Synergetic Codoping in Fluorinated Ti_1−<i>x</i>Zr_<i>x</i>O₂ Hollow Microspheres

The synergetic effects of codoped Zr4+ and F− ions within anatase hollow microspheres produced by a fluoride-mediated self-transformation strategy are investigated and discussed. The concomitant participation of F− promotes lattice substitution of Ti4+ ions by Zr4+ and facilitates the transformation of surface-segregated amorphous ZrOx clusters into Zr−F species. Codoping is associated with electron transfer-mediated charge compensation between the Zr/F impurities, which reduces the number of both bulk and surface defects and provides a stabilizing effect on the local structure. Moreover, these synergetic interactions influence the textural characteristics and surface states of the TiO2 host, such that the photocatalytic activity with regard to the decomposition of gaseous toluene is enhanced. Synergetic codoping of heterogeneous impurities within the host lattice or near-surface regions provides a general and effective alternative strategy for higher level doping and surface modification, which may be crucial for catalyst design and associated applications

Novel Bioinorganic Nanostructures Based on Mesolamellar Intercalation or Single-Molecule Wrapping of DNA Using Organoclay Building Blocks

Nanosheets or nanoclusters of aminopropyl-functionalized magnesium phyllosilicate (AMP) were prepared in water by exfoliation and used as structural building blocks for the preparation of DNA-based hybrid nanostructures in the form of ordered mesolamellar nanocomposites or highly elongated nanowires, respectively. The former consisted of alternating layers of single sheets of AMP interspaced with intercalated monolayers of intact double-stranded DNA molecules of relatively short length (∼700 base pairs) that were accessible to small molecules such as ethidium bromide. In contrast, the nanowires comprised isolated micrometer-long molecules of λ-DNA or plasmid DNA that were sheathed in an ultrathin organoclay layer and which were either protected from or remained accessible to endonuclease-mediated clipping depending on the extent of biomolecule wrapping. Both types of hybrid nanostructures showed a marked increase in the DNA melting (denaturation) temperature, indicating significant thermal stabilization of the confined biomolecules. Our results suggest that nanoscale building blocks derived from organically modified inorganic clays could be useful agents for enhancing the chemical, thermal, and mechanical stability of isolated molecules or ensembles of DNA. Such constructs should have increased potential as functional components in bionanotechnology and nonviral gene transfection

Design and Construction of Higher-Order Structure and Function in Proteinosome-Based Protocells

The design and construction of higher-order structure and function in proteinosome microcompartments enclosed by a cross-linked membrane of amphiphilic bovine serum albumin/poly­(N-isopropylacrylamide) (BSA-NH2/PNIPAAm) nanoconjugates is described. Three structure/function relationships are investigated: (i) differential chemical cross-linking for the control of membrane disassembly and regulated release of encapsulated genetic polymers; (ii) enzyme-mediated hydrogel structuring of the internal microenvironment to increase mechanical robustness and generate a molecularly crowded reaction environment; and (iii) self-production of a membrane-enclosing outer hydrogel wall for generating protease-resistant forms of the protein–polymer protocells. Our results highlight the potential of integrating aspects of supramolecular and polymer chemistry into the design and construction of novel bioinspired microcompartments as a step toward small-scale materials systems based on synthetic cellularity

Secretion and Reversible Assembly of Extracellular-like Matrix by Enzyme-Active Colloidosome-Based Protocells

The secretion and reversible assembly of an extracellular-like matrix by enzyme-active inorganic protocells (colloidosomes) is described. Addition of N-fluorenyl-methoxycarbonyl-tyrosine-(O)-phosphate to an aqueous suspension of alkaline phosphatase-containing colloidosomes results in molecular uptake and dephosphorylation to produce a time-dependent sequence of supramolecular hydrogel motifs (outer membrane wall, cytoskeletal-like interior and extra-protocellular matrix) that are integrated and remodelled within the microcapsule architecture and surrounding environment. Heat-induced disassembly of the extra-protocellular matrix followed by cooling produces colloidosomes with a densely packed hydrogel interior. These procedures are exploited for the fabrication of nested colloidosomes with spatially delineated regions of hydrogelation

