Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 88
Filtrar
1.
Nat Commun ; 15(1): 5326, 2024 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-38909017

RESUMO

Solid-water interfaces are crucial for clean water, conventional and renewable energy, and effective nuclear waste management. However, reflecting the complexity of reactive interfaces in continuum-scale models is a challenge, leading to oversimplified representations that often fail to predict real-world behavior. This is because these models use fixed parameters derived by averaging across a wide physicochemical range observed at the molecular scale. Recent studies have revealed the stochastic nature of molecular-level surface sites that define a variety of reaction mechanisms, rates, and products even across a single surface. To bridge the molecular knowledge and predictive continuum-scale models, we propose to represent surface properties with probability distributions rather than with discrete constant values derived by averaging across a heterogeneous surface. This conceptual shift in continuum-scale modeling requires exponentially rising computational power. By incorporating our molecular-scale understanding of solid-water interfaces into continuum-scale models we can pave the way for next generation critical technologies and novel environmental solutions.

2.
ACS Appl Mater Interfaces ; 16(22): 29390-29401, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38787535

RESUMO

In natural and engineered environmental systems, calcium sulfate (CaSO4) nucleation commonly occurs at dynamic liquid-liquid interfaces. Although CaSO4 is one of the most common minerals in oil spills and oil-water separation, the mechanisms driving its nucleation at these liquid-liquid interfaces remain poorly understood. In this study, using in situ small-angle X-ray scattering (SAXS), we examined CaSO4 nucleation at oil-water interfaces and found that within 60 minutes of reaction, short rod-shaped nanoparticles (with a radius of gyration (Rg) of 17.2 ± 2.7 nm and a length of 38.2 ± 5.8 nm) had formed preferentially at the interfaces. Wide-angle X-ray scattering (WAXS) analysis identified these nanoparticles as gypsum (CaSO4·2H2O). In addition, spherial nanoparticles measuring 4.1 nm in diameter were observed at oil-water interfaces, where surface-enhanced Raman spectroscopy (SERS) revealed an elevated pH compared to the bulk solution. The negatively charged oil-water interfaces preferentially adsorb calcium ions, collectively promoting CaSO4 formation there. CaSO4 particle formation at the oil-water interface follows a nonclassical nucleation (N-CNT) pathway by forming ultrasmall amorphous spherical particles which then aggregate to form intermediate nanoparticles, subsequently growing into nanorod-shaped gypsum. These findings of this study provide insights into mineral scaling during membrane separation and can inform more efficient oil transport in energy recovery systems.

3.
Environ Sci Technol ; 57(30): 11056-11066, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37467155

RESUMO

Because of its favorable thermodynamics and fast kinetics, heterogeneous solid nucleation on membranes triggers early-stage mineral scaling. Iron (hydr)oxide, a typical membrane scale, initially forms as nanoparticles that interact with surface functional groups on membranes, but these nanoscale phenomena are difficult to observe in real time. In this study, we utilized in situ grazing incidence small angle X-ray scattering and ex situ atomic force microscopy to examine the heterogeneous nucleation of iron (hydr)oxide on surface functional groups commonly used in membranes, including hydroxyl (OH), carboxyl (COOH), and fluoro (F) groups. We found that, compared to nucleation on hydrophilic OH- and COOH-surfaces, the high hydrophobicity of an F-modified surface significantly reduced the extents of both heterogeneously and homogeneously formed iron (hydr)oxide nucleation. Moreover, on the OH-surface, the high functional group density of 0.76 nmol/cm2 caused faster heterogeneous nucleation than that on a COOH-surface, with a density of 0.28 ± 0.04 nmol/cm2. The F-surface also had the highest heterogeneous nucleation energy barrier (26 ± 0.6 kJ/mol), followed by COOH- (23 ± 0.8 kJ/mol) and OH- (20 ± 0.9 kJ/mol) surfaces. The kinetic and thermodynamic information provided here will help us better predict the rates and extents of early-stage scaling of iron (hydr)oxide nanoparticles in membrane processes.

