Deformation twin traces on gold surfaces: A pathway to tailored epitaxial growth of 1D semiconductors.

The field of one-dimensional semiconducting materials holds a wide variety of captivating applications, such as photovoltaic cells, electronic devices, catalysis cells, lasers, and more. The tunability of electrical, mechanical, or optical attributes of a semiconductor crystal relies on the ability to control and pattern the crystal's growth direction, orientation, and dimensions. In this study, we harvest the unique properties of crystallographic defects in Au substrates, specifically twin boundaries, to fabricate selective epitaxial growth of semiconducting nanocrystals. Different crystallographic defects were previously shown to enhance materials properties, such as, screw dislocations providing spiral crystal growth, dislocation outcrops, and vacancies increasing their catalytic activity, dislocation strengthening, and atomic doping changing the crystal's electrical properties. Here, we present a unique phenomenon of directed growth of semiconductor crystals of gold(I)-cyanide (AuCN) on the surface of thin Au layers, using traces of deformation twins on the surface. We show that emergence of deformation twins to the {111} Au surface leads to the formation of ledges, exposing new {001} and {111} facets on the surface. We propose that this phenomenon leads to epitaxial growth of AuCN on the freshly exposed {111} facets of the twin boundary trace ledges. Specific orientations of the twin boundaries with respect to the Au surface allow for patterned growth of AuCN in the <110> orientations. Nano-scale patterning of AuCN semiconductors may provide an avenue for property tuning, particularly the band gap acquired.

How Does Local Strain Affect Stokes Shifts in Halide Double Perovskite Nanocrystals?

Lead-free perovskite nanocrystals are of interest due to their nontoxicity and potential application in the display industry. However, engineering their optical properties is nontrivial and demands an understanding of emission from both self-trapped and free excitons. Here, we focus on tuning silver-based double perovskite nanocrystals' optical properties via two iso-valent dopants, Bi and Sb. The photoluminescence quantum yield of the intrinsic Cs2Ag1-yNayInCl6 perovskite increased dramatically upon doping. However, the two dopants affect the optical properties very differently. We hypothesize that the differences arise from their differences in electronic level contributions and ionic sizes. This hypothesis is validated through absorption and temperature dependence photoluminescence measurements, namely, by employing the Huang-Rhys factor, which indicates the coupling of the exciton to the lattice environment. The larger ionic size of Bi also plays a role in inducing significant microstraining verified via synchrotron measurements. These differences make Bi more sensitive to doping concentration over antimony which displays brighter emission (QY ∼40%). Such understanding is important for engineering optical properties in double perovskites, especially in light of recent achievements in boosting the photoluminescence quantum yield.

Self-assembled fatty acid crystalline coatings display superhydrophobic antimicrobial properties.

Superhydrophobicity is a well-known wetting phenomenon found in numerous plants and insects. It is achieved by the combination of the surface's chemical properties and its surface roughness. Inspired by nature, numerous synthetic superhydrophobic surfaces have been developed for various applications. Designated surface coating is one of the fabrication routes to achieve the superhydrophobicity. Yet, many of these coatings, such as fluorine-based formulations, may pose severe health and environmental risks, limiting their applicability. Herein, we present a new family of superhydrophobic coatings comprised of natural saturated fatty acids, which are not only a part of our daily diet, but can be produced from renewable feedstock, providing a safe and sustainable alternative to the existing state-of-the-art. These crystalline coatings are readily fabricated via single-step deposition routes, namely thermal deposition or spray-coating. The fatty acids self-assemble into highly hierarchical crystalline structures exhibiting a water contact angle of ∼165° and contact angle hysteresis lower than 6°, while their properties and morphology depend on the specific fatty acid used as well as on the deposition technique. Moreover, the fatty acid coatings demonstrate excellent thermal stability. Importantly, this new family of coatings displays excellent anti-biofouling and antimicrobial properties against Escherichia coli and Listeria innocua, used as relevant model Gram-negative and Gram-positive bacteria, respectively. These multifunctional coatings hold immense potential for application in numerous fields, ranging from food safety to biomedicine, offering sustainable and safe solutions.

Tuning the Magnetization of Manganese (II) Carbonate by Intracrystalline Amino Acids.

