Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles.

The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix[4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix[4]pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1- and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.

Stabilization of iron oxide nanoparticles in high sodium and calcium brine at high temperatures with adsorbed sulfonated copolymers.

A series of sulfonated random and block copolymers were adsorbed on the surface of ~100 nm iron oxide (IO) nanoparticles (NPs) to provide colloidal stability in extremely concentrated brine composed of 8% wt NaCl + 2% wt CaCl2 (API brine; 1.4 M NaCl + 0.2 M CaCl2) at 90 °C. A combinatorial materials chemistry approach, which employed Ca(2+)-mediated adsorption of anionic acrylic acid-containing sulfonated polymers to preformed citrate-stabilized IO nanoclusters, enabled the investigation of a large number of polymer coatings. Initially a series of poly(2-methyl-2-acrylamidopropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) (1:8 to 1:1 mol:mol), poly(styrenesulfonate-block-acrylic acid) (2.4:1 mol:mol), and poly(styrenesulfonate-alt-maleic acid) (3:1 mol:mol) copolymers were screened for solubility in API brine at 90 °C. The ratio of AMPS to AA groups was varied to balance the requirement of colloid dispersibility at high salinity (provided by AMPS) against the need for anchoring of the polymers to the iron oxide surface (via the AA). Steric stabilization of IO NPs coated with poly(AMPS-co-AA) (1:1 mol:mol) provided colloidal stability in API brine at room temperature and 90 °C for up to 1 month. The particles were characterized before and after coating at ambient and elevated temperatures by a variety of techniques including colloidal stability experiments, dynamic light scattering, zeta potential, and thermogravimetric analysis.

Stabilization of superparamagnetic iron oxide nanoclusters in concentrated brine with cross-linked polymer shells.

Iron oxide nanoparticles, in the form of sub-100-nm clusters, were synthesized in the presence of poly(acrylic acid) (PAA) or poly(styrene sulfonate-alt-maleic acid) (PSS-alt-MA) to provide electrosteric stabilization. The superparamagnetic nanoclusters were characterized using a superconducting quantum interference device (SQUID), transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA), and zeta potential measurements. To anchor the polymer shell on the nanoparticle surface, the polymer was cross-linked for a range of cross-linking densities. For nanoclusters with only 12% (w/w) PSS-alt-MA, electrosteric stabilization was sufficient even in 8 wt % NaCl. For PAA, the cross-linked polymer shell was essentially permanent and did not desorb even upon dilution of the nanoparticles for iron oxide concentrations down to 0.014 wt %. Without cross-linking, over half of the polymer desorbed from the particle surfaces. This general approach of the adsorption of polymer stabilizers onto nanoparticles followed by cross-linking may be utilized for a wide variety of cross-linkable polymers without the need to form covalent bonds between the nanoparticles and polymer stabilizer. Thus, this cross-linking approach is an efficient and inexpensive method of stabilizing nanoparticles for large-scale applications, including the electromagnetic imaging of subsurface reservoirs, even at high salinity.

Surface engineered gold nanoparticles through highly stable metal-surfactant complexes.

Monodispersed Au nanoparticles were synthesized by the reduction of Au-decyltrimethylammonium bromide (Au-DTAB), which was easily prepared via the reaction of HAuCl4 and DTAB. This Au-DTAB complex is highly stable in air and moisture, and suitable for large-scale synthesis of uniform-sized Au nanoparticles. The nanoparticles were characterized by transmission electron microscopy, optical absorption spectrometry, X-ray diffraction, and Fourier Transform infrared spectroscopy. The size of Au nanoparticles was controlled in the range of 5-10nm by changing the concentrations of reducing agent and Au precursor. The resulting Au nanoparticles were transferred to the aqueous phase after surface engineering using multidentate polymeric ligands with multiple imidazole functional groups. Polymeric imidazole ligands (PILs) demonstrated enhanced binding stability with the Au surface, and overcame the disadvantage of multidentate thiol ligand systems which have oxidative cross-linking and the formation of disulfide bonding. The colloidal stability of surface engineered Au nanoparticles with PILs was investigated by dynamic light scattering (DLS) characterization.