4.
Sci Rep ; 13(1): 9400, 2023 Jun 09.
Artigo em Inglês | MEDLINE | ID: mdl-37296283

RESUMO

Many challenges related to carbon-dioxide ([Formula: see text]) sequestration in subsurface rock are linked to the injection of fluids through induced or existing fracture networks and how these fluids are altered through geochemical interactions. Here, we demonstrate that fluid mixing and carbonate mineral distributions in fractures are controlled by gravity-driven chemical dynamics. Using optical imaging and numerical simulations, we show that a density contrast between two miscible fluids causes the formation of a low-density fluid runlet that increases in areal extent as the fracture inclination decreases from 90[Formula: see text] (vertical fracture plane) to 30[Formula: see text]. The runlet is sustained over time and the stability of the runlet is controlled by the gravity-driven formation of 3D vortices that arise in a laminar flow regime. When homogeneous precipitation was induced, calcium carbonate covered the entire surface for horizontal fractures (0[Formula: see text]). However, for fracture inclinations greater than 10[Formula: see text], the runlet formation limited the areal extent of the precipitation to less than 15% of the fracture surface. These insights suggest that the ability to sequester [Formula: see text] through mineralization along fractures will depend on the fracture orientation relative to gravity, with horizontal fractures more likely to seal uniformly.


Assuntos
Carbonato de Cálcio , Dióxido de Carbono
5.
Chem Rev ; 123(10): 6413-6544, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37186959

RESUMO

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

6.
Gut and Liver ; : 69-77, 2023.
Artigo em Inglês | WPRIM (Pacífico Ocidental) | ID: wpr-966881

RESUMO

Background/Aims@#Epstein-Barr virus (EBV) and Helicobacter pylori (HP) coinfection may synergistically induce severe inflammatory responses in the stomach tissue, increasing the risk of developing gastric cancer. We aimed to analyze the effect of EBV and HP coinfection on the clinicopathologic features and prognosis of gastric cancer, as well as to evaluate the role of EBV infection in non-gastric carcinoma with lymphoid stroma (non-GCLS). @*Methods@#Overall, 956 patients who underwent surgery for gastric cancer between September 2014 and August 2015 were eligible and divided into groups, according to GCLS morphology, EBV infection, and HP infection. Clinicopathologic characteristics and oncologic outcomes were analyzed retrospectively. @*Results@#EBV and HP coinfection was significantly associated with male sex, proximal location, GCLS morphology, and equivocal p53 expression (p<0.001). Multivariate analysis revealed that EBV infection alone (hazard ratio [HR], 0.362; 95% CI, 0.131 to 0.996; p=0.049) and lower third location (HR, 0.624; 95% CI, 0.413 to 0.943; p=0.025) were inversely correlated with overall survival. During median follow-up period of 72 months, overall survival rate was not significantly different between the EBV and HP coinfection group and others (97.6% vs 86.8%, log-rank p=0.144). In non-GCLS patients (n=920), overall survival rate was not significantly different between the EBV infection group and others (96.9% vs 86.4%, log-rank p=0.126). @*Conclusions@#EBV and HP coinfection is not an independent prognostic factor for gastric cancer. EBV infection status, regardless of HP infection, affects the clinicopathologic features of all types of gastric cancer. However, it does not lead to a significant difference in overall survival of nonGCLS patients.

7.
Sci Rep ; 12(1): 22163, 2022 12 22.
Artigo em Inglês | MEDLINE | ID: mdl-36550285

RESUMO

Engineered cyanobacterium Synechococcus elongatus can use light and CO2 to produce sucrose, making it a promising candidate for use in co-cultures with heterotrophic workhorses. However, this process is challenged by the mutual stresses generated from the multispecies microbial culture. Here we demonstrate an ecosystem where S. elongatus is freely grown in a photo-bioreactor (PBR) containing an engineered heterotrophic workhorse (either ß-carotene-producing Yarrowia lipolytica or indigoidine-producing Pseudomonas putida) encapsulated in calcium-alginate hydrogel beads. The encapsulation prevents growth interference, allowing the cyanobacterial culture to produce high sucrose concentrations enabling the production of indigoidine and ß-carotene in the heterotroph. Our experimental PBRs yielded an indigoidine titer of 7.5 g/L hydrogel and a ß-carotene titer of 1.3 g/L hydrogel, amounts 15-22-fold higher than in a comparable co-culture without encapsulation. Moreover, 13C-metabolite analysis and protein overexpression tests indicated that the hydrogel beads provided a favorable microenvironment where the cell metabolism inside the hydrogel was comparable to that in a free culture. Finally, the heterotroph-containing hydrogels were easily harvested and dissolved by EDTA for product recovery, while the cyanobacterial culture itself could be reused for the next batch of immobilized heterotrophs. This co-cultivation and hydrogel encapsulation system is a successful demonstration of bioprocess optimization under photobioreactor conditions.