Incorporation of organic molecules into the lattice of inorganic crystalline hosts is a common phenomenon in biomineralization and is shown to alter various properties of the crystalline host. Taking this phenomenon as a source of inspiration, it is shown herein that incorporation of specific single amino acids into the lattice of manganese (II) carbonate strongly alters its inherent magnetic properties. At room temperature, the magnetic susceptibility of the amino-acid-incorporating paramagnetic MnCO3 decreases, following a simple rule of mixtures. When cooled below the Néel temperature, however, the opposite trend is observed, namely an increase in magnetic susceptibility measured in a high magnetic field. Such an increase, accompanied by a drastic change in the Néel phase transformation temperature, results from a decrease in MnCO3 orbital overlapping and the weakening of superexchange interactions. It may be that this is the first time that the magnetic properties of a host crystal are tuned via the incorporation of amino acids.

Adsorption of SARS CoV-2 spike proteins on various functionalized surfaces correlates with the high transmissibility of Delta and Omicron variants.

The SARS-CoV-2 virus emerged at the end of 2019 and rapidly developed several mutated variants, specifically the Delta and Omicron, which demonstrate higher transmissibility and escalating infection cases worldwide. The dominant transmission pathway of this virus is via human-to-human contact and aerosols which once inhaled interact with the mucosal tissue, but another possible route is through contact with surfaces contaminated with SARS-CoV-2, often exhibiting long-term survival. Here we compare the adsorption capacities of the S1 and S2 subunits of the spike (S) protein from the original variant to that of the S1 subunit from the Delta and Omicron variants on self-assembled monolayers by Quartz Crystal â€‹Microbalance. The results clearly show a significant difference in adsorption capacity between the different variants, as well as between the S1 and S2 subunits. Overall, our study demonstrates that while the Omicron variant is able to adsorb much more successfully than the Delta, both variants show enhanced adsorption capacity than that of the original strain. We also examined the influence of pH conditions on the adsorption ability of the S1 subunit and found that adsorption was strongest at pH 7.4, which is the physiological pH. The main conclusion of this study is that there is a strong correlation between the adsorption capacity and the transmissibility of the various SARS-CoV-2 variants.

On the mechanism of calcium carbonate polymorph selection via confinement.

Organisms deposit various biominerals in the course of their biomineralisation. The most abundant of these is calcium carbonate, which manifests itself in several polymorphs. While organisms possess the ability to control the specific polymorph deposited, the exact mechanism by which polymorph selection takes place is not yet fully understood. Because biominerals often grow within confined spaces, one of the suggested possibilities was that polymorph selection might be an outcome of confinement. Confining conditions have indeed been extensively shown to have a strong impact on the nucleation and crystal growth of calcium carbonate and, in particular, on its polymorph selection. However, despite numerous studies on the crystal growth of calcium carbonate in confined spaces, the mechanism of polymorph selection under confinement has not been elucidated. Herein, we discuss previously reported results and suggest a mechanistic explanation of the observed selective formation of calcite or aragonite or vaterite. We consider the possible effects of charged confining inner surfaces and of the sizes of the confining pores, and discuss whether the predominantly precipitating phase is amorphous calcium carbonate. We also discuss two possible scenarios of crystallization from amorphous calcium carbonate under conditions of confinement: via solid-state transformation or via a mechanism of dissolution-reprecipitation.

High-Mg calcite nanoparticles within a low-Mg calcite matrix: A widespread phenomenon in biomineralization.

During the process of biomineralization, organisms utilize various biostrategies to enhance the mechanical durability of their skeletons. In this work, we establish that the presence of high-Mg nanoparticles embedded within lower-Mg calcite matrices is a widespread strategy utilized by various organisms from different kingdoms and phyla to improve the mechanical properties of their high-Mg calcite skeletons. We show that such phase separation and the formation of high-Mg nanoparticles are most probably achieved through spinodal decomposition of an amorphous Mg-calcite precursor. Such decomposition is independent of the biological characteristics of the studied organisms belonging to different phyla and even kingdoms but rather, originates from their similar chemical composition and a specific Mg content within their skeletons, which generally ranges from 14 to 48 mol % of Mg. We show evidence of high-Mg calcite nanoparticles in the cases of six biologically different organisms all demonstrating more than 14 mol % Mg-calcite and consider it likely that this phenomenon is immeasurably more prevalent in nature. We also establish the absence of these high-Mg nanoparticles in organisms whose Mg content is lower than 14 mol %, providing further evidence that whether or not spinodal decomposition of an amorphous Mg-calcite precursor takes place is determined by the amount of Mg it contains. The valuable knowledge gained from this biostrategy significantly impacts the understanding of how biominerals, although composed of intrinsically brittle materials, can effectively resist fracture. Moreover, our theoretical calculations clearly suggest that formation of Mg-rich nanoprecipitates greatly enhances the hardness of the biomineralized tissue as well.

