Surface-bound Water Research Articles

Mussel adhesion is dictated by time-regulated secretion and molecular conformation of mussel adhesive proteins.

Interfacial water constitutes a formidable barrier to strong surface bonding, hampering the development of water-resistant synthetic adhesives. Notwithstanding this obstacle, the Asian green mussel Perna viridis attaches firmly to underwater surfaces via a proteinaceous secretion (byssus). Extending beyond the currently known design principles of mussel adhesion, here we elucidate the precise time-regulated secretion of P. viridis mussel adhesive proteins. The vanguard 3,4-dihydroxy-L-phenylalanine (Dopa)-rich protein Pvfp-5 acts as an adhesive primer, overcoming repulsive hydration forces by displacing surface-bound water and generating strong surface adhesion. Using homology modelling and molecular dynamics simulations, we find that all mussel adhesive proteins are largely unordered, with Pvfp-5 adopting a disordered structure and elongated conformation whereby all Dopa residues reside on the protein surface. Time-regulated secretion and structural disorder of mussel adhesive proteins appear essential for optimizing extended nonspecific surface interactions and byssus' assembly. Our findings reveal molecular-scale principles to help the development of wet-resistant adhesives.

Water interaction with hydrogenated and oxidized detonation nanodiamonds — Microscopic and spectroscopic analyses

Water interaction with surface modified nanodiamonds (NDs) is critical for many possible applications of NDs e.g. in biomedicine. Here we report on investigation of water interaction with hydrogenated and oxidized detonation nanodiamonds (H-DNDs, O-DNDs) by means of Fourier transform infrared spectroscopy (FTIR), thermal analysis, and Kelvin probe force microscopy (KPFM). Higher water content (4.4%) as well as weaker interaction of water with H-DNDs are identified by thermal analysis. It is explained by hydrophobicity of the H-DND surface, as revealed by the analysis of bending and stretching vibrations of surface water in FTIR spectra. On the other hand, hydrophilic nature of O-DNDs leads to lower water content (3.1%) but stronger interaction with the O-DND surface. This is evidenced by as high as 300°C desorption temperature of the surface water from O-DNDs. KPFM analysis shows that the surface-bound water can have significant screening effect on contact potential difference (CPD) of nanodiamonds (up to 510mV) as well as on the CPD difference between H-DNDs and O-DNDs (from 50mV to 210mV). Nevertheless, H-DNDs exhibit always lower work function.

Nonfreezing Water Structuration in Heteroprotein Coacervates.

Surface-bound water in protein solutions has been identified with a reduction in its freezing point. We studied the presence of such nonfreezing water (NFW) in various protein-polyelectrolyte, micelle-polyelectrolyte, and protein-protein (heteroprotein) coacervates, along with appropriate concentrated solutions of macromolecules alone, finding up to 15% w/w NFW for the heteroprotein coacervate of lactoferrin (LF) and β-lactoglobulin (BLG). The level of NFW is always higher in coacervates than in the control (single macromolecule) systems, particularly for protein-containing coacervates: a coacervate of bovine serum albumin (BSA) and poly(dimethyldiallylammonium chloride) (PDADMAC) showed a ratio of NFW/protein twice that of BSA alone (0.6 vs 0.3), with a similarly high ratio for LF-BLG coacervate. These results are attributed to the maximization of water-protein contacts, structural features that reflect the mode of sample assembly, as they are not seen in a noncoacervated LF-BLG solution with identical concentrations of all species.

Mechanisms of photoconductivity in atomically thin MoS2.

Atomically thin transition metal dichalcogenides have emerged as promising candidates for sensitive photodetection. Here, we report a photoconductivity study of biased mono- and bilayer molybdenum disulfide field-effect transistors. We identify photovoltaic and photoconductive effects, which both show strong photogain. The photovoltaic effect is described as a shift in transistor threshold voltage due to charge transfer from the channel to nearby molecules, including SiO2 surface-bound water. The photoconductive effect is attributed to the trapping of carriers in band tail states in the molybdenum disulfide itself. A simple model is presented that reproduces our experimental observations, such as the dependence on incident optical power and gate voltage. Our findings offer design and engineering strategies for atomically thin molybdenum disulfide photodetectors, and we anticipate that the results are generalizable to other transition metal dichalcogenides as well.

