Ultrathin hybrid films of clay minerals

Smectites or swelling clay minerals are naturally occurring nanomaterials that can be fully delaminated to elementary clay mineral platelets in dilute aqueous dispersion. This review article gives an overview of the recent progress on how the elementary clay mineral platelets can be reorganized in monolayered or multilayered hybrid nanofilms by layer-by-layer assembly or the Langmuir-Blodgett technique. In the latter case one hybrid layer consists of one layer of elementary clay mineral platelets with a theoretical thickness of 0.96 nm, covered on one side by amphiphilic cations. The organization of the elementary clay mineral platelets and that of the adsorbed amphiphilic cations in the nanofilms has been studied in great detail by ATR-FTIR, UV-Vis and fluorescence spectroscopy, XRD and AFM. The nanofilms carry functional properties, such as chirality, optical nonlinearity and magnetism, which are due to the nature of the amphiphilic cations and to the organization of both the amphiphilic molecules and the elementary clay mineral platelets.     

Analysis, purification and properties of a 50,000-dalton membrane-associated phosphoprotein from human platelets

Recently, the development of a monospecific antiserum against a 46,000/50,000-dalton membrane protein from human platelets which was stoichiometrically and reversibly phosphorylated in intact human platelets in response to vasodilators was reported. Using this antiserum, the subcellular distribution and the purification of this vasodilator-stimulated phosphoprotein (VASP) from human platelets has now been analysed. The VASP of human platelets is primarily a membrane-associated protein and can be purified to apparent homogeneity by salt extraction and sequential ion-exchange and dye-ligand chromatography with a purification factor of 1200 and a yield of 13%. Sodium dodecyl sulphate-polyacrylamide gel electrophoresis under reducing and non-reducing conditions indicated that purified monomers of this VASP are linked by interchain disulphide bonding.     

First isolation of individual silicate platelets from clay exfoliation and their unique self-assembly into fibrous arrays

Thin silicate platelets in a dimension of approximately 80 x 80 x 1 nm(3) are isolated for the first time by a newly developed process involving one-step exfoliation of natural montmorillonite clay and toluene/aqueous NaOH extraction. The platelets are observed to be polygon shape by transmission electron microscopy (TEM) and round bent-leaf shape by dynamic force microscopy (DFM). Individual platelets possessing high-aspect-ratio dimension and ionic character are able to self-assemble into microscale fiber bundles after water evaporation. The self-stacking mechanism indicated strong face-to-face ionic charge stacking propensity in triggering a vertical growth. Regularity of fibrous bundles in an average 5 microm length has been observed.     

Dielectrophoretic separation of platelets from diluted whole blood in microfluidic channels

The dielectrophoresis (DEP) phenomenon is used to separate platelets directly from diluted whole blood in microfluidic channels. By exploiting the fact that platelets are the smallest cell type in blood, we utilize the DEP-activated cell sorter (DACS) device to perform size-based fractionation of blood samples and continuously enrich the platelets in a label-free manner. Cytometry analysis revealed that a single pass through the two-stage DACS device yields a high purity of platelets (approximately 95%) at a throughput of approximately 2.2 x 10(4) cells/second/microchannel with minimal platelet activation. This work demonstrates gentle and label-free dielectrophoretic separation of delicate cells from complex samples and such a separation approach may open a path toward continuous screening of blood products by integrated microfluidic devices.     

