Direct, Broad-Spectrum Antimicrobial Activity of Ag-Doped Hydroxyapatite against Fastidious Anaerobic Periodontal and Aerobic Dental Bacteria.

Periodontitis and caries, while seemingly innocuous medical conditions, actually pose significant challenges because of their potential etiology with far more serious conditions. Efficacious treatment is hindered by bacterial antibiotic resistance. Standard AgNPs are ineffective against periodontal anaerobic bacteria, because they require oxidative dissolution to release Ag ions, which are the actual antimicrobial agents, but oxidation is not possible under anaerobic conditions.

Bioenergetics of iron snow fueling life on Europa.

The main sources of redox gradients supporting high-productivity life in the Europan and other icy ocean world oceans were proposed to be photolytically derived oxidants, such as reactive oxygen species (ROS) from the icy shell, and reductants (Fe(II), S(-II), CH, H) from bottom waters reacting with a (ultra)mafic seafloor. Important roadblocks to maintaining life, however, are that the degree of ocean mixing to combine redox species is unknown, and ROS damage biomolecules. Here, we envisage a unique solution using an acid mine drainage (AMD)-filled pit lakes analog system for the Europan ocean, which previous models predicted to be acidic.

Novel Chimeric Amino Acid-Fatty Alcohol Ester Amphiphiles Self-Assemble into Stable Primitive Membranes in Diverse Geological Settings.

Primitive cells are believed to have been self-assembled vesicular structures with minimal metabolic components, that were capable of self-maintenance and self-propagation in early Earth geological settings. The coevolution and self-assembly of biomolecules, such as amphiphiles, peptides, and nucleic acids, or their precursors, were essential for protocell emergence. Here, we present a novel class of amphiphiles-amino acid-fatty alcohol esters-that self-assemble into stable primitive membrane compartments under a wide range of geochemical conditions.

Side Group of Hydrophobic Amino Acids Controls Chiral Discrimination among Chiral Counterions and Metal-Organic Cages.

The self-assembly of chiral PdL metal-organic cages (MOCs) based on hydrophobic amino acids, including alanine (Ala), valine (Val), and leucine (Leu), into single-layered hollow spherical blackberry-type structures is triggered by nitrates through counterion-mediated attraction. In addition to nitrates, anionic -(-butoxycarbonyl) (Boc)-protected Ala, Val, and Leu were used as chiral counterions during the self-assembly of d-MOCs. Previously, we showed that l-Ala suppresses the self-assembly process of d-PdAla but has no effect on l-PdAla, i.

Freshwater and Evaporite Brine Compositions on Hadean Earth: Priming the Origins of Life.

The chemical composition of aqueous solutions during the Hadean era determined the availability of essential elements for prebiotic synthesis of the molecular building blocks of life. Here we conducted quantitative reaction path modeling of atmosphere-water-rock interactions over a range of environmental conditions to estimate freshwater and evaporite brine compositions. We then evaluated the solution chemistries for their potential to influence ribonucleotide synthesis and polymerization as well as protocell membrane stability.

Spatial survey of non-collagenous proteins in mineralizing and non-mineralizing vertebrate tissues .

Bone biomineralization is a complex process in which type I collagen and associated non-collagenous proteins (NCPs), including glycoproteins and proteoglycans, interact closely with inorganic calcium and phosphate ions to control the precipitation of nanosized, non-stoichiometric hydroxyapatite (HAP, idealized stoichiometry Ca(PO)(OH)) within the organic matrix of a tissue. The ability of certain vertebrate tissues to mineralize is critically related to several aspects of their function. The goal of this study was to identify specific NCPs in mineralizing and non-mineralizing tissues of two animal models, rat and turkey, and to determine whether some NCPs are unique to each type of tissue.

Toward the Understanding of Small Protein-Mediated Collagen Intrafibrillar Mineralization.

The design of improved materials for orthopedic implants and bone tissue engineering scaffolds relies on materials mimicking the properties of bone. Calcium phosphate (Ca-PO)-mineralized collagen fibrils arranged in a characteristic hierarchical structure constitute the building blocks of mineralized vertebrate tissues and control their biomechanical and biochemical properties. Large, flexible, acidic noncollagenous proteins (ANCPs) have been shown to influence collagen mineralization but little is known about mineralization mechanisms with the aid of small proteins.

Strong Enantiomeric Preference on the Macroion-Counterion Interaction Induced by Weakly Associated Chiral Counterions.