Hydrogen titanium oxide hydrate: excellent performance on degradation of methyl blue in aqueous solutions

Nanotube-assembled flower-like hydrogen titanium oxide hydrate (H2Ti2O4(OH)2), which has degradation capacity for methyl blue (MB) even in darkness, was prepared via a microwave solvothermal process. Physicochemical features of the hydrogen titanium oxide hydrate powders were characterized by X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy, Fourier transform-infrared spectroscopy and UV/VIS/NIR spectrometry. The degradation of methyl blue (MB), methyl orange (MO) and Rhodamine B (Rhb) solution with a water-cooling system was carried out to study the photocatalytic properties of the powders. Results indicate that the H2Ti2O4(OH)2 has excellent performance on degradation of MB, which can be attributed to the hydroxyl group (–OH) from the surface of the catalysts confirmed by electron spin resonance signals (ESR). Furthermore, the intensity of ESR signals rapidly increased with the irradiation time and did not reach maximum after 11 min, which indicated that the photogenerated holes in the valence band of H2Ti2O4(OH)2 catalysts reacted rapidly with surface-bound water or the hydroxyl group and produced a large amount of ˙OH, which was beneficial for degrading MB. The degradation results indicate that these catalysts have potential uses in removing harmful carcinogens from water, in addition to possible applications in reducing the harmful effects of oil spills.

Complex dielectric permittivity of organically modified bentonite suspensions (0.2–1.3 GHz)

To quantify the impact of organic carbon on the complex dielectric permittivity of organoclays, nine organically modified clays were synthesized with controlled organic carbon structure and density of loading. Resonance polarization responses were observed for six of the organoclays at resonant frequencies from 0.74 to 1.37 GHz; however, organoclays synthesized with the smallest organic cations did not exhibit resonant frequency. A structural model of water molecules near the surface of organoclay and in the diffuse layer was proposed, which consists of a surface-bound water layer, an organic cation-interactive zone, and bulk water. The Cole–Cole equation was used to fit the resonance response. Increasing the density of loading (30% to 100% of the cation exchange capacity of the base clay) on the clay surface led to a reduction in the resonance time of the clay, while increasing the size of the organic cation led to a longer dielectric resonance time for the clay, which indicates that altering the structure and density of the organic carbon phase changed the degree of constraint of water molecules within the clay’s interlayer. However, the impact of organic carbon content on real permittivity was not significant. Water content had no obvious effect on the resonant frequency of the organoclays at high water content (porosity ranging from 0.7 to 1.0) in this study. In addition, it was shown that a linear approximation was sufficient in relating real permittivity of organoclay suspensions to porosity, and the effective conductivity decreased linearly proportional to porosity. That is, the real permittivity and effective conductivity were dominated by that of the aqueous phase until the inception of resonance polarization.

ChemInform Abstract: Molecular Surface Chemistry in Marine Bioadhesion

AbstractReview: 261 refs.

Structure and Stability of SnO2 Nanocrystals and Surface-Bound Water Species

The structure of SnO2 nanoparticles (avg. 5 nm) with a few layers of water on the surface has been elucidated by atomic pair distribution function (PDF) methods using in situ neutron total scattering data and molecular dynamics (MD) simulations. Analysis of PDF, neutron prompt gamma, and thermogravimetric data, coupled with MD-generated surface D2O/OD configurations demonstrates that the minimum concentration of OD groups required to prevent rapid growth of nanoparticles during thermal dehydration corresponds to ~0.7 monolayer coverage. Surface hydration layers not only stabilize the SnO2 nanoparticles but also induce particle-size-dependent structural modifications and are likely to promote interfacial reactions through hydrogen bonds between adjacent particles. Upon heating/dehydration under vacuum above 250 °C, nanoparticles start to grow with low activation energies, rapid increase of nanoparticle size, and a reduction in the a lattice dimension. This study underscores the value of neutron diffraction and prompt-gamma analysis, coupled with molecular modeling, in elucidating the influence of surface hydration on the structure and metastable persistence of oxide nanomaterials.

Do the Physical Properties of Water in Mixed Reverse Micelles Follow a Synergistic Effect: A Spectroscopic Investigation

In this contribution we have tried to investigate whether the mechanical properties of the reverse micellar (RM) interface dictate the physical properties of entrapped water molecules in the RM waterpool. We choose AOT/Igepal-520/cyclohexane (Cy) mixed RM as a model system which exhibits synergistic water solubilization behavior as a function of interfacial stoichiometry. Such a phenomenon associates systematic modification of the interface curvature. Dynamic light scattering (DLS) studies reveal linear increase in the droplet size and aggregation number of the RMs with increasing XIgepal (mole fraction of Igepal in the surfactant mixture). FTIR study in the 3000-3800 cm(-1) region identifies that the relative population of the surface-bound water molecules is higher in AOT RM compared to that in Igepal RM, and in mixed systems it also follows a linear trend with XIgepal. Water relaxation dynamics as probed by time-resolved fluorescence spectroscopy using Coumarin-500 also reveals an overall linear trend with no characteristic feature around the solubilization inflation point. Our study clearly identifies that the physical properties of water in RM are mostly governed by the interfacial stoichiometry and water content, and merely bares any dependence on the mechanical properties of the interface.

