interaction using cyclic YAP-like peptides.

Hippo signaling pathway is emerging as a novel target for anticancer therapy because it plays key roles in organ size control and tumorigenesis. As the downstream effectors, Yes-associated protein (YAP)-transcriptional enhancer activation domain family member (TEAD) association is essential for YAP-driven oncogenic activity, while TEAD is largely dispensable for normal tissue growth. We present the design of YAP-like peptides (17mer) to occupy the interface 3 on TEAD. Introducing cysteines at YAP sites 87 and 96 can induce disulfide formation, as confirmed by crystallography. The engineered peptide significantly improves the potency in disrupting YAP-TEAD interaction in vitro. To confirm that blocking YAP-TEAD complex formation by directly targeting on TEAD is a valid approach, we report a significant reduction in tumor growth rate in a hepatocellular carcinoma xenograft model after introducing the dominant-negative mutation (Y406H) of TEAD1 to abolish YAP-TEAD interaction. Our results suggest that targeting TEAD is a promising strategy against YAP-induced oncogenesis.

Impact of interfacial high-density water layer on accurate estimation of adsorption free energy by Jarzynski's equality.

The interactions between proteins/peptides and materials are crucial to research and development in many biomedical engineering fields. The energetics of such interactions are key in the evaluation of new proteins/peptides and materials. Much research has recently focused on the quality of free energy profiles by Jarzynski's equality, a widely used equation in biosystems. In the present work, considerable discrepancies were observed between the results obtained by Jarzynski's equality and those derived by umbrella sampling in biomaterial-water model systems. Detailed analyses confirm that such discrepancies turn up only when the target molecule moves in the high-density water layer on a material surface. Then a hybrid scheme was adopted based on this observation. The agreement between the results of the hybrid scheme and umbrella sampling confirms the former observation, which indicates an approach to a fast and accurate estimation of adsorption free energy for large biomaterial interfacial systems.

HTR+: a novel algorithm for identifying type and polycrystal of gas hydrates.

In this work, the hierarchical topology ring (HTR+) algorithm, an extension of the HTR algorithm, was developed for identifying gas hydrate types, cage structures, and grain boundaries (GBs) within polycrystalline structures. Utilizing molecular dynamics trajectories of polycrystalline hydrates, the accuracy of the HTR+ algorithm is validated in identifying sI, sII and sH hydrate types, hydrate grains, and GBs in multi-hydrate polycrystals, as well as clathrate cages at GBs. Additionally, during the hydrate nucleation and growth processes, clathrate cages, hydrate type, hydrate grains and ice structures are accurately recognized. Significantly, this algorithm demonstrates high efficiency, particularly for large hydrate systems. HTR+ algorithm emerges a powerful tool for identifying micro/mesoscopic structures of gas hydrates, enabling an in-depth understanding of the formation mechanisms and properties of gas hydrates.