The role of chiral counterions on the attraction and self-assembly of chiral PdL metal organic cages (MOCs) with NO being the original counterion is studied by laser light scattering and isothermal titration calorimetry. Nitrates can trigger the self-assembly of macrocationic PdL into hollow spherical blackberry-type supramolecular structures counterion-mediated attraction. Although chiral counteranions, such as -(-butoxycarbonyl)-alanine (Boc-Ala), have weaker interaction with the MOCs compared to NO, they can induce different assembly behaviors between two enantiomeric MOCs by inhibiting the MOC-nitrate binding and weakening the interaction between them.

Oligo(l-glutamic acids) in Calcium Phosphate Precipitation: Mechanism of Delayed Phase Transformation.

Proteins and their mimics that contain negatively charged sequences are important in natural and biomimetic mineralization. The mechanism by which these sequences affect calcium phosphate mineralization is not well understood. Here, peptides containing different numbers of repeat units of contiguous glutamic acid residues, oligo(l-glutamic acid) ( = 3, 7, 8, 10), were investigated with regards to the mechanism in delaying the crystallization of amorphous calcium phosphate (ACP) while holding the amount of carboxylic acid groups in solution constant.

Oligo(l-glutamic acids) in Calcium Phosphate Precipitation: Chain Length Effect.

The understanding of calcium phosphate precipitation is of major interest in different fields of science, including medicine, biomaterials, and physical chemistry. The presence of additive biomacromolecules has been known to influence various stages of the precipitation process from nucleation to crystal growth. In the current work, well-defined sequences of short, negatively charged peptides, oligo(l-glutamic acids), were utilized as a model, inspired by contiguous sequences of acidic amino acids in natural biomineralization proteins.

Semipermeable Mixed Phospholipid-Fatty Acid Membranes Exhibit K/Na Selectivity in the Absence of Proteins.

Two important ions, K and Na, are unequally distributed across the contemporary phospholipid-based cell membrane because modern cells evolved a series of sophisticated protein channels and pumps to maintain ion gradients. The earliest life-like entities or protocells did not possess either ion-tight membranes or ion pumps, which would result in the equilibration of the intra-protocellular K/Na ratio with that in the external environment. Here, we show that the most primitive protocell membranes composed of fatty acids, that were initially leaky, would eventually become less ion permeable as their membranes evolved towards having increasing phospholipid contents.

Unraveling Chiral Selection in the Self-assembly of Chiral Fullerene Macroions: Effects of Small Chiral Components Including Counterions, Co-ions, or Neutral Molecules.

Lactic acid-functionalized chiral fullerene (C) molecules are used as models to understand chiral selection in macroionic solutions involving chiral macroions, chiral counterions, and/or chiral co-ions. With the addition of Zn cations, the C macroions exhibit slow self-assembly behavior into hollow, spherical, blackberry-type structures, as confirmed by laser light scattering (LLS), transmission electron microscopy (TEM), and atomic force microscopy (AFM) techniques. Chiral counterions with high charge density show no selection to the chirality of AC macroions (LAC and DAC) during their self-assembly process, while obvious chiral discrimination between the assemblies of LAC and DAC is observed when chiral counterions with low charge density are present.

Structure-Activity Relationships of Hydroxyapatite-Binding Peptides.

Elucidating the structure-activity relationships between biomolecules and hydroxyapatite (HAP) is essential to understand bone mineralization mechanisms, develop HAP-based implants, and design drug delivery vectors. Here, four peptides identified by phage display were selected as model HAP-binding peptides (HBPs) to examine the effects of primary amino acid sequence, phosphorylation of serine, presence of charged amino acid residues, and net charge of the peptide on (1) HAP-binding affinity, (2) secondary conformation, and (3) HAP nucleation and crystal growth. Binding affinities were determined by obtaining adsorption isotherms by mass depletion, and the conformations of the peptides in solution and bound states were observed by circular dichroism.

Accuracy of Thermodynamic Databases for Hydroxyapatite Dissolution Constant.

Discrepancies have been noted in the solubility constant values of calcium phosphate minerals between various databases employed in widely used aqueous speciation calculation software programs. This can cause serious errors in the calculated speciation of waters when using these software programs. The aim of this communication was to bring to light these discrepancies.

Bacterial Membrane Selective Antimicrobial Peptide-Mimetic Polyurethanes: Structure-Property Correlations and Mechanisms of Action.