Anomalous columnar order of charged colloidal platelets

Monte Carlo computer simulations are carried out for a model system of like-charged colloidal platelets in the isothermal-isobaric ensemble (NpT). The aim is to elucidate the role of electrostatic interactions on the structure of synthetic clay systems at high particle densities. Short-range repulsions between particles are described by a suitable hard-core model representing a discotic particle. This potential is supplemented with an electrostatic potential based on a Yukawa model for the screened Coulombic potential between infinitely thin disklike macro-ions. The particle aspect-ratio and electrostatic parameters were chosen to mimic an aqueous dispersion of thin, like-charged, rigid colloidal platelets at finite salt concentration. An examination of the fluid phase diagram reveals a marked shift in the isotropic-nematic transition compared to the hard cut-sphere reference system. Several statistical functions, such as the pair correlation function for the center-of-mass coordinates and structure factor, are obtained to characterize the structural organization of the platelets phases. At low salinity and high osmotic pressure we observe anomalous hexagonal columnar structures characterized by interpenetrating columns with a typical intercolumnar distance corresponding to about half of that of a regular columnar phase. Increasing the ionic strength leads to the formation of glassy, disordered structures consisting of compact clusters of platelets stacked into finite-sized columns. These so-called "nematic columnar" structures have been recently observed in systems of charge-stabilized gibbsite platelets. Our findings are corroborated by an analysis of the static structure factor from a simple density functional theory.     

Intercalation of solvent and polymer in galleries of mobile clay platelets by a Monte Carlo simulation

The intercalation of solvent particles and polymer chains of concentration C_w = 0.2 and C_p = 0.2, respectively, in a layer of (4) clay platelets is studied by a Monte Carlo simulation on a cubic lattice. Polymer chains and platelets are modeled by bond fluctuations. Besides the excluded volume, a set of polymer-clay (cs) and solvent-clay (ws) interactions with (i) cs = 1, ws = −2, (ii) cs = −2, ws = 1 and (iii) cs = ws = −2 are considered. The global dynamics of platelets is constrained due to the presence of three components, i.e., solvent, polymer, and platelets, which retain their interstitial spacing with well-defined galleries. Intercalation of solvent particles and polymer chains (low molecular weight) occurs with their attractive interaction with the platelets, which further reinforces the layered clay morphology. The density profiles of the solvent particles are similar to previous studies with platelets in a mobile solvent. The density profile of polymer chains differs considerably from the platelets in a polymer matrix alone, particularly with its attractive interaction (ii). For the same attractive interaction of solvent and polymer chains with the clay platelets (iii), the solvent particles (the smallest constituents) intercalate the fastest in the clay galleries, whereas the intercalation of polymer chains decreases with their molecular weight. The polymer density profiles, both longitudinal (x) and transverse (y), show maxima peaks around outer platelets (surface) of the layer and decay sharply both in the adjacent galleries and in the bulk. The amplitude of oscillation in the transverse density profiles, a measure of the degree of intercalation, decreases with increasing molecular weight of the polymer. The intercalation of the polymer is driven by its attractive interaction at the low molecular weight, but reduces considerably at high molecular weight because of both entanglement and larger radius of gyration. Variations of the gyration radius of the diffusing polymer chains with molecular weight and interaction with the clay are consistent with the results of their corresponding density profiles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2487–2500, 2009     

Changes in blood platelets exposed to UV-B radiation.

The effects of UV-B radiation (312 nm) on the pig-blood platelet secretory process (platelet activation) and platelet lipid peroxidation have been studied. The responses of platelets to UV-B radiation are compared with the response of these cells to thrombin, which is a strong platelet agonist. The obtained results show that exposure of blood platelets to UV-B radiation (1.2 mW/cm2, 0.072-8.64 J/cm2) causes dose-dependent platelet lipid peroxidation (measured as thiobarbituric acid reactive substances, TBARS) and release of adenine nucleotides and proteins from irradiated platelets. The dose-dependent release of platelet compounds from irradiated platelet does not correlate with the activity of platelet lactic dehydrogenase (marker of cell lysis) in the extracellular medium. It seems that UV-B radiation can partly activate platelets by stimulating the platelet secretory process and metabolism of arachidonate.     