Assuntos
Alginatos , Hidrogéis , Técnicas de Cocultura , beta Caroteno , Ecossistema , Sacarose/metabolismo , Fotobiorreatores
8.
ACS Nano ; 16(12): 20238-20250, 2022 12 27.
Artigo em Inglês | MEDLINE | ID: mdl-36441924

RESUMO

Every year, large quantities of plastics are produced and used for diverse applications, growing concerns about the waste management of plastics and their release into the environment. Plastic debris can break down into millions of pieces that adversely affect natural organisms. In particular, the photolysis of micro/nanoplastics can generate reactive oxygen species (ROS). However, their oxidative roles in initiating redox chemical reactions with heavy and transition metals have received little attention. In this study, we investigated whether the photolysis of polystyrene (PS) nanoplastics can induce the oxidation of Mn2+(aq) to Mn oxide solids. We found that PS nanoplastics not only produced peroxyl radicals (ROO•) and superoxide radicals (O2•-) by photolysis, which both play a role in unexpected Mn oxidation, but also served as a substrate for facilitating the heterogeneous nucleation and growth of Mn oxide solids and controlling the formation rate and crystalline phases of Mn oxide solids. These findings help us to elucidate the oxidative roles of nanoplastics in the oxidation of redox-active metal ions. The production of ROS from nanoplastics in the presence of light can endanger marine life and human health, and affect the mobility of the nanoplastics in the environment via redox reactions, which in turn may negatively impact their environmental remediation.


Assuntos
Poliestirenos , Poluentes Químicos da Água , Humanos , Poliestirenos/química , Microplásticos , Espécies Reativas de Oxigênio , Iluminação , Plásticos , Óxidos , Oxirredução , Estresse Oxidativo , Poluentes Químicos da Água/química
9.
Water Res ; 222: 118831, 2022 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-35872522

RESUMO

Manganese (Mn) oxide solids are ubiquitous in nature, acting as both electron donors and acceptors in diverse redox reactions in the environment. Reactions of Mn(III/IV) oxides with dissolved natural organic matter (DOM) are commonly described as reductive dissolutions that generate Mn2+(aq). In this study, we investigated the role of photochemical reactions of DOM in Mn2+(aq) oxidation and the resulting formation of Mn oxide solids. During the photolysis of DOM, reactive intermediates can be generated, including excited triplet state DOM (3DOM*), hydroxyl radicals (•OH), superoxide radicals (O2•-), hydrogen peroxide, and singlet oxygen. Among these, we found that O2•- radicals were mainly responsible for Mn oxidation. The solution pH controlled the formation of Mn oxide solids by affecting both Mn2+ oxidation by O2•- during photolysis of DOM and reductive dissolutions of Mn oxide solids by DOM. Further, with the addition of bromide ions (Br-), reactions between 3DOM* and Br-, together with reactions between •OH and Br-, can form reactive bromide radicals. The formed Br radicals also promoted Mn oxide formation. In DOM with more aromatic functional groups, more Mn2+ was oxidized to Mn oxide solids. This enhanced oxidation could be the result of promoted pathways from charge-transfer state DOM (DOM•+/•-) to O2•-. These new observations advance our understanding of natural Mn2+ oxidation and Mn(III/IV) oxide formation and highlight the underappreciated oxidative roles of DOM in the oxidation of metal ions in surface water illuminated by sunlight.