Coral micro- and macro-morphological skeletal properties in response to life-long acclimatization at CO2 vents in Papua New Guinea.

This study investigates the effects of long-term exposure to OA on skeletal parameters of four tropical zooxanthellate corals naturally living at CO2 seeps and adjacent control sites from two locations (Dobu and Upa Upasina) in the Papua New Guinea underwater volcanic vent system. The seeps are characterized by seawater pH values ranging from 8.0 to about 7.7. The skeletal porosity of Galaxea fascicularis, Acropora millepora, massive Porites, and Pocillopora damicornis was higher (up to ~ 40%, depending on the species) at the seep sites compared to the control sites. Pocillopora damicornis also showed a decrease of micro-density (up to ~ 7%). Thus, further investigations conducted on this species showed an increase of the volume fraction of the larger pores (up to ~ 7%), a decrease of the intraskeletal organic matrix content (up to ~ 15%), and an increase of the intraskeletal water content (up to ~ 59%) at the seep sites. The organic matrix related strain and crystallite size did not vary between seep and control sites. This multi-species study showed a common phenotypic response among different zooxanthellate corals subjected to the same environmental pressures, leading to the development of a more porous skeletal phenotype under OA.

Self-catalytic growth of one-dimensional materials within dislocations in gold.

Dislocations in metals affect their properties on the macro- and the microscales. For example, they increase a metal's hardness and strength. Dislocation outcrops exist on the surfaces of such metals, and atoms in the proximity of these outcrops are more loosely bonded, facilitating local chemical corrosion and reactivity. In this study, we present a unique autocatalytic mechanism by which a system of inorganic semiconducting gold(I) cyanide nanowires forms within preexisting dislocation lines in a plastically deformed Au-Ag alloy. The formation occurs during the classical selective dealloying process that forms nanoporous Au. Nucleation of the nanowire originates at the surfaces of the catalytic dislocation outcrops. The nanowires are single crystals that spontaneously undergo layer-by-layer one-dimensional growth. The continuous growth of nanowires is achieved when the dislocation density exceeds a critical value evaluated on the basis of a kinetic model that we developed.

Sclerites of the soft coral Ovabunda macrospiculata (Xeniidae) are predominantly the metastable CaCO3 polymorph vaterite.

Soft corals (Cnidaria, Anthozoa, Octocorallia, Alcyonacea) produce internal sclerites of calcium carbonate previously shown to be composed of calcite, the most stable calcium carbonate polymorph. Here we apply multiple imaging and physical chemistry analyses to extracted and in-vivo sclerites of the abundant Red Sea soft coral, Ovabunda macrospiculata, to detail their mineralogy. We show that this species' sclerites are comprised predominantly of the less stable calcium carbonate polymorph vaterite (> 95%), with much smaller components of aragonite and calcite. Use of this mineral, which is typically considered to be metastable, by these soft corals has implications for how it is formed as well as how it will persist during the anticipated anthropogenic climate change in the coming decades. This first documentation of vaterite dominating the mineral composition of O. macrospiculata sclerites is likely just the beginning of establishing its presence in other soft corals. STATEMENT OF SIGNIFICANCE: Vaterite is typically considered to be a metastable polymorph of calcium carbonate. While calcium carbonate structures formed within the tissues of octocorals (phylum Cnidaria), have previously been reported to be composed of the more stable polymorphs aragonite and calcite, we observed that vaterite dominates the mineralogy of sclerites of Ovabunda macrospiculata from the Red Sea. Based on electron microscopy, Raman spectroscopy, and X-ray diffraction analysis, vaterite appears to be the dominant polymorph in sclerites both in the tissue and after extraction and preservation. Although this is the first documentation of vaterite in soft coral sclerites, it likely will be found in sclerites of other related taxa as well.