Protein adsorption in three dimensions

Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and initially adsorbed protein. Interphase protein concentration CI increases as VI decreases, resulting in slow reduction in interfacial energetics. Steady state is governed by a net partition coefficient P=(CI/CB). In the process of occupying space within the interphase, adsorbing protein molecules must displace an equivalent volume of interphase water. Interphase water is itself associated with surface-bound water through a network of transient hydrogen bonds. Displacement of interphase water thus requires an amount of energy that depends on the adsorbent surface chemistry/energy. This “adsorption–dehydration” step is the significant free energy cost of adsorption that controls the maximum amount of protein that can be adsorbed at steady state to a unit adsorbent surface area (the adsorbent capacity). As adsorbent hydrophilicity increases, adsorbent capacity monotonically decreases because the energetic cost of surface dehydration increases, ultimately leading to no protein adsorption near an adsorbent water wettability (surface energy) characterized by a water contact angle θ→65°. Consequently, protein does not adsorb (accumulate at interphase concentrations greater than bulk solution) to more hydrophilic adsorbents exhibiting θ<65°. For adsorbents bearing strong Lewis acid/base chemistry such as ion-exchange resins, protein/surface interactions can be highly favorable, causing protein to adsorb in multilayers in a relatively thick interphase. A straightforward, three-component free energy relationship captures salient features of protein adsorption to all surfaces predicting that the overall free energy of protein adsorption ΔGadso is a relatively small multiple of thermal energy for any surface chemistry (except perhaps for bioengineered surfaces bearing specific ligands for adsorbing protein) because a surface chemistry that interacts chemically with proteins must also interact with water through hydrogen bonding. In this way, water moderates protein adsorption to any surface by competing with adsorbing protein molecules. This Leading Opinion ends by proposing several changes to the protein-adsorption paradigm that might advance answers to the three core questions that frame the “protein-adsorption problem” that is so fundamental to biomaterials surface science.

The Goldilocks Surface

A minimum in the biological response to materials that is observed to occur within a narrow surface energy range is related to the properties of water at these biology-contacting surfaces. Wetting energetics are calculated using a published theory from which it is further estimated that water molecules bind to these special surfaces through a single hydrogen bond, leaving three other hydrogen bonds to interact with proximal water molecules. It is concluded that, at this Goldilocks Surface, the local chemical environment of surface-bound water is nearly identical to that experienced in bulk water; neither deprived of hydrogen bond opportunities, as it is in contact with a more hydrophobic surface, nor excessively hydrogen bonded to a more hydrophilic surface. A minimum in the biological response occurs because water vicinal (near) to the Goldilocks Surface is not chemically different than bulk water. A more precise definition of the relative terms hydrophobic and hydrophilic for use in biomaterials becomes evident from calculations: >1.3 kJ/mole-of-surface-sites is expended in wetting a hydrophilic surface whereas <1.3 kJ/mole-of-surface-sites is expended in wetting hydrophobic surfaces; hydrophilic surfaces wet with >1 hydrogen bond per water molecule whereas hydrophobic surfaces wet with <1 hydrogen bond per water molecule.

Activation Energies for the Rate-Limiting Step in Water Photooxidation by Nanostructured α-Fe2O3 and TiO2

Competition between charge recombination and the forward reactions required for water splitting limits the efficiency of metal-oxide photocatalysts. A key requirement for the photochemical oxidation of water on both nanostructured α-Fe(2)O(3) and TiO(2) is the generation of photoholes with lifetimes on the order of milliseconds to seconds. Here we use transient absorption spectroscopy to directly probe the long-lived holes on both nc-TiO(2) and α-Fe(2)O(3) in complete PEC cells, and we investigate the factors controlling this slow hole decay, which can be described as the rate-limiting step in water oxidation. In both cases this rate-limiting step is tentatively assigned to the hole transfer from the metal oxide to a surface-bound water species. We demonstrate that one reason for the slow hole transfer on α-Fe(2)O(3) is the presence of a significant thermal barrier, the magnitude of which is found to be independent of the applied bias at the potentials examined. This is in contrast to nanocrystalline nc-TiO(2), where no distinct thermal barrier to hole transfer is observed.

