Solvent induced ordered-supramolecular assembly of highly branched protoporphyrin IX derivative

Protoporphyrin IX species bearing highly branched alkyl chains were self-assembled into well-defined nanostructures such as rod-like in CHCl₃–cylcohexane (1:9, v/v) and a honeycomb-like morphology in a polar solvent dimethyl sulfoxide (DMSO). The rod-like morphologies observed in the atomic force microscopy (AFM) and transmission electron microscopy (TEM) suggest that the lamellar phase self-organises into multilamellar vesicles. The X-ray diffraction (XRD) results indicate molecular arrangements resulting from longitudinal and transverse stacking of the porphyrin head groups in the lamellar structure. The typical nanostructures were derived from a high level of cooperativity between the porphyrin cores via π–σ interactions and supported by hydrogen bonding and van der Waals interactions. The nanostructures were characterised by means of UV–vis, fluorescence, AFM, TEM and XRD analysis. Our methodology confirms the potential of protoporphyrin IX derivatives in supramolecular chemistry.     

Single laser pulse induced aggregation of gold nanoparticles

Gold nanoparticles with an average diameter of 11 nm (Au(39000)) were prepared in an SDS aqueous solution. A 80-microm liquid droplet (microdroplet) of the solution was ejected into the atmosphere from a microdroplet nozzle. Structural changes of the gold nanoparticles in the microdroplet, after they were irradiated with a focused single-nanosecond laser pulse at the wavelength of 532 nm, were studied by transmission electron microscopy (TEM) and optical absorption spectroscopy. It was revealed that the gold nanoparticles are fragmented into small particles and then the small fragments aggregate with each other. The aggregation was found to be terminated 100 micros after the laser-pulse excitation.     

Red cell zinc protoporphyrin and protoporphyrin by HPLC with fluorescence detection

A high performance liquid chromatographic (HPLC) method was developed for the determination of zinc protoporphyrin (ZnPP) and protoporphyrin (PP) in whole blood. After adding the blood to dilute acetic acid, ZnPP and PP were extracted with dimethyl sulfoxide-acetone containing mesoporphyrin as internal standard. Following evaporation of the acetone, the haemin-free extract was analysed by HPLC. ZnPP and PP were separated on a reversed-phase column and quantitated by measuring fluorescence peak areas. The extraction method is simple, and applicable to batch analysis, and the HPLC separation is rapid and repoducible. The coefficient of variation for ZnPP was 5.6% and 3.3% for total red cell porphyrin levels of 3.5 and 10.2 mumol per litre RBC respectively. Results are discussed in patients with erythrohepatic protoporphyria, lead exposure, iron-deficiency and nonspecifically elevated total red cell porphyrins.     

Rapid aggregation of gold nanoparticles induced by non-cross-linking DNA hybridization

To date, aggregation of DNA-functionalized gold nanoparticles by hybridization of target DNA in a cross-linking configuration has been intensively studied. Here, we report that aggregation in a non-cross-linking configuration is also possible and is even better from the viewpoint of genetic analysis because of its speed and sensitivity. In this system, 15 nm diameter gold nanoparticles functionalized with (alkanethiol)-15mer DNA are hybridized to target 15mer DNA at room temperature. At high NaCl concentration (>/=0.5 M), hybridization with complementary target DNA induces nanoparticle aggregation based on the salting-out effect. The aggregation can be detected by a colorimetric change of the colloidal solution within 3 min. Furthermore, unusual sensitivity of this system for single-base mismatch at the terminus opposite to the anchored side has been discovered. In fact, target DNA with such a kind of mismatch does not induce the colorimetric change at all, while target DNA with single-base mismatch at the middle of it cannot be discriminated from the fully complementary target. This non-cross-linking aggregation system opens up a new possibility of rapid and reliable genetic analysis.     

Solvent extraction of gold

The separation of gold by solvent extraction is reviewed.     