Structural and chemical variations in Mg-calcite skeletal segments of coralline red algae lead to improved crack resistance.

The calcareous alga Jania sp. is an articulated coralline red seaweed that is abundant in the shallow waters of oceans worldwide. We have previously demonstrated that its structure is highly intricate and exhibits hierarchical organization across multiple length scales from the macro to the nano scale. Moreover, we have proven that the inner pores of its structure are helical, conveying the alga greater compliance as compared to a cylindrical configuration. Herein, we reveal new insights into the structure of Jania sp., particularly, its crystallographic variations and the internal elemental distribution of Mg and Ca. We show that the high-Mg calcite cell wall nanocrystals of Jania sp. are arranged in layers with alternating Mg contents. Moreover, we show that this non-homogenous elemental distribution assists the alga in preventing fracture caused by crack propagation. We further reveal that each one of the cell wall nanocrystals in Jania sp. is not a single crystal as was previously thought, but rather comprises Mg-rich calcite nanoparticles demonstrating various crystallographic orientations, arranged periodically within the layered structure. We also show that these Mg-rich nanoparticles are present in yet another species of the coralline red algae, Corallina sp., pointing to the generality of this phenomenon. To the best of our knowledge this is a first report on the existence of Mg-rich nanoparticles in algal mineralized tissue. We envisage that our findings on the bio-strategy found in the algae to enhance their fracture toughness will have an impact on the design of structures with superior mechanical properties. STATEMENT OF SIGNIFICANCE: Understanding the structure-property relation in biomineralized tissues is of great importance in unveiling Nature's material design strategies, which form the basis for the development of novel structural materials. Crystallographic and elemental variations in the skeletal parts of the coralline red algae and their cumulative contribution to prevention of mechanical failure are yet poorly studied. Herein, we reveal that the high-Mg calcite cell wall nanocrystals of Jania sp. are arranged in layers with alternating Mg concentrations and that this organization facilitates crack deflection, thereby preventing catastrophic fracture. We further discovered that the nanocrystals contain incoherent Mg-rich nanoparticles and suggest that they form via spinodal decomposition of the Mg-ACC precursor and self-arrange periodically throughout the alga's mineralized cell wall, a phenomenon most likely to be widespread in high-Mg calcite biomineralization.

Climate variation during the Holocene influenced the skeletal properties of Chamelea gallina shells in the North Adriatic Sea (Italy).

Understanding how marine taxa will respond to near-future climate changes is one of the main challenges for management of coastal ecosystem services. Ecological studies that investigate relationships between the environment and shell properties of commercially important marine species are commonly restricted to latitudinal gradients or small-scale laboratory experiments. This paper aimed to explore the variations in shell features and growth of the edible bivalve Chamelea gallina from the Holocene sedimentary succession to present-day thanatocoenosis of the Po Plain-Adriatic Sea system (Italy). Comparing the Holocene sub-fossil record to modern thanatocoenoses allowed obtaining an insight of shell variations dynamics on a millennial temporal scale. Five shoreface-related assemblages rich in C. gallina were considered: two from the Middle Holocene, when regional sea surface temperatures were higher than today, representing a possible analogue for the near-future global warming, one from the Late Holocene and two from the present-day. We investigated shell biometry and skeletal properties in relation to the valve length of C. gallina. Juveniles were found to be more porous than adults in all horizons. This suggested that C. gallina promoted an accelerated shell accretion with a higher porosity and lower density at the expense of mechanically fragile shells. A positive correlation between sea surface temperature and both micro-density and bulk density were found, with modern specimens being less dense, likely due to lower aragonite saturation state at lower temperature, which could ultimately increase the energetic costs of shell formation. Since no variation was observed in shell CaCO3 polymorphism (100% aragonite) or in compositional parameters among the analyzed horizons, the observed dynamics in skeletal parameters are likely not driven by a diagenetic recrystallization of the shell mineral phase. This study contributes to understand the response of C. gallina to climate-driven environmental shifts and offers insights for assessing anthropogenic impacts on this economic relevant species.

