In Situ Liquid-Cell TEM Observation of Multiphase Classical and Nonclassical Nucleation of Calcium Oxalate

Calcium oxalate (CaOx) is the major phase in kidney stones and the primary calcium storage medium in plants. CaOx can form crystals with different lattice types, water contents, and crystal structures. However, the conditions and mechanisms leading to nucleation of particular CaOx crystals are unclear. Here, liquid-cell transmission electron microscopy and atomistic molecular dynamics simulations are used to study in situ CaOx nucleation at different conditions. The observations reveal that rhombohedral CaOx monohydrate (COM) can nucleate via a classical pathway, while square COM can nucleate via a non-classical multiphase pathway. Citrate, a kidney stone inhibitor, increases the solubility of calcium by forming calcium-citrate complexes and blocks oxalate ions from approaching calcium. The presence of multiple hydrated ionic species draws additional water molecules into nucleating CaOx dihydrate crystals. These findings reveal that by controlling the nucleation pathways one can determine the macroscale crystal structure, hydration state, and morphology of CaOx.     

Multifunctional Block Copolymers for Simultaneous Solubilization of Poorly Water‐Soluble Cholesterol and Hydroxyapatite Crystals

The solubilization of targeted compounds represents key criteria in the sophisticated field of medical chemistry but also in technical applications like scale removal. Especially, the simultaneous dissolution of two chemically different compounds remains challenging. Herein, macromolecular solubilizers are introduced for the simultaneous dissolution and encapsulation of poorly water‐soluble cholesterol and hydroxyapatite. The peptide‐based, amphiphilic block copolymers possess physicochemically disparate segments combined in one polymer chain as binding sites for hydrophobic as well as ionic materials. Small polymer libraries are synthesized and screened for structure–property relationships. Complementary analytical techniques suggest polymeric self‐assembly into spherical adaptive nanoparticles with the fundamental ability to passively absorb significant amounts of hydrophobic cholesterol up to 33 wt%. Furthermore, the additional incorporation of acidic domains enables the simultaneous dissolution of hydrophobic compounds and mineral phases such as hydroxyapatite. Ultimately, those nontoxic block copolymers can be used to solubilize and absorb other lipophilic and ionic compounds such as Sudan III dye and calcium ions. Such multifunctional nanomaterials have a wide range of direct application for simultaneous dissolution or delivery of hydrophobic molecules and cations resp. minerals for instance in the field of atherosclerosis.     

Inorganic Ionic Oligomers Induced Organic-Inorganic Synergistic Toughening Enabling Mechanical Robust and Recyclable Nanocomposite Hydrogels

Mechanical robust hydrogels are ideal for applications in energy, environment, biomedicine, and structural engineering materials fields. However, high strength and high toughness are usually in conflict with each other, and simultaneously achieving both of them within a hydrogel has been challenging. Herein an organic-inorganic synergistic toughening strategy is reported via in-situ inorganic ionic polymerization of calcium phosphate oligomers within polymer composite networks composed of polyvinyl alcohol chains and aramid nanofibers. The composite hydrogels are provided with a prestress-induced hierarchically fibrous structure through the assembly, which resulted in the mechanical strength and toughness up to 24.15 ± 1.12 MPa and 15.68 ± 1.78 MJ m⁻³, respectively, surpassing most toughened hydrogels. Through lamination and crosslinking, bulk hydrogels with controllable mechanical anisotropy and significant energy absorption/dissipation ability are produced. Moreover, the recycling and regeneration of the hydrogels are easily realized owing to the physically crosslinked network and acid-induced dissolution of the inorganic units of the hydrogels, which lays a foundation for the sustainable large-scale production and application of the hydrogels. This study provides an alternative approach for the development of mechanical robust and recyclable nanocomposite hydrogels for various applications including soft body armor, flexible electronics, soft robotics, etc.     

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.     

Additives Control the Stability of Amorphous Calcium Carbonate via Two Different Mechanisms: Surface Adsorption versus Bulk Incorporation

The mechanisms by which organisms control the stability of amorphous calcium carbonate (ACC) are yet not fully understood. Previous studies have shown that the intrinsic properties of ACC and its environment are critical in determining ACC stability. Here, the question, what is the effect of bulk incorporation versus surface adsorption of additives on the stability of synthetic ACC, is addressed. Using a wide range of in situ characterization techniques, it is shown that surface adsorption of poly(Aspartic acid) (pAsp) has a much larger stabilization effect than bulk incorporation of pAsp and only 1.5% pAsp could dramatically increase the crystallization temperature from 141 to 350 °C. On the contrary, surface adsorption of PO₄^3? ions and OH^? ions does not effectively stabilize ACC. However, bulk incorporation of these ions could significantly improve the ACC stability. It is concluded that the stabilization mechanism of pAsp is entirely different from that of PO₄^3? and OH^? ions: while pAsp is effectively inhibiting calcite nucleation at the surface of ACC particle, the latter acts to modify the ion mobility and delay crystal propagation. Thus, new insights on controlling the stability and crystallization processes of metastable amorphous materials are provided.     