Dynamics of Water Filaments in Disordered Environments

The formation, stability, and dynamics of water filaments in disordered environments is investigated by using atomistic molecular dynamics simulations. It is found that in an alkyl-chain arrangement representative of that used in liquid chromatography, extended water filaments can form for up to 1 ns before they are destroyed again due to thermal fluctuations. The water dynamics in the disordered stationary phase is surprisingly intense with about 10(7) per alkyl chain per second of water molecules flowing in and out of the stationary phase. This is compatible with estimates based on Fick's law using a homogeneous solubility-diffusion model. The simulations also establish the existence of different types of water molecules as was predicted 30 years ago. From the current simulations they can be identified as (SiOH-) surface-bound, interfacial, and bulk water molecules.

Intrinsic doping and gate hysteresis in graphene field effect devices fabricated onSiO2 substrates

We have studied the intrinsic doping level and gate hysteresisof graphene-based field effect transistors (FETs) fabricated overSi/SiO2 substrates. It was found that the high p-doping level of graphene in some as-prepareddevices can be reversed by vacuum degassing at room temperature or abovedepending on the degree of hydrophobicity and/or hydration of the underlyingSiO2 substrate. Charge neutrality point (CNP) hysteresis, consisting of the shift of thecharge neutrality point (or Dirac peak) upon reversal of the gate voltage sweepdirection, was also greatly reduced upon vacuum degassing. However, another type ofhysteresis, consisting of the change in the transconductance upon reversal of thegate voltage sweep direction, persists even after long-term vacuum annealing at200 °C, whenSiO2 surface-bound water is expected to be desorbed. We propose a mechanismfor this transconductance hysteresis that involves water-related defects,formed during the hydration of the near-surface silanol groups in the bulkSiO2, that can act as electron traps.

Polarization at metal–biomolecular interfaces in solution

Metal surfaces in contact with water, surfactants and biopolymers experience attractive polarization owing to induced charges. This fundamental physical interaction complements stronger epitaxial and covalent surface interactions and remains difficult to measure experimentally. We present a first step to quantify polarization on even gold (Au) surfaces in contact with water and with aqueous solutions of peptides of different charge state (A3 and Flg-Na3) by molecular dynamics simulation in all-atomic resolution and a posteriori computation of the image potential. Attractive polarization scales with the magnitude of atomic charges and with the length of multi-poles in the aqueous phase such as the distance between cationic and anionic groups. The polarization energy per surface area is similar on aqueous Au {1 1 1} and Au {1 0 0} interfaces of approximately -50 mJ m(-2) and decreases to -70 mJ m(-2) in the presence of charged peptides. In molecular terms, the polarization energy corresponds to -2.3 and -0.1 kJ mol(-1) for water in the first and second molecular layers on the metal surface, and to between -40 and 0 kJ mol(-1) for individual amino acids in the peptides depending on the charge state, multi-pole length and proximity to the surface. The net contribution of polarization to peptide adsorption on the metal surface is determined by the balance between polarization by the peptide and loss of polarization by replaced surface-bound water. On metal surfaces with significant epitaxial attraction of peptides such as Au {1 1 1}, polarization contributes only 10-20% to total adsorption related to similar polarity of water and of amino acids. On metal surfaces with weak epitaxial attraction of peptides such as Au {1 0 0}, polarization is a major contribution to adsorption, especially for charged peptides (-80 kJ mol(-1) for peptide Flg-Na(3)). A remaining water interlayer between the metal surface and the peptide then reduces losses in polarization energy by replaced surface-bound water. Computed polarization energies are sensitive to the precise location of the image plane (within tenths of Angstroms near the jellium edge). The computational method can be extended to complex nanometre and micrometer-size surface topologies.

Product desorption limitations in selective photocatalytic oxidation

The rate of photocatalytic processes can be significantly improved if strongly bound products rapidly desorb to free up active sites. This paper deals with the rate of desorption of cyclohexanone, the product of the liquid-phase photo-oxidation of cyclohexane. Dynamic step-response and pulse-response experiments were performed, and the interaction with a TiO 2 surface was monitored using ATR FT-IR spectroscopy. A key result is that cyclohexanone desorbs readily from unexposed surfaces and desorbs an order of magnitude slower from UV-illuminated titania. The modification of the surface by UV is reversible: after 2 h without UV illumination the surface behaves as an unexposed one. The spectroscopic data support an explanation where without illumination, the cyclohexanone adsorbs on surface-bound water, from which it readily desorbs. Illumination, on the other hand, converts part of this water to accessible hydroxyl groups on titania. Cyclohexanone, forming during illumination, binds to these Ti–OH groups, and consequently desorbs much slower.