Design and Construction of Higher-Order Structure and Function in Proteinosome-Based Protocells

The design and construction of higher-order structure and function in proteinosome microcompartments enclosed by a cross-linked membrane of amphiphilic bovine serum albumin/poly­(<i>N</i>-isopropylacrylamide) (BSA-NH₂/PNIPAAm) nanoconjugates is described. Three structure/function relationships are investigated: (i) differential chemical cross-linking for the control of membrane disassembly and regulated release of encapsulated genetic polymers; (ii) enzyme-mediated hydrogel structuring of the internal microenvironment to increase mechanical robustness and generate a molecularly crowded reaction environment; and (iii) self-production of a membrane-enclosing outer hydrogel wall for generating protease-resistant forms of the protein–polymer protocells. Our results highlight the potential of integrating aspects of supramolecular and polymer chemistry into the design and construction of novel bioinspired microcompartments as a step toward small-scale materials systems based on synthetic cellularity

From Natural Attapulgite to Mesoporous Materials: Methodology, Characterization and Structural Evolution

In this paper, we report the synthesis of hexagonally ordered aluminum-containing mesoporous silica, Al-MCM-41, from natural attapulgite (Al-substituted Si8O20Mg5(OH)2(H2O)4·4H2O) without addition of silica or aluminum reagents. A pretreatment process involving sequential mechanical grinding and acid leaching is critical to the successful use of attapulgite as a source of both Si and Al in the surfactant-templated hydrothermal synthesis of Al-MCM-41. The resulting mesophase had a surface area of 1030 m2/g and an average pore diameter of 3.7 nm with narrow pore size distribution. The influence of changes in processing parameters, such as grinding time, hydrothermal conditions, and calcination temperature, on the textural characteristics of the Al-MCM-41 products is studied. Investigations of the mechanism of structural evolution indicate that grinding of attapulgite results in amorphization and partial structural breakdown, transformation of the fibrous mineral bundles into rod-shaped particles, and partial displacement of octahedrally coordinated Al3+ ions into the Si−O tetrahedral framework. Subsequent acid etching dissolves the Mg-rich octahedral sheets to produce samples with variable texture due to modifications in the residual aluminum-containing silicate sheets and associated silica fragments. Solid-state magic-angle spinining NMR spectroscopy indicates that Al3+ ions are located in both octahedral and tetrahedral sites in the as-synthesized Al-MCM-41 samples, but that the calcined products consist primarily of Al3+ ions substituted in the tetrahedrally coordinated silica matrix of the ordered channel wall structure

Triggerable Protocell Capture in Nanoparticle-Caged Coacervate Microdroplets

Controlling the dynamics of mixed communities of cell-like entities (protocells) provides a step toward the development of higher-order cytomimetic behaviors in artificial cell consortia. In this paper, we develop a caged protocell model with a molecularly crowded coacervate interior surrounded by a non-cross-linked gold (Au)/poly­(ethylene glycol) (PEG) nanoparticle-jammed stimuli-responsive membrane. The jammed membrane is unlocked by either exogenous light-mediated Au/PEG dissociation at the Au surface or endogenous enzyme-mediated cleavage of a ketal linkage on the PEG backbone. The membrane assembly/disassembly process is used for the controlled and selective uptake of guest protocells into the caged coacervate microdroplets as a path toward an all-water model of triggerable transmembrane uptake in synthetic protocell communities. Active capture of the guest protocells stems from the high sequestration potential of the coacervate interior such that tailoring the surface properties of the guest protocells provides a rudimentary system of protocell sorting. Our results highlight the potential for programming surface-contact interactions between artificial membrane-bounded compartments and could have implications for the development of protocell networks, storage and delivery microsystems, and microreactor technologies