Enhanced thermal conductivity and mechanical properties of polymeric composites through formation of covalent bonds between boron nitride and rubber chains

Hexagonal boron nitride (BN) platelets, also known as white graphite, are often used to improve the thermal conductivities of polymeric matrices. Due to the poor interfacial compatibility between BN platelets and polymeric matrices, in this study, polyrhodanine (PRd) was used to modify BN platelets and prepared functionalized BN-PRd platelets, thereby enhancing the interfacial interaction between the thermal conductive filler and polymeric matrix. Then, BN-PRd platelets were dispersed into the nitrile butadiene rubber (NBR) matrix to yield high thermally conductive composites. The presence of N? C═S groups in PRd allowed the combination of PRd and NBR chains containing stable covalent bonds via vulcanization reaction. The thermal conductivity of the as-prepared 30 vol% BN-PRd/NBR composite reached 0.40 W/mK, representing an increment of 135% over pure NBR (0.17 W/mK). In addition, the largest tensile strength of NBR composite containing 30 vol% BN-PRd platelets was 880% times of pure NBR. The 30 vol% BN-PRd/NBR composite also displayed a relatively high dielectric constant (9.35 at 100 Hz) and a low dielectric loss tangent value (0.07 at 100 Hz), indicating their usefulness as dielectric flexible materials of microelectronics. In sum, the simplicity and good efficiency of formation of covalent bonds between boron nitride and rubber chains look very promising for large-scale industrial production of high thermally conductive composites.     

Effect of polydispersity and soft interactions on the nematic versus smectic phase stability in platelet suspensions

We theoretically discuss, using density-functional theory, the phase stability of nematic and smectic ordering in a suspension of platelets of the same thickness but with a high polydispersity in diameter, and study the influence of polydispersity on this stability. The platelets are assumed to interact like hard objects, but additional soft attractive and repulsive interactions, meant to represent the effect of depletion interactions due to the addition of nonabsorbing polymer, or of screened Coulomb interactions between charged platelets in an aqueous solvent, respectively, are also considered. The aspect (diameter-to-thickness) ratio is taken to be very high, in order to model solutions of mineral platelets recently explored experimentally. In this regime a high degree of orientational ordering occurs; therefore, the model platelets can be taken as completely parallel and are amenable to analysis via a fundamental-measure theory. Our focus is on the nematic versus smectic phase interplay, since a high degree of polydispersity in diameter suppresses the formation of the columnar phase. When interactions are purely hard, the theory predicts a continuous nematic-to-smectic transition, regardless of the degree of diameter polydispersity. However, polydispersity enhances the stability of the smectic phase against the nematic phase. Predictions for the case where an additional soft interaction is added are obtained using mean-field perturbation theory. In the case of the one-component fluid, the transition remains continuous for repulsive forces, and the smectic phase becomes more stable as the range of the interaction is decreased. The opposite behavior with respect to the range is observed for attractive forces, and in fact the transition becomes of first order below a tricritical point. Also, for attractive interactions, nematic demixing appears, with an associated critical point. When platelet polydispersity is introduced the tricritical temperature shifts to very high values.     

Clay-mediated synthesis of silver nanoparticles exhibiting low-temperature melting

Nanohybrids of silver nanoparticles (AgNPs) supported on mica clay were synthesized by in situ reduction of silver nitrate in an aqueous solution. The required mica platelets of high aspect ratio were previously prepared by the exfoliation of mica clay stacks in a multilayered structure through an ionic exchange reaction with poly(oxypropylene)-amine-salt. The exfoliated nanoscale mica platelets (Mica) are polydispersed such that each platelet is 300-1000 nm in width and 1 nm in thickness. These platelets possess ionic charges in the form of ≡SiO(-)Na(+) at 120 mequiv/100 g and are suitable for supporting AgNPs in the process of in situ reduction of silver nitrate. Transmission electronic microscopy revealed the formation of AgNPs with a narrow size distribution of ca. 8 nm in diameter on the rim of individual Mica platelets. However, the pristine layered Mica structure without exfoliation failed to produce a fine AgNP distribution but instead generated particles larger than 30 nm and some precipitates. Characterization by differential scanning calorimetry and field emission scanning electron microscopy revealed that the fine AgNPs on Mica platelets exhibited a low melting temperature of 110 °C. The AgNP/Mica nanohybrid not containing an organic dispersant is considered to be a "naked" silver particle.     