Control of magnetite primary particle size in aqueous dispersions of nanoclusters for high magnetic susceptibilities.

Aqueous dispersions of iron oxide nanoparticles with a high initial magnetic susceptibility (χi) are of interest as contrast agents in electromagnetic tomography. Nanoclusters composed of iron oxide primary particles were formed by co-precipitation of Fe(II) and Fe(III) chlorides at alkaline conditions and high temperature of 95°C. Two-step addition of citrate was used to produce large primary particles and then stabilize the nanoclusters. The size of the primary particles was tuned from 5nm to 15nm by varying the citrate/iron precursor ratio during the normal phase hydrolysis reaction, while the second iteration of citrate stabilized the nanoclusters with hydrodynamic diameters of 30-75nm. The crystallinity of the iron oxide nanoparticles was promoted by annealing at 95°C and systematically studied with Superconducting Quantum Interference Device (SQUID), Vibrating Sample Magnetometer (VSM), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). The dependence of χi was examined over a range of low volume fractions (0.005<θ<0.02) to understand the magnetic behavior of dispersions. The χi of the dispersions increased markedly with the size and concentration of the constituent primary particles, reaching an unusually high value of 0.85 at 1.6% v/v for 15nm primary particles, which is 2-3 times higher than that for typical commercial ferrofluids. The high χi values are favored by the high crystallinity and the large magnetic diameter of 9.3nm, indicating a relatively thin surface nonmagnetic layer where the spin orientations are disordered.

Synthesis of monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex.

We successfully synthesized monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex.

Graphene oxide nanoplatelet dispersions in concentrated NaCl and stabilization of oil/water emulsions.

Stable dispersions of graphene oxide nanoplatelets were formed in water at pH 2-10 even with 5 wt% NaCl. For these conditions, oil-in-water emulsions stabilized with graphene oxide nanoplatelets remained partially stable for 1 year. The droplet sizes were as small as ~1 µm with a low nanoplatelet concentration of 0.2 wt%. The emulsions were stable even for nanoplatelet concentrations down to 0.001 wt%. The stabilities of the emulsions even at high salinity may be attributed to the high anion density at the graphene oxide nanoplatelet edges which protrude into the water phase. Furthermore, the graphene oxide nanoplatelets are shown to adsorb on the surfaces of the oil droplets. The conceptual picture of graphene oxide nanoplatelets adsorbed to a greater extent on the water side of the oil/water interface, along with the high density of anions on their edges, cause the oil/water interface to curve about the oil phase, resulting in oil-in-water emulsion droplets. The dispersion stability with a very small amount of graphene oxide-based stabilizer, offers an intriguing opportunity for applications including CO2 sequestration and enhanced oil recovery in deep subsurface formations, which generally contain high-salinity brines.

Iron oxide nanoparticles grafted with sulfonated copolymers are stable in concentrated brine at elevated temperatures and weakly adsorb on silica.

Magnetic nanoparticles that can be transported in subsurface reservoirs at high salinities and temperatures are expected to have a major impact on enhanced oil recovery, carbon dioxide sequestration, and electromagnetic imaging. Herein we report a rare example of steric stabilization of iron oxide (IO) nanoparticles (NPs) grafted with poly(2-acrylamido-2-methylpropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) that not only display colloidal stability in standard American Petroleum Institute (API) brine (8% NaCl + 2% CaCl2 by weight) at 90 °C for 1 month but also resist undesirable adsorption on silica surfaces (0.4% monolayer NPs). Because the AMPS groups interacted weakly with Ca(2+), they were sufficiently well solvated to provide steric stabilization. The PAA groups, in contrast, enabled covalent grafting of the poly(AMPS-co-AA) chains to amine-functionalized IO NPs via formation of amide bonds and prevented polymer desorption even after a 40,000-fold dilution. The aforementioned methodology may be readily adapted to stabilize a variety of other functional inorganic and organic NPs at high salinities and temperatures.