Molecular and skeletal fingerprints of scleractinian coral biomineralization: From the sea surface to mesophotic depths.

Reef-building corals, the major producers of biogenic calcium carbonate, form skeletons in a plethora of morphological forms. Here we studied skeletal modifications of Stylophora pistillata (clade 4) colonies that adapt to increasing depths with decreasing ambient light. The coral show characteristic transitions from spherical morphologies (shallow depths, 5 m deep) to flat and branching geometries (mesophotic depths, 60 m deep). Such changes are typically ascribed to the algal photosymbiont physiological feedback with the coral that host them. We find specific fine-scale skeletal variability in accretion of structure at shallow- and mesophotic depth morphotypes that suggest underlying genomic regulation of biomineralization pathways of the coral host. To explain this, we conducted comparative morphology-based analyses, including optical and electron microscopy, tomography and X-ray diffraction analysis coupled with a comprehensive transcriptomic analysis of S. pistillata. The samples originated from Gulf of Eilat in the Red Sea collected along a depth gradient from shallow to mesophotic depths (5 to 60 m). Additional samples were experimentally transplanted from 5 m to 60 m and from 60 m to 5 m. Interestingly, both morphologically and functionally, transplanted corals partly adapt by exhibiting typical depth-specific properties. In mesophotic depths, we find that the organic matrix fraction is enriched in the coralla, well matching the overrepresentation of transcripts encoding biomineralization "tool-kit" structural extracellularproteins that was observed. These results provide insights into the molecular mechanisms of calcification and skeletal adaptation that repeatedly allowed this coral group to adapt to a range of environments presumably with a rich geological past. STATEMENT OF SIGNIFICANCE: Understanding the reef coral physiological plasticity under a rapidly changing climate is of crucial importance for the protection of coral reef ecosystems. Most of the reef corals operate near their upper limit of heat tolerance. A possible rescue for some coral species is migration to deeper, cooler mesophotic depths. However, gradually changing environmental parameters (especially light) along the depth gradient pose new adaptative stress on corals with largely unknown influences on the various biological molecular pathways. This work provides a first comprehensive analysis of changes in gene expression, including biomineralization "tool kit" genes, and reports the fine-scale microstructural and crystallographic skeletal details in S. pistillata collected in the Red Sea along a depth gradient spannign 5 to 60 m.

Helical Microstructures of the Mineralized Coralline Red Algae Determine Their Mechanical Properties.

Through controlled biomineralization, organisms yield complicated structures with specific functions. Here, Jania sp., an articulated coralline red alga that secretes high-Mg calcite as part of its skeleton, is in focus. It is shown that Jania sp. exhibits a remarkable structure, which is highly porous (with porosity as high as 64 vol%) and reveals several hierarchical orders from the nano to the macroscale. It is shown that the structure is helical, and proven that its helical configuration provides the alga with superior compliance that allows it to adapt to stresses in its natural environment. Thus, the combination of high porosity and a helical configuration result in a sophisticated, light-weight, compliant structure. It is anticipated that the findings on the advantages of such a structure are likely to be of value in the design or improvement of lightweight structures with superior mechanical properties.

Acidic Monosaccharides become Incorporated into Calcite Single Crystals*.

Carbohydrates, along with proteins and peptides, are known to represent a major class of biomacromolecules involved in calcium carbonate biomineralization. However, in spite of multiple physical and biochemical characterizations, the explicit role of saccharide macromolecules (long chains of carbohydrate molecules) in mineral deposition is not yet understood. In this study, we investigated the influence of two common acidic monosaccharides (MSs), the two simplest forms of acidic carbohydrates, namely glucuronic and galacturonic acids, on the formation of calcite crystals in vitro. We show here that the size, morphology, and microstructure of calcite crystals are altered when they are grown in the presence of these MSs. More importantly, these MSs were found to become incorporated into the calcite crystalline lattice and induce anisotropic lattice distortions, a phenomenon widely studied for other biomolecules related to CaCO3 biomineralization, but never before reported in the case of single MSs. Changes in the calcite lattice induced by MSs incorporation were precisely determined by high-resolution synchrotron powder X-ray diffraction. We believe that the results of this research may deepen our understanding of the interaction of saccharide polymers with an inorganic host and shed light on the implications of carbohydrates for biomineralization processes.