Triggerable Protocell Capture in Nanoparticle-Caged Coacervate Microdroplets

Controlling the dynamics of mixed communities of cell-like entities (protocells) provides a step toward the development of higher-order cytomimetic behaviors in artificial cell consortia. In this paper, we develop a caged protocell model with a molecularly crowded coacervate interior surrounded by a non-cross-linked gold (Au)/poly­(ethylene glycol) (PEG) nanoparticle-jammed stimuli-responsive membrane. The jammed membrane is unlocked by either exogenous light-mediated Au/PEG dissociation at the Au surface or endogenous enzyme-mediated cleavage of a ketal linkage on the PEG backbone. The membrane assembly/disassembly process is used for the controlled and selective uptake of guest protocells into the caged coacervate microdroplets as a path toward an all-water model of triggerable transmembrane uptake in synthetic protocell communities. Active capture of the guest protocells stems from the high sequestration potential of the coacervate interior such that tailoring the surface properties of the guest protocells provides a rudimentary system of protocell sorting. Our results highlight the potential for programming surface-contact interactions between artificial membrane-bounded compartments and could have implications for the development of protocell networks, storage and delivery microsystems, and microreactor technologies

Mineralogical constraints on the genesis of an alkalic-type epithermal Au-Te deposit: Tuvatu, Fiji

To study the characteristics and genetic constraints on alkalic-type epithermal Au mineralisation, here we use the example of the Tuvatu Au-Ag deposit in Fiji, with an emphasis on detailed, quantitative mineralogy. Tuvatu mineralisation is hosted in a weakly altered potassic monzonite in parallel sided-veins of K-feldspar, biotite, sericite, calcite, and quartz, with epidote-bearing propylitic or sericite-rich selvages. Petrographic study of core and automated SEM-based mineralogical mapping of thin sections have been utilised to update previous parageneses of the deposit. Automated SEM techniques enable identification of small amounts of obscure minerals that form minuscule grains, which would otherwise be very difficult to identify and measure. As a result, our data show that gold fineness is extremely high, with the mean and median Au content of native-Au and Au-Ag alloy being 96.7% and 100% respectively, yet precious-metal tellurides make up the majority of the Au deportment. Tellurides show evidence of multiple phases and zoning with depth. For the first time at Tuvatu, Pt- and Pd-tellurides have been identified. Tuvatu has a number of features in common with alkalic systems elsewhere, including quartz-poor, carbonate-rich veins and alteration, abundant and varied telluride minerals, high gold grades, and Pt-Pd occurrences. We suggest these characteristics are a result of relatively high temperature (250–300 °C) fluids and immiscible semi-metal melts fluxing into the shallow epithermal environment. High pH fluids lead to quartz-poor alteration, but mildly acidic conditions dominate in areas of high fluid flux, where the lower pH causes precipitation of tellurides with quartz. Boiling of the fluids produces zonation of tellurides with depth but leaves relatively subtle textural evidence compared to boiling in most epithermal systems, in common with other quartz poor, carbonate-rich alkalic epithermal deposits around the world.</p

Autonomic Integration in Nested Protocell Communities

The self-driven organization of model protocells into higher-order nested cytomimetic systems with coordinated structural and functional relationships offers a step toward the autonomic implementation of artificial multicellularity. Here, we describe an endosymbiotic-like pathway in which proteinosomes are captured within membranized alginate/silk fibroin coacervate vesicles by guest-mediated reconfiguration of the host protocells. We demonstrate that interchange of coacervate vesicle and droplet morphologies through proteinosome-mediated urease/glucose oxidase activity produces discrete nested communities capable of integrated catalytic activity and selective disintegration. The self-driving capacity is modulated by an internalized fuel-driven process using starch hydrolases sequestered within the host coacervate phase, and structural stabilization of the integrated protocell populations can be achieved by on-site enzyme-mediated matrix reinforcement involving dipeptide supramolecular assembly or tyramine–alginate covalent cross-linking. Our work highlights a semi-autonomous mechanism for constructing symbiotic cell-like nested communities and provides opportunities for the development of reconfigurable cytomimetic materials with structural, functional, and organizational complexity