Electronic excitations induced by hydrogen surface chemical reactions on gold

Associated with chemical reactions at surfaces energy may be dissipated exciting surface electronic degrees of freedom. These excitations are detected using metal-insulator-metal (MIM) heterostructures (Ta-TaOx-Au) and the reactions of H with and on a Au surface are probed. A current corresponding to 5×10(-5) electrons per adsorbing H atom and a marked isotope effect are observed under steady-state conditions. Analysis of the current trace when the H atom flux is intermitted suggests that predominantly the recombination reaction creates electronic excitations. Biasing the front versus the back electrode of the MIM structure provides insights into the spectrum of electronic excitations. The observed spectra differ for the two isotopes H and D and are asymmetric when comparing negative and positive bias voltages. Modeling indicates that the excited electrons and the concurrently created holes differ in their energy distributions.     

Mercuric ions induced aggregation of gold nanoparticles as investigated by localized surface plasmon resonance light scattering and dynamic light scattering techniques

With the development of nanosciences, both localized surface plasmon resonance light scattering (LSPR-LS) and dynamic light scattering (DLS) techniques have been widely used for quantitative purposes with high sensitivity. In this contribution, we make a comparison of the two light scattering techniques by employing gold nanoparticles (AuNPs) aggregation induced by mercuric ions. It was found that citrate-stabilized AuNPs got aggregated in aqueous medium in the presence of mercuric ions through a chelation process, resulting in greatly enhanced LSPR-LS signals and increased hydrodynamic diameter. The enhanced LSPR-LS intensity ( I) is proportional to the concentration of mercuric ions in the range of 0.4-2.5 M following the linear regression equation of I = 84.7+516.4c, with the correlation coefficient of 0.983 (n = 6) and the limit of determination (3 ) about 0.10 M. On the other hand, the increased hydrodynamic diameter can be identified by the DLS signals only with a concentration of Hg 2+ in the range of 1.0-2.5 M, and a linear relationship between the average hydrodynamic diameters of the resulted aggregates and the concentration of Hg 2+ can be expressed as d = 6.16 + 45.9c with the correlation coefficient of 0.994. In such case, LSPR-LS signals were further applied to the selective determination of mercuric ions in lake water samples with high sensitivity and simple operation.     

Study of electrolyte induced aggregation of gold nanoparticles capped by amino acids

This work reports the electrolyte induced aggregation of gold nanoparticles directly conjugated to amino acid by chemical reduction in aqueous solution. The study was focused on three different classes of amino acids depending on the nature of alpha substituent, viz. l-cysteine, l-leucine, and l-asparagine. The band broadening and the red shift of surface plasmon band with increase in flocculation parameter showed the aggregation of gold nanoparticles with increase in electrolyte concentration and decrease in pH as monitored by UV-visible spectrophotometer. The (1)H NMR spectrum demonstrates that the sulfide bond of cysteine and alpha amino group of leucine and asparagine interact with nanoparticles surface. Furthermore, transmission electron microscope (TEM) and thermogravimetric analysis (TGA) were performed to characterize and to support the fate of stabilization of the gold nanoparticles by amino acid.     

Surface-grafted hybrid material consisting of gold nanoparticles and dextran exhibits mobility and reversible aggregation on a surface

Gold nanoparticles linked to linear carboxylated dextran chains were attached to 3-aminopropyltriethoxysilane-functionalized glass surfaces. This method provides novel hybrid nanostructures on a surface with the unique optical properties of gold nanoparticles. The particles attached to the surface retain the capability to aggregate and disaggregate in response to their environment. This procedure presents an alternative method to the immobilization of gold nanoparticles onto planar substrates. Compared to gold nanoparticle monolayers, larger particle surface densities were obtained. Exposure to hydrophobic environments changes the conformation of the hydrophilic dextran chains, causing the gold nanoparticles to aggregate and inducing changes in the absorption spectrum such as red-shifting and broadening of the plasmon absorption peaks. These changes, characteristic of particle aggregation, are reversible. When the substrates are dried and then immersed in an aqueous environment, these changes can be visually observed in a reversible fashion and the sample changes color from the red color of colloidal gold to a bluish-purple color of aggregated nanoparticles. Surface-bound nanoparticles that retain their mobility when attached to a surface by means of a flexible polymer chain could expand the use of aggregation-based assays to solid substrates.     