The rise in prevalence of antibiotic resistant strains of bacteria is a very significant challenge for treating life-threatening infections worldwide. A source of novel therapeutics that has shown great promise is a class of biomolecules known as antimicrobial peptides. Previously, within our laboratories, we developed a new family of water-soluble antimicrobial polyurethanes that mimic antimicrobial peptides.

Natural, incidental, and engineered nanomaterials and their impacts on the Earth system.

Nanomaterials are critical components in the Earth system's past, present, and future characteristics and behavior. They have been present since Earth's origin in great abundance. Life, from the earliest cells to modern humans, has evolved in intimate association with naturally occurring nanomaterials.

Biological Response of and Blood Plasma Protein Adsorption on Silver-Doped Hydroxyapatite.

Hydroxyapatite (HAP) is an extensively used orthopedic biomaterial because of its high biocompatibility and osteoconductivity. Implant-related infection is a major cause of orthopedic device failure. Previous research showed that silver-doped hydroxyapatite nanoparticles (Ag-HAP NPs) have prominent antimicrobial activity, but their biocompatibility and plasma protein response remained unexplored.

Mineral-Lipid Interactions in the Origins of Life.

Protocells, the first life-like entities, likely contained three molecular components: a membrane, an information-carrying molecule, and catalytic molecules. Minerals have a wide range of properties that might have contributed to the synthesis and self-assembly of these molecular components. Minerals could have mediated the formation and concentration of prebiotic organic monomers, catalyzed their polymerization into biomolecules, and catalyzed protometabolic pathways, leading to protocell self-assembly.

Effects of laser shock peening on the corrosion behavior and biocompatibility of a nickel-titanium alloy.

Nickel-titanium (NiTi) alloy is an attractive material for biomedical implant applications. In this study, the effects of laser shock peening (LSP) on the biocompatibility, corrosion resistance, ion release rate and hardness of NiTi were characterized. The cell culture study indicated that the LSP-treated NiTi samples had lower cytotoxicity and higher cell survival rate than the untreated samples.

Hierarchical structures on nickel-titanium fabricated by ultrasonic nanocrystal surface modification.

Hierarchical structures on metallic implants can enhance the interaction between cells and implants and thus increase their biocompatibility. However, it is difficult to directly fabricate hierarchical structures on metallic implants. In this study, we used a simple one-step method, ultrasonic nanocrystal surface modification (UNSM), to fabricate hierarchical surface structures on a nickel-titanium (NiTi) alloy.

Quantitatively Identifying the Roles of Interfacial Water and Solid Surface in Governing Peptide Adsorption.

Understanding the molecular mechanism of protein adsorption on solids is critical to their applications in materials synthesis and tissue engineering. Although the water phase at the surface/water interface has been recognized as three types: bulk water, intermediate water phase and surface-bound water layers, the roles of the water and surface in determining the protein adsorption are not clearly identified, particularly at the quantitative level. Herein, we provide a methodology involving the combination of microsecond strengthen sampling simulation and force integration to quantitatively characterize the water-induced contribution and the peptide-surface interactions into the adsorption free energy.

Osteocalcin facilitates calcium phosphate ion complex growth as revealed by free energy calculation.

The nanoscopic structural and thermodynamic basis of biomolecule-regulated assembly and crystallization of inorganic solids have a tremendous impact on the rational design of novel functional nanomaterials, but are concealed by many difficulties in molecular-level characterization. Here we demonstrate that the free energy calculation approach, enabled by combining advanced molecular simulation techniques, can unravel the structural and energetic mechanisms of protein-mediated inorganic solid nucleation. It is observed that osteocalcin (OCN), an important non-collagenous protein involved in regulating bone formation, promotes the growth of nanosized calcium phosphate (CaP) ion clusters from a supersaturated solution.

Structure analysis of collagen fibril at atomic-level resolution and its implications for intra-fibrillar transport in bone biomineralization.

Bone is a hierarchical biocomposite material in which a collagen fibril matrix self-assembled in a three-dimensional (3-D) pseudohexagonal array controls many important processes in mineralization such as providing the pathways by which calcium and phosphate species are delivered and a template for the earliest nucleation sites, determining the spatial distribution of the mineral and the topology for binding of associated non-collagenous proteins. However, the structural characteristics of collagen molecules in the fibril remain unclear at the atomic level. Here we performed the first large-scale molecular dynamics simulations to provide a comprehensive all-atom structural analysis of the entire fibril of Type I collagen including intra-fibrillar water distribution.