Probing the interaction of a glycoprotein IIb/IIIa receptor antagonist with bound platelets using electrochemical impedance

A label-free assay is described to monitor the interaction of abciximab, a glycoprotein IIb/IIIa receptor antagonist (ReoPro), with platelets bound to a fibrinogen-functionalised electrode surface. Firstly, fibrinogen is deposited in a defined pattern onto a gold electrode using microcontact printing, and then platelets from whole blood are captured on the patterned surface. Patterning influences the spreading of platelets, which is strikingly different to that observed on homogeneously coated surfaces. The drug–platelet interaction has been investigated using AC impedance on uniform and patterned fibrinogen-modified surfaces. The results demonstrate that patterned fibrinogen surfaces can provide deep insights into the interaction of abciximab with different platelet sub-populations. The key advantages of this approach are that it is rapid, label free and does not require pre-processing of patient blood samples.     

A pulsed EPR study of surfactant layer structure in composites of a synthetic layered silicate with polystyrene and polycaprolactone

Double electron electron resonance (DEER), deuterium electron spin-echo envelope modulation (ESEEM) spectroscopy and 31P electron nuclear double resonance (ENDOR) spectroscopy were applied to site-specifically spin-labeled surfactants in the organically modified layered silicate magadiite and its composites with polystyrene (PS) and polycaprolactone (PCL). The organomagadiite consist of stacks of silicate platelets with surfactant layers between these platelets. In PS composites the stacks are dispersed in the polymer matrix as a whole, while melt processing with PCL leads to intercalation of polymer chains into the galleries between the platelets. The DEER data prove that even in the case of the non-intercalated PS composites the density of surfactant molecules changes drastically during composite formation on length scales of a few nanometers. Deuterium ESEEM data demonstrate that spin labels attached both in the middle and at the end of the alkyl chain have contact with the headgroups of neighboring surfactant molecules. By analysis of the 31P ENDOR spectra, two characteristic distances are found between the spin labels and the headgroups of phosphonium surfactants. The shorter, proximal distance can be assigned to headgroups in the same surfactant layer. By comparison with the basal spacing between consecutive silicate platelets the longer, distal distance is assigned to a layer of surfactants that is not attached to the surface of the next platelet but rather located between platelets. Altogether the data support a picture of trilayers of disordered surfactant molecules with their alkyl chains oriented nearly parallel to the surface.     

Formation of nematic liquid crystals of sterically stabilized layered double hydroxide platelets

Colloidal platelets of hydrotalcite, a layered double hydroxide, have been prepared by coprecipitation at pH 11-12 of magnesium nitrate and aluminum nitrate at two different magnesium to aluminum ratios. Changing the temperature and ionic strength during hydrothermal treatment, the platelets were tailored to different sizes and aspect ratios. Amino-modified polyisobutylene molecules were grafted onto the platelets following a convenient new route involving freeze-drying. Organic dispersions in toluene were prepared of the particles with the largest size and highest aspect ratio. The colloidal dispersions prepared in this way showed isotropic-nematic phase transitions above a limiting concentration in a matter of days. The number density at the transition and the width of the biphasic region were determined and compared to theory. The orientation of the platelets in nematic droplets (tactoids) and at the isotropic-nematic interface were analyzed by polarization microscopy. It was observed that sedimentation induces a nematic layer in samples that are below the limiting concentration for isotropic-nematic phase separation. No nematic phase was observed in the initial aqueous suspensions of the ungrafted particles.     

Controlled nanoporosity of organic aerogels by dispersing clay platelets

A new class of organic-inorganic hybrid aerogels having small pores and narrow pore size distribution are synthesized from well-dispersed clay platelets in water as base catalyst. Clay-catalyzed organic gels have strong advantage in controlling nanopore structure as well as reducing drying shrinkage by reinforcing the organic network with inorganic platelets.     