Assuntos
Brometos , Matéria Orgânica Dissolvida , Compostos de Manganês , Óxidos , Fotólise
10.
Sci Total Environ ; 847: 157533, 2022 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-35878849

RESUMO

Harmful algal blooms (HAB) are a major environmental concern in eutrophic aquatic systems. To mitigate HABs and recover the phosphorus that drives algal growth, this study developed hydrogel composites seeded with calcium phosphate and wollastonite particles, which first adsorb phosphate (P) and then precipitate it as calcium phosphate. Using a fast-growing cyanobacterium, Synechococcus elongatus 2973, as a model microalga, we found that the mineral-hydrogel composites reduced dissolved P in BG11 media from 5.1 mg/L to 0.31 mg/L, initially reducing the biomass growth rate by up to 73 % and ultimately reducing the total biomass concentration by 75 %. When applied to municipal wastewater and agricultural run-off, the composites removed 96 % and 91 % of the dissolved P, respectively. Moreover, when the recovered P-enriched composites were reused as a slow-release bio-compatible fertilizer in a photobioreactor, they effectively supported algal growth without blocking light and interfering with photosynthesis. The P-enriched composites could tune the P concentration in the culture medium and significantly promote algal lipid accumulation. This study demonstrates the mineral-hydrogel composites' potential to treat point sources of P pollution and subsequently facilitate photoautotrophic biofuel production as a nutrient, effectively recycling the captured P.


Assuntos
Proliferação Nociva de Algas , Hidrogéis , Biocombustíveis , Fertilizantes , Lipídeos , Minerais , Fosfatos , Fósforo , Águas Residuárias
11.
Environ Sci Technol ; 56(12): 9063-9074, 2022 06 21.
Artigo em Inglês | MEDLINE | ID: mdl-35617118

RESUMO

Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO3's formation and is seldom found to significantly affect multiple CaCO3 formation processes. Here, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO3 precursors and nuclei, promoting CaCO3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO3. Meanwhile, adsorbed sulfate on CaCO3 nuclei may poison the surface of smaller CaCO3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.


Assuntos
Carbonato de Cálcio , Sulfatos , Eletricidade Estática
12.
Annu Rev Phys Chem ; 73: 453-477, 2022 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-35113740

RESUMO

All solid materials are created via nucleation. In this evolutionary process, nuclei form in solution or at interfaces, expand by monomeric growth and oriented attachment, and undergo phase transformation. Nucleation determines the location and size of nuclei, whereas growth controls the size, shape, and aggregation of newly formed nanoparticles. These physical properties of nanoparticles can affect their functionalities, reactivities, and porosities, as well as their fate and transport. Recent advances in nanoscale analytical technologies allow in situ real-time observations, enabling us to uncover the molecular nature of nuclei and the critical controlling factors for nucleation and growth. Although a single theory cannot yet fully explain such evolving processes, we have started to better understand how both classical andnonclassical theories can work together, and we have begun to recognize the importance of connecting these theories. This review discusses the recent convergence of knowledge about the nucleation and growth of nanoparticles.


Assuntos
Nanopartículas
13.
ACS Appl Mater Interfaces ; 13(41): 48457-48468, 2021 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-34633172

RESUMO

Strong underwater adhesives are attractive materials for biomedical healing and underwater repair, but their success in applications has been limited, owing to challenges with underwater setting and with balancing surface adhesion and cohesion. Here, we applied synthetic biology approaches to overcome these challenges through design and synthesis of a novel hybrid protein consisting of the zipper-forming domains of an amyloid protein, flexible spider silk sequences, and a dihydroxyphenylalanine (DOPA)-containing mussel foot protein (Mfp). This partially structured, hybrid protein can self-assemble into a semi-crystalline hydrogel that exhibits high strength and toughness as well as strong underwater adhesion to a variety of surfaces, including difficult-to-adhere plastics, tendon, and skin. The hydrogel allows selective debonding by oxidation or iron-chelating treatments. Both the material design and the biosynthetic approach explored in this study will inspire future work for a wide range of hybrid protein-based materials with tunable properties and broad applications.


Assuntos
Adesivos/química , Hidrogéis/química , Proteínas Recombinantes de Fusão/química , Adesividade , Proteínas Amiloidogênicas/química , Animais , Bivalves/química , Fibroínas/química , Engenharia de Proteínas , Proteínas/química , Aranhas/química , Substâncias Viscoelásticas/química , Água/química
14.
Environ Sci Technol ; 55(20): 13759-13769, 2021 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-34581181