Adsorption of iron oxide nanoclusters stabilized with sulfonated copolymers on silica in concentrated NaCl and CaCl2 brine.

Transport of metal oxide nanoparticles in porous rock is of interest for imaging and oil recovery in subsurface reservoirs, which often contain concentrated brine. Various copolymers composed of acrylic acid and either 2-acrylamido-2-methylpropanesulfonate or styrenesulfonate were synthesized and adsorbed on iron oxide nanoclusters to provide colloidal stability and to achieve low adsorption on silica in high salinity brine composed of 8%wt. NaCl+2%wt. CaCl2. Furthermore, the degree of adsorption of the nanoparticles on silica was controlled by modifying the acrylic acid groups in the copolymers with a series of diamines and triamines to add hydrophobicity. The adsorption on colloidal silica microparticles ranged from <1 mg/m(2) for highly charged hydrophilic surfaces on the iron oxide nanoparticles to 22 mg/m(2) for the most hydrophobic amine-modified surfaces, corresponding to monolayer coverages that ranged from 0.2% to 11.5%, respectively. The specific adsorption (mg-IO/m(2)-silica), monolayer coverage, and parameters for Langmuir isotherms were evaluated for various IO nanoclusters as a function of the properties of the copolymers on their surfaces.

Superparamagnetic nanoclusters coated with oleic acid bilayers for stabilization of emulsions of water and oil at low concentration.

Emulsions of water and dodecane with drop sizes down to 1 microm were stabilized with 30-100 nm interfacially active nanoclusters of sub-15 nm iron oxide primary particles at an extremely low loading of 0.14 wt.%. The nanoclusters, coated with a bilayer of oleic acid, formed stable dispersions in water at pH 7-10. The phase behavior and droplet morphologies of the emulsions of water and dodecane were tuned with pH. The oil/water emulsions at pH 9-10 were converted to middle phase emulsions at pH 6-7 and water/oil emulsions as the pH was further lowered. The magnetization per gram of Fe is similar for the nanoclusters and the primary particles, indicating the spacing between the particles is sufficient to avoid magnetic coupling. The larger volume of nanoclusters relative to the individual primary particles is beneficial for magnetomotive sensing applications including imaging of oil reservoirs, as it increases the force on the particles for a given magnetic field.

Generalized synthesis of metal phosphide nanorods via thermal decomposition of continuously delivered metal-phosphine complexes using a syringe pump.

We synthesized uniform-sized nanorods of transition metal phosphides from the thermal decomposition of continuously delivered metal-phosphine complexes using a syringe pump. MnP nanorods with dimensions of 8 nm x 16 nm and 6 nm x 22 nm sized were synthesized by the thermal decomposition of Mn-TOP complex, which was prepared from the reaction of Mn(2)(CO)(10) and tri-n-octylphosphine (TOP), using a syringe pump with constant injection rates of 10 and 20 mL/h, respectively. When Co-TOP complex, which was prepared from the reaction of cobalt acetylacetonate and TOP, was reacted in a mixture solvent composed of octyl ether and hexadecylamine at 300 degrees C using a syringe pump, uniform 2.5 nm x 20 nm sized Co(2)P nanorods were generated. When cobaltocene was employed as a precursor, uniform Co(2)P nanorods with 5 nm x 15 nm were obtained. When Fe-TOP complex was added to trioctylphosphine oxide (TOPO) at 360 degrees C using a syringe pump and then allowed to age at 360 degrees C for 30 min, uniform-sized FeP nanorods with an average dimension of 12 nm x 500 nm were produced. Nickel phosphide (Ni(2)P) nanorods with 4 nm x 8 nm were synthesized successfully by thermally decomposing the Ni-TOP complex, which was synthesized by reacting acetylacetonate [Ni(acac)(2)] and TOP. We measured the magnetic properties of these nanorods, and some of the nanorods exhibited different magnetic characteristics compared to the bulk counterparts.