UV-B-induced generation of free radicals in blood platelets

UV-B irradiation of blood-platelet concentrates is used in transfusion practice to prevent the development of post-transfusion alloimmunization and inactivate viruses and bacteria in the concentrates. UV-B radiation may affect the blood-platelet metabolism and function; therefore we have investigated the effect of UV-B irradiation on free radical production in blood platelets. Our results show that exposure of pig blood platelets to UV-B radiation (0.36 and 1.08 J/cm2) induces the generation of free radicals measured by the chemiluminescence method (respectively 28 and 148.6% above the control). The superoxide radical level after UV-B irradiation measured by the cytochrome c reduction method shows only a slight increase (p > 0.05). Free radical generation induced by UV-B radiation is dependent partly on blood-platelet activation and enzymatic pathways, since we have shown that wortmannin, an inhibitor of phosphatidylinositide 3-kinase, reduces the level of radicals formed in blood platelets after UV-B irradiation. This indicates that free radicals generated in blood platelets after stimulation by UV-B radiation are involved in platelet activation and metabolism of platelet polyphosphoinositides.     

Blood platelet adhesion to protein studied by on-line acoustic wave sensor

The attachment of blood platelets to the surface of bare and protein-coated thickness-shear mode acoustic wave devices operating in a flow-through configuration has been studied. Platelets in washed from bind to the gold electrodes of such sensors, but the resulting frequency shifts are far less than predicted by the conventional mass-based model of device operation. Adherence to albumin and various types of collagen can be produced by on-line introduction of protein or by a pre-coating strategy. Differences in attachment of platelets to collagen types I and IV and the Horm variety can be detected. Platelets attached to collagen yield an interesting delayed, but reversible signal on exposure to a flowing medium of low pH. Scanning electron microscopy of sensor surfaces at various time points in this experiment reveals that originally intact platelets are eventually destroyed by the high acidity of the medium. The reversible frequency is attributed to the presence of removable platelet granular components at the sensor-liquid interface.     

Electrochemical evaluation of the viability of platelets

The difference between the open-circuit redox potentials of a platinum electrode measured in blood plasma before and after the cryolysis of platelets depends linearly on the content of granule-rich platelets in the plasma. This phenomenon can be used to determine the viability of platelets.     

Activated Platelet‐Derived Vesicles for Efficient Hemostatic Activity

In this study, activated platelet‐derived vesicles (Act‐VEs) are developed as a novel hemostatic biomaterial. Spherical Act‐VEs (114.40 ± 11.69 nm in size) with surface charges of ?24.73 ± 1.32 mV are successfully prepared from thrombin‐activated murine platelets with high surface expression of active glycoprotein IIb/IIIa (GP IIb/IIIa, also known as αIIbβ3) and P‐selectin. Although nanosized vesicles from resting platelets (VEs) and Act‐VEs showed similar sizes and surface charges, Act‐VEs formed much larger aggregates in the presence of thrombin and CaCl₂, compared to VEs. After incubation with fibrinogen, Act‐VEs formed much denser fibrin networks compared to platelets or VEs, probably due to active αIIbβ3 on the surfaces of the Act‐VEs. After intravenous injection of the Act‐VEs, tail bleeding time and the blood loss are greatly reduced by Act‐VEs in vivo. In addition, Act‐VEs showed approximately sevenfold lower release of pro‐inflammatory interleukin‐1β (IL‐1β) during incubation for 4 days, compared to platelets. Taken together, the formulated Act‐VEs can serve as a promising hemostatic biomaterial for the efficient formation of fibrin clots without releasing pro‐inflammatory cytokine.     

Design and Preparation of Highly Filled Water‐Borne Polymer–Gibbsite Nanocomposites

Highly filled, high solids content, water‐borne polymer–Gibbsite nanocomposites are prepared with Gibbsite contents as high as 35 wt%. The polymer–Gibbsite nanocomposites are synthesised via conventional starved feed emulsion polymerization using negatively charged butyl acrylate‐co‐acrylic acid oligomers, which functioned as electrosteric stabilizers for the initial platelets and the subsequently formed latex particles. A simple mathematical model describing the amount of cooligomer required for the colloidal stability of the initial Gibbsite platelets and the subsequently formed particles was derived. This model was used to determine the reaction conditions required for obtaining colloidally stable nanocomposites with a targeted filler content. Cryogenic transmission electron microscopy characterization of the resulting nanocomposites with filler contents up to 20 wt% revealed fully encapsulated Gibbsite platelets and a mixed morphology of “muffin‐like” and encapsulated particles was obtained at higher filler contents.