Solvent polarity driven helicity inversion and circularly polarized luminescence in chiral aggregation induced emission fluorophores

Development of functional materials capable of exhibiting chirality tunable circularly polarized luminescence (CPL) is currently in high demand for potential technological applications. Herein we demonstrate the formation of both left- and right-handed fluorescent helical superstructures from each enantiomer of a chiral tetraphenylethylene derivative through judicious choice of the solution processing conditions. Interestingly, both the aggregation induced emission active enantiomers exhibit handedness inversion of their supramolecular helical assemblies just by varying the solution polarity without any change in their molecular chirality. The resulting helical supramolecular aggregates from each enantiomer are capable of emitting circularly polarized light, thus enabling both right- and left-handed CPL from a single chiral material. The left- and right-handed supramolecular helical aggregates in the dried films have been characterized using spectroscopy, scanning electron microscopy, and transmission electron microscopy techniques. These new chiral aggregation induced emission compounds could find applications in devices where CPL of opposite handedness is required from the same material and would facilitate our understanding of the formation of helical assemblies with switchable supramolecular chirality.

The formation of both left- and right-handed helical superstructures with circularly polarized luminescence has been achieved in a chiral tetraphenylethylene derivative just by varying the solution polarity without any change in molecular chirality.     

Novel catalysis of gold deposited on metal oxides

Gold exhibits a unique catalytic nature and action when it is deposited as nanoparticles on a variety of metal oxides. Most reactions are noticeably structure sensitive over such supported gold catalysts. Typical examples obtained in Japan of the low-temperature catalytic combustion, partial oxidation of hydrocarbons, hydrogenation of carbon oxides and unsaturated hydrocarbons, reduction of nitrogen oxides, and so forth, are presented. Another line of advance is also introduced in the thin films of gold metal oxide composites, which are applicable to electrical and optical gassensing.     

The origin of surface stress induced by adsorption of iodine on gold

The cantilever technique for the measurement of film stress on both macroscopic and microscopic cantilevers is validated, then applied to the experimental determination of film stress induced by the adsorption of a monolayer of iodine onto a gold substrate. A model is proposed that relates the change in the interatom potential upon chemisorption of iodine onto gold to the measured film stress. Excellent agreement is found with the experimentally determined value. This result gives insight into the origins of film stress that is observed in all thin film and coating applications.     

Visual and surface plasmon resonance sensor for zirconium based on zirconium-induced aggregation of adenosine triphosphate-stabilized gold nanoparticles

Owing to its high affinity with phosphate, Zr(IV) can induce the aggregation of adenosine 5′-triphosphate (ATP)-stabilized AuNPs, leading to the change of surface plasmon resonance (SPR) absorption spectra and color of ATP-stabilized AuNP solutions. Based on these phenomena, visual and SPR sensors for Zr(IV) have been developed for the first time. The A_660 nm/A_518 nm values of ATP-stabilized AuNPs in SPR absorption spectra increase linearly with the concentrations of Zr(IV) from 0.5 μM to 100 μM (r = 0.9971) with a detection limit of 95 nM. A visual Zr(IV) detection is achieved with a detection limit of 30 μM. The sensor shows excellent selectivity against other metal ions, such as Cu²⁺, Fe³⁺, Cd²⁺, and Pb²⁺. The recoveries for the detection of 5 μM, 10 μM, 25 μM and 75 μM Zr(IV) in lake water samples are 96.0%, 97.0%, 95.6% and 102.4%, respectively. The recoveries of the proposed SPR method are comparable with those of ICP-OES method.     