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.     

流沙湾海水养殖珍珠微观结构及形成机制研究

利用扫描电子显微镜(SEM)、原子力显微镜(AFM),研究流沙湾海水珍珠珍珠质层和棱柱层的微尺度生长结构,采用傅里叶变换红外光谱仪(FTIR)对珍珠质层及棱柱层的成分组成进行分析.结果表明:构成海水珍珠珍珠层的珍珠质层,棱柱层和过渡层的微结构和组成是有所不同的,珍珠质层主要为文石型碳酸钙,纳米文石微晶颗粒与有机质颗粒交织形成文石板片,棱柱层中存在方解石和文石两种晶型的碳酸钙,过渡层是由有机质和少量的碳酸钙共同组成;通过对珍珠层结构和成分的研究,初步推断出其生长模式分三个阶段:(1)珠母贝从海水环境中富集钙离子,并分泌有机质诱导碳酸钙成核结晶,二者共同生长形成棱柱层;(2)棱柱层生长到一定阶段,晶体生长的同时珠母贝分泌的有机质发生变化形成一层有机质过渡层,调控碳酸钙的生长;(3)在有机质层上初始成核的纳米文石微晶颗粒与有机质颗粒交织堆砌生长,形成文石板片,文石板片层层堆叠形成结构致密排列有序的珍珠质层.     

Salty Ice Electrolyte with Superior Ionic Conductivity Towards Low-Temperature Aqueous Zinc Ion Hybrid Capacitors

Aqueous electrochemical energy storage (EES) devices have attracted considerable attention due to their advantages of low cost and high safety. However, the freeze of aqueous electrolytes usually causes the dramatic loss of ionic conduction capacity, thereby seriously restricting the low-temperature application of such EES devices. Herein, different from traditional frozen electrolytes, a Zn(ClO₄)₂ salty ice with superior ionic conductivity (1.3 × 10⁻³ S cm⁻¹ even at −60 °C) is discovered. It is attributed to the unique 3D ionic transport channels inside such ice, which enables the fast transport of both Zn²⁺ ions and ClO₄⁻ ions inside the ice at low temperatures. Using this Zn(ClO₄)₂ salty ice as an electrolyte, as-built zinc ion hybrid capacitor is able to work even at −60 °C (with 74.2% of the room temperature capacity), and exhibits an ultra-long cycle life of 70 000 cycles at low temperature. This discovery provides a new insight for constructing low-temperature EES devices using salty ices as electrolytes.     

Iron-Doped,Mullite-Impregnated PVDF Composite: An Alternative Separator for a High Charge Storage Ceramic Capacitor

In this communication, the formation mechanism of the electroactive β phase, morphology and the dielectric activities of increasing doping concentration (0–1.2 M.W % of mullite) of Fe²⁺ ion-doped, mullite-impregnated polyvinylidene fluoride (PVDF) nanocomposite have been investigated. Differential thermal analysis (DTA) confirms the formation of an electroactive β phase, and Fourier transform infrared spectroscopy (FTIR) showed that the β phase increases simultaneously and attains the maximum increment of 2.6 times compared to pristine PVDF. X-ray diffraction (XRD) spectra also agreed well with the β-phase increment behaviour and also confirmed the presence of required mullite phases. Field emission scanning electron microscopy (FESEM) images indicate the strong interaction between the polymer matrix and different concentrations of Fe²⁺ ion-doped mullite particles, resulting in enhanced electroactive β phase formation and large dielectric constant of the nanocomposite films followed by significant low dielectric loss with high ac conductivity compared to pristine PVDF films at room temperature. This doped polymer composite can be used as a high dielectric separator and, using this separator, we have successfully fabricated a high-charge-storage device. This paper also demonstrates that the loading of conductive Fe²⁺ ions within the highly insulating mullite matrix has a critical concentration for the enhancement and nucleation of the electroactive β phase of the PVDF polymer. In this critical concentration, the highest formation of a β network and maximum numbers of homogeneously distributed iron-doped mullite (FeM) particles in PVDF matrix improves the effective interfacial polarization by Maxwell–Wagner–Sillar (MWS) polarization effect which is responsible for the enhancement of dielectric constant and ac conductivity followed by significant tangent loss. So, it can be concluded that the incorporation of Fe²⁺-doped mullite into PVDF matrix is an effective way to fabricate a high dielectric separator of high-charge-storage electronic devices.     

