Photoluminescent nanoparticles of organic-inorganic hybrids prepared by phase transfer complexation at the organic-aqueous solution interface

Monodispersed nanoparticles of Ag(I)-polymer hybrids have been prepared by using designed crown-ether-centred two-armed copolymers to chelate Ag+ ions at the interface of organic-aqueous solutions. The copolymer-Ag+ complex nanoparticles, as well as the reduced copolymer-Ag nanoparticles, have been characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), and x-ray photoelectron spectroscopy (XPS). The particle size can be varied by simply changing the polymer concentration, the monomers, and/or the molecular weight. The copolymer-Ag(I) hybrids exhibit weak photoluminescence, which was substantially enhanced after the hybrids were reduced to copolymer-silver nanoparticles with UV irradiation.

Self-assembly of polypeptide-containing ABC-type triblock copolymers in aqueous solution and its pH dependence

Self-assembling of novel biodegradable ABC-type triblock copolymer poly(ethylene glycol)-poly(L-lactide)-poly(L-glutamic acid) (PEG-PLLA-PLGA) is studied. In aqueous media, it self-assembles into a spherical micelle with the hydrophobic PLLA segment in the core and the two hydrophilic segments PEG and PLGA in the shell. With the lengths of PEG and PLLA blocks fixed, the diameter of the micelles depends on the length of the PLGA block and on the volume ratio of H2O/dimethylformamide (DMF) in the media. When the PLGA block is long enough, morphology of the self-assembly is pH-dependent. It assembles into the spherical micelle in aqueous media at pH 4.5 and into the connected rod at or below pH 3.2. The critical micelle concentration (cmc) of the copolymer changes accordingly with decreasing solution pH. Both aggregation states can convert to each other at the proper pH value. This reversibility is ascribed to the dissociation and neutralization of the COOH groups in the LGA residues. When the PLGA block is short compared to the PEG or PLLA block, it assembles only into the spherical micelle at various pH values.

Polyelectrolyte-functionalized ionic liquid for electrochemistry in supporting electrolyte-free aqueous solutions and application in amperometric flow injection analysis

As a green process, electrochemistry in aqueous solution without a supporting electrolyte has been described based on a simple polyelectrolyte-functionalized ionic liquid (PFIL)-modified electrode. The studied PFIL material combines features of ionic liquids and traditional polyelectrolytes. The ionic liquid part provides a high ionic conductivity and affinity to many different compounds. The polyelectrolyte part has a good stability in aqueous solution and a capability of being immobilized on different substrates. The electrochemical properties of such a PFIL-modified electrode assembly in a supporting electrolyte-free solution have been investigated by using an electrically neutral electroactive species, hydroquinone ( HQ) as the model compound. The partition coefficient and diffusion coefficient of HQ in the PFIL film were calculated to be 0.346 and 4.74 X 10(-6) cm(2) s(-1), respectively. Electrochemistry in PFIL is similar to electrochemistry in a solution of traditional supporting electrolytes, except that the electrochemical reaction takes place in a thin film on the surface of the electrode. PFILs are easily immobilized on solid substrates, are inexpensive and electrochemically stable. A PFIL-modified electrode assembly is successfully used in the flow analysis of HQ by amperometric detection in solution without a supporting electrolyte.

Partitioning behavior of amino acids in aqueous two-phase systems containing polyethylene glycol and phosphate buffer

The partitioning behavior of four amino acids, cysteine, phenylalanine, methionine, and lysine in 15 aqueous two-phase systems (ATPSs) with different polyethylene glycol (PEG) molecular weights and phosphate buffers has been studied in the present paper. The phase diagrams of the systems are investigated together with the effect of the PEG molecular weight and pH of the phosphate solutions. The composition of these systems and some parameters such as density and refractive index are determined. The influences of salts in ATPSs, side chain structure of the amino acids, pH of ATPSs, and the PEG molecular weight on the distribution ratios of the amino acids have been studied. This work is useful for the purification of amino acids and the separation of some proteins whose main surface exposed amino acid residues are these four amino acids, respectively.

Analysis of interfacial phenomena of aqueous solutions of polyethylene oxide and polyethylene glycol flowing in hydrophilic and hydrophobic capillary viscometers

Viscosities of aqueous solutions of five polyethylene oxide (PEO) samples with molar masses from 1.5 x 10(5) to 1.0 x 10(6) were carefully measured in a polytetrafluoroethylene (PTFE) capillary Ubbelohde viscometer in the concentration range from dilute down to extremely dilute concentration regions and compared with those of the same sample obtained from a glass capillary viscometer. At the same time, viscosities of aqueous solutions of three PEG samples in glass and paraffin-coated capillary viscosity were measured. The wall effects occurred in viscosity measurements for PEO and PEG aqueous solutions in different capillary viscometers were theoretically analyzed and discussed. It was found that different interfacial behaviors occurred in both hydrophobic and hydrophilic capillary viscometers respectively and the interfacial behaviors also exhibit molar mass dependence.