Solvent effects on the aggregation state of lithium dialkylaminoborohydrides

DFT calculations were performed to determine the effects of ethereal solvents on the aggregation state of lithium dialkylaminoborohydrides (LABs). The calculations included dimerization energies in the gas phase, with continuum solvation only, microsolvation with coordinating ethereal ligands, and a combination of the microsolvation and continuum models. The continuum model alone overestimates the stability of the dimers, apparently due to the lack of steric effects from the coordinating ethereal ligands. The use of the combined microsolvation and continuum solvation models predicts lithium dimethylaminoborohydride to be a mixture of monomer and dimer in THF, and more sterically hindered lithium aminoborohydrides to exist primarily as monomers. The kinetics of amination of 1-chlorodecane by lithium dimethylaminoborohydride showed no detectable change in reaction rate with time, suggesting that the LAB reagent may exist primarily as a monomer in THF.     

Reversible aggregation/deaggregation of gold nanoparticles induced by a cleavable dithiol linker

Aqueous solutions of Au colloids (12 +/- 4 nm size) when treated with a blend of mono- and dithiols aggregate forming stable clusters, as evidenced by the shift of their surface plasmon (SP) band from 512 to ca. 600 nm. The presence of carboxylate ester functions on the dithiol allows its cleavage by addition of a cleaving agent, such as hydrazine. The cleavage process results in the breaking down of the clusters of nanoparticles and the shift of the SP band back to lower wavelengths. Further addition of dithiol causes the formation of the clusters again. The aggregation/deaggregation process may be monitored visually by following the color change from pink-red to purple and vice versa in the forward and backward steps, respectively.     

Electrochemical properties of protoporphyrin IX zinc(II) films

The electrochemical properties of protoporphyrin IX zinc(II) (ZnPP) films on indium-tin oxide (ITO) substrate have been studied for three types of films with different arrangements, which were an adsorbed film of ZnPP and LB films of ZnPP and its hybrid with hexadecyltrimethylammonium bromide. Cyclic voltammetry (CV) measurement showed that, as the adsorbed amount of ZnPP increases, an irreversible oxidation peak of ZnPP film is intensified. This reveals that electrochemical properties depend on the adsorbed amount rather than the orientation of porphyrin molecules. It was also supported from CV measurement and ultraviolet-visible absorption spectroscopy that porphyrins adsorbed on ITO substrate were desorbed after the single scan of potential. Additionally, photoresponse of these ZnPP films was investigated by photocurrent measurement. The photocurrent generation is due to carboxylic acid moieties but not ZnPP macrocycles.     

Solvent effect on the aggregation behavior of rod-coil diblock copolymers

The water-induced aggregation behavior of rod-coil diblock copolymers based on poly(ethylene oxide) (PEO) and poly{(+)-2,5-bis[4'-((S)-2-methylbutoxy)phenyl]styrene} (PMBPS), PEO104-b-PMBPS53, was investigated in the common solvent THF and in the selective solvent dioxane. Before adding water, PEO104-b-PMBPS53 stayed as single polymer chains no matter what conformation the PEO block took (i.e., either the random coil conformation in THF or the compact globule conformation in dioxane). The critical water content ( approximately 6 wt %) at which PEO104-b-PMBPS53 began to aggregate was also similar in both solvents, indicating that PMBPS dominated the aggregation process. However, the size, the size distribution, and the morphology of aggregates in THF/water were quite different from those in dioxane/water. Narrowly distributed spheres with Rh approximately 20 nm were observed in dioxane, whereas in THF, a bimodal distribution peaked at 3 and approximately 300 nm, was observed. The results from 2D wide-angle X-ray diffraction and polarized optical microscopy demonstrated that the PMBPS blocks packed in a parallel pattern upon aggregation in dioxane/water. The anisotropic disclike structures observed in THF/water also indicated the orientation of the PMBPS blocks upon forming aggregates in dilute solution.     

Solvent extraction of gold with N-substituted benzoylthioureas

Summary Benzoylthioureas are excellent reagents for the solvent extraction of gold. Very effective separations of gold from platinum group metals and base metals are possible due to control of the extraction parameters. The best results, a fast extraction and low residual gold concentrations <1 g/l are obtained with N,N-Di-n-hexylbenzoylthiourea/toluene.