RESUMO

The distinctive optical and electronic properties of two-dimensional (2D) molybdenum disulfide (MoS2) make it a promising photocatalyst and photothermal agent in aqueous applications. In terms of environmental stability, MoS2 has been considered insoluble, but 2D MoS2 nanosheets can be susceptible to dissolution, owing to their large surface areas and highly accessible reactive sites, including defects at the basal plane and edge sites. Under light illumination, the dissolution of 2D MoS2 nanosheets can be further accelerated by their photochemical reactivity. To elucidate MoS2 reactivity in the environment, here we investigated the thickness-dependent dissolution of MoS2 under illumination. To synthesize nanoscale thicknesses of MoS2, we exfoliated bulk MoS2 by ultrasonication and controlled the layer thickness by iterative cascade centrifugation, producing MoS2 nanosheets averaging either ∼18 nm or ∼46 nm thick, depending on the centrifugation rate. Under simulated sunlight, MoS2 dissolution was accelerated, the Mo6+ composition increased, and the solution pH decreased compared to those in the dark. These results suggest that light exposure promotes the oxidation of MoS2, causing faster dissolution. Importantly, 18 nm thick MoS2 exhibited faster dissolution than either 46 nm or bulk MoS2, driven by the superoxide radical (O2•-) generation promoted by its relative thinness. These findings highlight the important role of the thickness-dependent photochemistry of MoS2 nanosheets in their dissolution, which is directly linked to their environmental behavior and stability.


Assuntos
Molibdênio , Estresse Oxidativo , Oxirredução , Solubilidade
15.
Nat Commun ; 12(1): 5182, 2021 08 30.
Artigo em Inglês | MEDLINE | ID: mdl-34462443

RESUMO

Manmade high-performance polymers are typically non-biodegradable and derived from petroleum feedstock through energy intensive processes involving toxic solvents and byproducts. While engineered microbes have been used for renewable production of many small molecules, direct microbial synthesis of high-performance polymeric materials remains a major challenge. Here we engineer microbial production of megadalton muscle titin polymers yielding high-performance fibers that not only recapture highly desirable properties of natural titin (i.e., high damping capacity and mechanical recovery) but also exhibit high strength, toughness, and damping energy - outperforming many synthetic and natural polymers. Structural analyses and molecular modeling suggest these properties derive from unique inter-chain crystallization of folded immunoglobulin-like domains that resists inter-chain slippage while permitting intra-chain unfolding. These fibers have potential applications in areas from biomedicine to textiles, and the developed approach, coupled with the structure-function insights, promises to accelerate further innovation in microbial production of high-performance materials.


Assuntos
Conectina/química , Conectina/genética , Escherichia coli/metabolismo , Fibras Musculares Esqueléticas/química , Animais , Fenômenos Biomecânicos , Conectina/metabolismo , Cristalização , Escherichia coli/genética , Expressão Gênica , Peso Molecular , Fibras Musculares Esqueléticas/metabolismo , Polimerização , Polímeros/química , Polímeros/metabolismo , Dobramento de Proteína , Coelhos
16.
Environ Sci Technol ; 55(15): 10442-10450, 2021 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-34292702

RESUMO

The hydroxyl radical, •OH, is one of the most reactive free radicals and plays significant roles in the oxidative degradation of organic pollutants and the electron transfer of inorganic ions in natural and engineered environmental processes. To quantitatively determine the contribution of •OH to oxidative reactions, a specific scavenger, such as tert-butyl alcohol (TBA), is usually added to eliminate •OH effects. Although TBA is commonly assumed to transform •OH into oxidatively inert products, this study demonstrates that utilizing TBA as an •OH scavenger generates the secondary peroxyl radical (ROO•), influencing the oxidation of transition metals, such as Mn. Although ROO• is less reactive than •OH, it has an extended half-life and a longer diffusion distance that enables more redox reactions, such as the oxidation of Mn2+(aq) to MnIV oxide solids. In addition to promoting Mn2+(aq) oxidation kinetics, TBA can also affect the crystalline phases, oxidation states, and morphologies of Mn oxide solids. Thus, the oxidative roles of •OH in aqueous redox reactions cannot be examined simply by adding TBA: the effects of secondary ROO• must also be considered. This study urges a closer look at the potential formation of secondary radicals during scavenged oxidative reactions in environmental systems.