制备工艺对0-3型压电复合材料的d33的影响

采用固化、热压、冷压工艺制备0-3型PZNN／PVDF压电复合材料，用准静态压电测试仪测试了压电复合材料的压电应变常数d33,通过对以上三种制备工艺的对比，结果表明：在无机和有机压电材料的体积比大于70％时，冷压工艺优于固化和热压工艺，在它们的体积比小于70％时，热压工艺优于冷压和固化工艺。     

Genetically Engineered Chimeric Silk–Silver Binding Proteins

Composite or hybrid materials are commonly found in Nature, formed through the concentration and subsequent nucleation of ions upon organic templates that are most often protein based. Examples include the deposition of calcium containing salts in bone, teeth and the inner ear and iron oxide structures in magnetotactic bacteria. Biological organisms use a limited number of metal ions, the principal ones being calcium and iron, with lesser amounts of strontium, and barium. The ability to utilize other ions to generate composites offers the possibility of new material properties. New materials incorporating silver would be useful in the context of antimicrobial functions. Therefore, in the present study, a new route to such functionalized biomaterials is reported. Genetically engineered fusion proteins are created by the incorporation of nucleotides corresponding to short silver binding peptides identified by a combinatorial biopanning process into the consensus sequence of silk from the spider, Nephila clavipes. The resulting chimeric silk–silver binding proteins nucleated Ag ions from a solution of silver nitrate while the silk protein provided a stable template material which could be processed into films, fibers, and three‐dimensional scaffolds. The silk films inhibited microbial growth of both Gram‐positive and Gram‐negative microrganisms on agar plates and in liquid culture, thus highlighting the potential of these chimeric material systems as antimicrobial biomedical coatings.     

Synthesis and Patterning of Luminescent CaCO3–Poly(p‐phenylene) Hybrid Materials and Thin Films

Nature employs specialized macromolecules to produce highly complex structures and understanding the role of these macromolecules allows us to develop novel materials with interesting properties. Herein, we report the role of modified conjugated polymers in the nucleation, growth, and morphology of calcium carbonate (CaCO₃) crystals. In situ incorporation of sulfonated poly(p‐phenylene) (s(PPP)) into a highly oriented calcium carbonate matrix is investigated along with the synthesis and patterning of luminescent CaCO₃–PPP hybrid materials. Functionalized PPP with polar and nonpolar groups are used as additives in the mineralization medium. The polymer (P1) with polar groups give iso‐oriented calcite crystals, whereas PPP with an additional alkyl chain (P2) results in vaterite crystals. The crystallization mechanism can be explained based on self‐assembly and aggregation of polymers in an aqueous environment. Such light‐emitting hybrid composites with tunable optical properties are excellent candidates for optoelectronics and biological applications.     

Artificial Soft–Rigid Protective Layer for Dendrite‐Free Lithium Metal Anode

Lithium (Li) metal has been pursued as “Holy Grail” among various anode materials due to its high specific capacity and the lowest reduction potential. However, uncontrolled growth of Li dendrites and extremely unstable interfaces during repeated Li plating/stripping ineluctably plague the practical applications of Li metal batteries. Herein, an artificial protective layer with synergistic soft–rigid feature is constructed on the Li metal anode to offer superior interfacial stability during long‐term cycles. By suppressing random Li deposition and the formation of isolated Li, such a protective layer enables a dendrite‐free morphology of Li metal anode and suppresses the depletion of Li metal and electrolyte. Additionally, sufficient ionic conductivity is guaranteed through the synergy between soft and rigid structural units that are uniformly dispersed in the layer. Dendrite‐free and dense Li deposition, as well as a greatly reduced interfacial resistance after cycling, is achieved owing to the stabilized interface, accounting for significantly prolonged cycle life of Li metal batteries. This work highlights the ability of synergistic organic/inorganic protective layer in stabilizing Li metal anode and provides fresh insights into the energy chemistry and mechanics of anode in a working battery.     

金属支架对BLM的K+离子敏感特性的影响

BLM(双层类脂膜)的金属支撑构成了一种电化学传感器.这种传感器的化学反应和电现象之间的转化,是通过金属对BLM的支撑来实现的,不同于经典的电化学换能器.用缬氨霉素修饰的BLM作为敏感膜,制成金属-BLM和经典电化学K+离子电极.通过两种电极对K+离子检测的对比实验,以及不同直径和新鲜面不同给出方法的金属-BLM电极的对比实验,探讨了BLM的金属支撑对BLM的K+离子敏感特性的影响.从实验数据看,BLM的金属支撑在性能上优于经典电化学传感器,但支撑介质的新鲜面对BLM的K+离子敏感特性有影响.     