Isothermal Titration Calorimetry Reveals Differential Binding Thermodynamics of Variable Region-identical Antibodies Differing in Constant Region for a Univalent Ligand

The classical view of immunoglobulin molecules posits two functional domains defined by the variable (V) and constant (C) regions, which are responsible for antigen binding and antibody effector functions, respectively. These two domains are thought to function independently. However, several lines of evidence strongly suggest that C region domains can affect the specificity and affinity of an antibody for its antigen (Ag), independent of avidity-type effects. In this study, we used isothermal titration calorimetry to investigate the thermodynamic properties of the interactions of four V region-identical monoclonal antibodies with a univalent peptide antigen. Comparison of the binding of IgG1, IgG2a, IgG2b, and IgG3 with a 12-mer peptide mimetic of Cryptococcus neoformans polysaccharide revealed a stoichiometry of 1.9-2.0 with significant differences in thermodynamic binding parameters. Binding of this peptide to the antibodies was dominated by favorable entropy. The interaction of these antibodies with biotinylated peptides manifested greater enthalpy than for native peptides indicating that biotin labeling affected the types of Ag-Ab complexes formed. Our results provide unambiguous thermodynamic evidence for the notion that the C region can affect the interaction of the V region with an Ag.

Electrical characterization of hydroxyapatite-based bioceramics

This paper studies the AC conductivity and permittivity of hydroxyapatite (HA)-based ceramics from 0.1Hz–1MHz at temperatures from room temperature to 1000°C. HA-based ceramics were prepared either as dense ceramics or in porous form with interconnected porosity and were sintered in either air or water vapour. Samples were thermally cycled to examine the influence of water desorption on AC conductivity and permittivity. Surface-bound water was thought to contribute to conductivity for both dense and porous materials at temperatures below 200°C. At temperatures below 700°C the permittivity and AC conductivity of HA was also influenced by the degree of dehydration and thermal history. At higher temperatures (700–1000°C), bulk ionic conduction was dominant and activation energies were of the order of ∼2eV, indicating that hydroxyl ions are responsible for conductivity.

Programming/Erasing Characteristics of Hysteresis-Based Nonvolatile Memory Devices of Single-Wall Carbon Nanotubes

Hysteresis effect in carbon nanotube field-effect transistors can be commonly employed to construct the nonvolatile memory devices of single-wall carbon nanotubes. In this paper, we investigate in detail the programming/erasing characteristics of such memory devices, which may present great importance for their availabilities. In order to write and erase the memory devices with reproducibility and stability, it is essential to set the writing and erasing time appropriately. The writing and erasing process of such memory devices is, in general, found to be much slower compared with traditional CMOS memory devices, typically operating on a time scale of the order of a second, which may pose a serious challenge to their practical exploitation. Furthermore, the stability of charge storage in such memories is slightly affected by temperature. A model based on electric polarization of surface-bound water molecules on SiO2 insulator has also been proposed to explain qualitatively the hysteresis and memory effect of these devices. Keywords: Carbon nanotube, nonvolatile memory, hysteresis, transistor

Quantum Chemistry and Computational Kinetics of the Reaction between OH Radicals and Formaldehyde Adsorbed on Small Silica Aerosol Models

Heterogeneous reactions of atmospheric volatile organic compounds (VOCs) on aerosol particles may play an important role in atmospheric chemistry. Clay particles are present in mineral dust in atmospheric aerosols, and radical reactions are thought to be heterogeneously catalyzed on them. However, the kinetics and mechanisms of adsorption and reaction of atmospheric VOCs on aerosol surfaces are not well understood. In this work, quantum chemical methods are used to study the reaction of OH radicals with formaldehyde adsorbed on small (SiO4)n cluster models, with n = 1 to 6. We show that surface adsorbed formaldehyde can react in the presence of gas-phase OH radicals to yield surface-bound formyl radicals and water. Significant exothermic adsorption energies are found, supporting the notion that silicate surfaces are good quenchers of VOCs. With the models employed, the reaction appears to be less favored on the silicate surfaces than in the gas phase. The effect of the model surface on the reaction mechan...