Assuntos
Radical Hidroxila , terc-Butil Álcool , Radicais Livres , Oxirredução , Estresse Oxidativo
17.
Biomater Sci ; 9(17): 5907-5916, 2021 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-34286730

RESUMO

The adaptive response of bones to mechanical loading is essential for musculoskeletal development. Despite the importance of collagen in bone mineralization, little is known about how cyclic strain influences physicochemical responses of collagen, especially at the early stage of mineralization when the levels of strain are higher than those in mature bones. The findings in this study show that, without any cell-mediated activity, cyclic strain increases nucleation rates of calcium phosphate (CaP) nanocrystals in highly-organized collagen matrices. The cyclic strain enhances the transport of mineralization fluids with nucleation precursors into the matrix, thus forming more CaP nanocrystals and increasing the elastic modulus of the collagen matrix. The results also suggest that the multiscale spatial distribution of nanocrystals in the fibrous collagen network determines tissue-level mechanical properties more critically than the total mineral content. By linking nano- and micro-scale observations with tissue-level mechanical properties, we provide new insights into designing better biomaterials.


Assuntos
Matriz Óssea , Calcificação Fisiológica , Osso e Ossos , Colágeno , Minerais
18.
ACS Nano ; 15(7): 11843-11853, 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34251182

RESUMO

The ability of amyloid proteins to form stable ß-sheet nanofibrils has made them potential candidates for material innovation in nanotechnology. However, such a nanoscale feature has rarely translated into attractive macroscopic properties for mechanically demanding applications. Here, we present a strategy by fusing amyloid peptides with flexible linkers from spidroin; the resulting polymeric amyloid proteins can be biosynthesized using engineered microbes and wet-spun into macroscopic fibers. Using this strategy, fibers from three different amyloid groups were fabricated. Structural analyses unveil the presence of ß-nanocrystals that resemble the cross-ß structure of amyloid nanofibrils. These polymeric amyloid fibers have displayed strong and molecular-weight-dependent mechanical properties. Fibers made of a protein polymer containing 128 repeats of the FGAILSS sequence displayed an average ultimate tensile strength of 0.98 ± 0.08 GPa and an average toughness of 161 ± 26 MJ/m3, surpassing most recombinant protein fibers and even some natural spider silk fibers. The design strategy and the biosynthetic approach can be expanded to create numerous functional materials, and the macroscopic amyloid fibers will enable a wide range of mechanically demanding applications.


Assuntos
Fibroínas , Nanopartículas , Aranhas , Animais , Resistência à Tração , Seda/química , Fibroínas/química , Proteínas Amiloidogênicas
19.
Environ Sci Technol ; 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34314155

RESUMO

Unveiling the effects of an environmental abundant anion "sulfate" on the formation of calcium carbonate (CaCO3) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate-CaCO3 interactions at the explicit first step of CaCO3 formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO3 nucleation is monitored in real time as a function of sulfate concentrations (0-10 mM Na2SO4) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO3 nucleation rate, causing a 120% increase in the CaCO3 nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO3 and finds a non-linear trend, suggesting that CaCO3 heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO3 interfacial energies, a key step toward achieving natural and engineered controls on CaCO3 nucleation.

20.
Adv Mater ; 33(28): e2000922, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32537817

RESUMO

Herein, the recent advances in realizing highly efficient cellulose-based solar evaporators for alleviating the global water crisis are summarized. Fresh water scarcity is one of the most threatening issues for sustainable development. Solar steam generation, which harnesses the abundant sunlight, has been recognized as a sustainable approach to harvest fresh water. In contrast to synthetic polymeric materials that can pose serious negative environmental impacts, cellulose-based materials, owing to their biocompatibility, renewability, and sustainability, are highly attractive for realizing solar steam generators. The molecular and macromolecular features of cellulose and the physicochemical properties of extracted cellulose nanoparticles (cellulose nanocrystals and cellulose nanofibrils (CNF)) and natural cellulose materials (wood and bacterial nanocellulose (BNC)) that make them attractive as supporting substrate materials in solar steam generators are briefly discussed. Recent progress in designing highly efficient cellulose-based solar evaporators, including utilizing extracted cellulose nanoparticles via bottom-up assembly CNF, natural cellulose materials with intrinsic hierarchical structure (wood and BNC), and commercial planar cellulose substrates (air-laid paper, cellulose paper, and cotton fabric) is reviewed. The outstanding challenges that need to be addressed for these materials and devices to be utilized in the real-world and in overcoming global water crisis are also briefly highlighted.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...