Suppressing Sodium Dendrites by Multifunctional Polyvinylidene Fluoride (PVDF) Interlayers with Nonthrough Pores and High Flux/Affinity of Sodium Ions toward Long Cycle Life Sodium Oxygen‐Batteries

Rechargeable sodium–oxygen (Na–O₂) batteries are of interest due to their high specific capacity, high equilibrium potential output, and the abundance of sodium resources; however, their cycle life is still very poor due to instability of electrolytes and especially the uncontrollable growth of Na dendrites. Herein, as a proof‐of‐concept experiment, a facile and low‐cost strategy is first proposed and demonstrated to effectively suppress growth of Na dendrites by using a fibrillar polyvinylidene fluoride film (f‐PVDF) with nonthrough pore as a multifunctional blocking interlayer. Unexpectedly, the f‐PVDF interlayer endows Na–O₂ battery with superior electrochemical performances, including high rate capability and long cycle life (up to 87 cycles), which is superior to those of the compact PVDF (c‐PVDF), PVDF with through pores (p‐PVDF), polyethylene oxide (PEO), and conventional polytetrafluoroethylene (PTFE) counterparts due to the following combined advantages: (1) the stronger C? F polar function groups provide a better affinity to Na ions, thus enabling a more homogeneous Na deposition than that of C? O function groups in PEO interlayer; (2) compared with c‐PVDF and p‐PVDF interlayers, f‐PVDF holds more electrolyte uptake for higher ion conductivity; (3) the good wettability of the f‐PVDF interlayer with electrolyte benefits Na dendrite suppression compared with PTFE interlayer.     

libRadtran的云辐射传输模式及其与SBDART的比较

介绍了libRadtran辐射传输模式中对水云和冰云辐射特征（单次散射反照率、体消光系数和不对称因子）的参数化方案,利用该模式对水云和冰云在0.65 um、1.64 um和2.13 um的反射率进行了模拟计算,并将计算结果与SBDART的模拟结果进行了比较。结果表明,在相同条件下,水云的libRadtran的参数化计算结果要比SBDART米散射的计算结果要小,二者在可见光区域符合的较好,在近红外区域相差较大;不同形状冰晶的参数化模拟计算结果要比SBDART球形米散射的计算结果更为详细和准确,libRadtran在考虑冰晶形状时的辐射传输计算要比SBDART有优势。在云微物理参数反演需要预先计算的冰云辐射查找表可以用libRadtran代替目前广泛使用的SBDART辐射传输模式。     

Droplet Microfluidics XRD Identifies Effective Nucleating Agents for Calcium Carbonate

The ability to control crystallization reactions is required in a vast range of processes including the production of functional inorganic materials and pharmaceuticals and the prevention of scale. However, it is currently limited by a lack of understanding of the mechanisms underlying crystal nucleation and growth. To address this challenge, it is necessary to carry out crystallization reactions in well‐defined environments, and ideally to perform in situ measurements. Here, a versatile microfluidic synchrotron‐based technique is presented to meet these demands. Droplet microfluidic‐coupled X‐ray diffraction (DMC‐XRD) enables the collection of time‐resolved, serial diffraction patterns from a stream of flowing droplets containing growing crystals. The droplets offer reproducible reaction environments, and radiation damage is effectively eliminated by the short residence time of each droplet in the beam. DMC‐XRD is then used to identify effective particulate nucleating agents for calcium carbonate and to study their influence on the crystallization pathway. Bioactive glasses and a model material for mineral dust are shown to significantly lower the induction time, highlighting the importance of both surface chemistry and topography on the nucleating efficiency of a surface. This technology is also extremely versatile, and could be used to study dynamic reactions with a wide range of synchrotron‐based techniques.     

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.     

Zwitterionic Nanohydrogel Grafted PVDF Membranes with Comprehensive Antifouling Property and Superior Cycle Stability for Oil‐in‐Water Emulsion Separation

Fouling caused by oil and other pollutants is one of the most serious challenges for membranes used for oil/water separation. Aiming at improving the comprehensive antifouling property of membranes and thus achieving long‐term cyclic stability, it is reported in this work the design of a kind of zwitterionic nanosized hydrogels grafted poly(vinylidene fluoride) (PVDF) microfiltration membrane (ZNG‐g‐PVDF) with superior fouling‐tolerant property for oil‐in‐water emulsion separation. Sulfobetaine zwitterionic nanohydrogels with the diameter of ≈ 50 nm are synthesized by an inverse microemulsion polymerization process. They are then grafted onto the surface of PVDF microfiltration membrane, endowing the membrane a superhydrophilic and nearly zero oil adhesion property. This ZNG‐g‐PVDF membrane exhibits great tolerance and resistance to salts pH, especially an excellent antifouling property to oil‐in‐water emulsions containing various pollutants such as surfactants, proteins, and natural organic materials (e.g., humic acid). The comprehensive antifouling property of the membrane gives rise to the cyclic stability of the membrane greatly improved. A nearly 100% recovery ratio of permeating flux is achieved during several cycles of oil‐in‐water emulsion filtration. The ZNG‐g‐PVDF membrane shows great potential in treating practical oily wastewater containing complicated components in the effluent.