Formation equilibria of ternary metal complexes with citric acid and glutamine (alanine) in aqueous solution

The species and their formation constants in the ternary, systems were obtained by the Scogs2 software from potentiometric titration data. The Comics software was used to calculate the distribution of species in the ternary systems. MLXH, MLXH2 and MLXH3 are the common species in these systems. The coordination behaviors of the rare earths are very similar and their stability is closely matched. The ternary rare earth complexes are more stable than the corresponding ternary complexes of calcium. The ternary zinc complex with glutamine as the secondary ligand is more stable than the corresponding complexes of rare earths, but the ternary complex with alanine as the secondary ligand shows an inverse trend. The distributions of species in the ternary systems vary with pH changing. A prediction can be made that exogenous rare earths can affect the species of Ca and Zn in human body.

Probing the micellization of diblock and triblock copolymers of poly(L-lactide) and poly(ethylene glycol) in aqueous and NaCl salt solutions

The micelle formation of a series of amphiphilic block copolymers in aqueous and NaCl solutions was studied by a fluorescent probe technique using pyrene as a 'model drug'. These copolymers were synthesized from poly (ethylene glycol) (PEG) and L-lactide by a new calcium ammoniate catalyst. They had fixed PEG block lengths (44, 104 or 113 ethylene oxide units) and various poly(L-lactide) (PLLA) block lengths (15-280 lactide units). The critical micelle concentration (cmc) was found to decrease with increasing PLLA content. The distinct dissimilarity of the cmc values of diblock and triblock copolymers based on the same block length of PEG provided evidence for the different configurations of their micelles. It was also observed that the introduction of NaCl salt significantly contributed to a decrease in the cmcs of the copolymers with short PEG and PLLA blocks, while it had less influence on the cmcs of copolymers with long PEG or PLLA blocks. The dependence of partition coefficients ranging from 0.2x10(5) to 1.9x10(5) on the PLLA content in the copolymer and on the micelle configuration was also discussed.

Surface-enhanced Raman scattering studies on aggregated silver nanoplates in aqueous solution

Four different sizes of citrate-protected silver nanoplates with the corresponding in-plane dipole resonance band at 530, 619, 778, and 858 nm, respectively, are synthesized for surface-enhanced Raman scattering (SERS) study. Their aggregation behaviors are monitored by use of UV-vis spectroscopy. During the aggregation process, a marked red shift of the in-plane dipole resonance of silver nanoplates is observed, whereas other resonance modes of them only have small alterations in the site or intensity. Aggregated silver nanoplates can serve as active SERS substrates with an enhancement factor of about 4.5 x 10(5) using 2-aminothiophenol as a probing molecule. The SERS performance of silver nanoplates is even superior to the commonly used Lee-Meisel silver colloid, making them very attractive for SERS applications.

Noncovalent functionalization of multiwalled carbon nanotubes: Application in hybrid nanostructures

We developed a reproducible, noncovalent strategy to functionalize multiwalled carbon nanotubes (MWNTs) via embedding nanotubes in polysiloxane shells. (3-Aminopropyl)triethoxysilane molecules adsorbed to the nanotube surfaces via hydrophobic interactions are polymerized simply by acid catalysis and form a thin polysiloxane layer. On the basis of the embedded MWNTs, negatively charged gold nanoparticles are anchored to the nanotube surfaces via electrostatic interactions between the protonated amino groups and the gold nanoparticles. Furthermore, these gold nanoparticles can further grow and magnify along the nanotubes through heating in HAuCl4 aqueous solution at 100 degrees C; as a result these nanoparticles are joined to form continuous gold nanowires with MWNTS acting as templates.

PEG-supported dipyridyl ligand for palladium-catalyzed Suzuki and Suzuki-type reactions in PEG and aqueous media

An air- and water-stable PEG-supported bidentate nitrogen ligand is prepared and its applications in the palladium-catalyzed Suzuki reaction of aryl halides with arylboronic acids in PEG and Suzuki-type reaction of aryl halides with sodium tetraphenylborate in aqueous media are reported. The homogeneous catalyst system is environmentally friendly and offers the advantages of high activity, reusability and easy separation.

The first synthesis of a water-soluble alpha-cyclodextrin/C-60 supramolecular complex using anionic C-60 as a building block

A novel supramolecular inclusion complex of alpha-CD/C-60 was synthesized using anionic C-60. The reaction progress was monitored in situ by visible and near-IR spectroscopy. The obtained complex was characterized by UV-vis, C-13 NMR, MALDI-TOF, and cyclic voltammetry. The induction and dispersion forces are considered to be the major driving forces for the formation of a resulting alpha-CD/C-60(.-) inclusion complex.