Photocatalytic activity of exfoliated graphite-TiO2 nanoparticle composites.

We investigate the photocatalytic performance of composites prepared in a one-step process by liquid-phase exfoliation of graphite in the presence of TiO2 nanoparticles (NPs) at atmospheric pressure and in water, without heating or adding any surfactant, and starting from low-cost commercial reagents. These show enhanced photocatalytic activity, degrading up to 40% more pollutants with respect to the starting TiO2-NPs, in the case of a model dye target, and up to 70% more pollutants in the case of nitrogen oxides. In order to understand the photo-physical mechanisms underlying this enhancement, we investigate the photo-generation of reactive species (trapped holes and electrons) by ultrafast transient absorption spectroscopy. We observe an electron transfer process from TiO2 to the graphite flakes within the first picoseconds of the relaxation dynamics, which causes the decrease of the charge recombination rate, and increases the efficiency of the reactive species photo-production.

Non-stoichiometric hydrated magnesium-doped calcium carbonate precipitation in ethanol.

The effect of Mg2+ on the precipitation pathway of CaCO3 in absolute ethanol has been studied to investigate the role of ion solvation in the crystallization process. Our data reveal that high concentrations of Mg2+ promote the precipitation of an amorphous transient phase together with non-stoichometric hydrated phases of calcium carbonate.

From spinodal decomposition to alternating layered structure within single crystals of biogenic magnesium calcite.

As organisms can form crystals only under ambient conditions, they demonstrate fascinating strategies to overcome this limitation. Recently, we reported a previously unknown biostrategy for toughening brittle calcite crystals, using coherently incorporated Mg-rich nanoprecipitates arranged in a layered manner in the lenses of a brittle star, Ophiocoma wendtii. Here we propose the mechanisms of formation of this functional hierarchical structure under conditions of ambient temperature and limited solid diffusion. We propose that formation proceeds via a spinodal decomposition of a liquid or gel-like magnesium amorphous calcium carbonate (Mg-ACC) precursor into Mg-rich nanoparticles and a Mg-depleted amorphous matrix. In a second step, crystallization of the decomposed amorphous precursor leads to the formation of high-Mg particle-rich layers. The model is supported by our experimental results in synthetic systems. These insights have significant implications for fundamental understanding of the role of Mg-ACC material transformation during crystallization and its subsequent stability.

Retinoic acid/calcite micro-carriers inserted in fibrin scaffolds modulate neuronal cell differentiation.

The controlled release of cell differentiating agents is crucial in many aspects of regenerative medicine. Here we propose the use of hybrid calcite single crystals as micro-carriers for the controlled and localized release of retinoic acid, which is entrapped within the crystalline lattice. The release of retinoic acid occurs only in the proximity of stem cells, upon dissolution of the calcite hybrid crystals that are dispersed in the fibrin scaffold. These hybrid crystals provide a sustained dosage of the entrapped agent. The environment provided by this composite scaffold enables differentiation towards neuronal cells that form a three-dimensional neuronal network.

A fungal mycelium templates the growth of aragonite needles.

Fungi live within diverse environments and survive well under extreme conditions that are usually beyond the tolerance of most other organisms. In different environments fungi are known to induce precipitation of a wide range of minerals. Various species of fungi have been shown to facilitate calcium carbonate mineralization. Here, inspired by examples of needle-fiber calcite formed via fungus-induced biomineralization typically observed in soils and sediments, we utilized inactivated fungus to synthetically induce precipitation of CaCO3 needles. To our knowledge, the feasibility of growing aragonitic needles within fungal mycelium in vitro has not been previously demonstrated. The needles we obtained were curved, displayed hexagonal facets, and demonstrated high-aspect ratios close to 60. The size and shape of these synthetic needles matched those of the mycelium of the natural fungus. Utilizing high-resolution characterization techniques, we studied the morphology and the micro- and nanostructures of the aragonitic needles. Our findings showed that even inactivated fungal mycelium, if present in the crystallization environment, can serve as a template for the formation of high-aspect ratio fibers and can stabilize metastable polymorphs.