Pt Nanoparticles Supported on TiO2 Colloidal Spheres with Nanoporous Surface: Preparation and Use as an Enhancing Material for Biosensing Applications

An easy surface-modified method has been developed to link -NH2 groups to the TiO2 colloidal spheres with nanoporous surface (f-TiO2). It was found that the as-prepared f-TiO2 is positively charged in neutral conditions and could act as an electrostatic anchor for nanosructures with opposite charge, Furthermore, platinum nanoparticles (Pt NPs) are successfully assembled on the f-TiO2 mainly via electrostatic interaction to fabricate a new kind of Pt NPs/TiO2 hybrid nanomaterial (f-TiO2-Pt NPs). The morphology, structure, and composition of the hybrids were characterized by the means of diverse techniques such as transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, and Raman spectra. Electrochemical experiments indicate the electrode modified with f-TiO2-Pt NPs shows prominent electrocatalytic activity toward the oxidation of hydrogen peroxide.

Preparation and characterization of poly (N-isopropylacrylamide)/polyvinylamine core-shell microgels

In this paper, well-defined temperature- and pH-sensitive core-shell microgels were synthesized by graft copolymerization in the absence of surfactant and stabilizer. The microgel particles consisted of poly (N-isopropylacrylamide (NIPAm)) core crosslinked with N, N'-methylene-bisacrylamide (MBA) and polyvinylamine (PVAm) shell. The effect of MBA content and NIPAm/PVAm ratio on microgel size was investigated. SEM showed that the microgels were spherical and had narrow particle-size distribution. TEM images of the microgels clearly displayed well-defined core-shell morphologies. Zeta-potential measurement further elucidated that the microgels possessed positively charged PVAm molecules on the microgel surface. Turbidity measurement and H-1-nuclear magnetic resonance (NMR) experiments indicated that the VPTT of microgels was the same as the LCST of PNIPAm.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).

Counterions in polyelectrolyte multilayers: A vehicle for introducing functionalities

Counterions present at the surface of polyelectrolyte multilayers were utilized for the introduction of charged species into the multilayer via ion exchange. A typical polyelectrolyte multilayer film with Na+ counterions in the outermost layer was immersed in an AgNO3 aqueous solution and the rapid ion-exchange process was complete within 1 min. The silver ions thus introduced were then reduced in situ and silver nanoparticles were produced at the surface of the multilayer assembly. This example demonstrates that the counterions naturally occurring in every polyelectrolyte multilayer film can be a convenient vehicle for the introduction of various functionalities to the film.

Type I collagen-mediated synthesis and assembly of UV-photoreduced gold nanoparticles and their application in surface-enhanced Raman scattering

We reported a simple method to synthesize gold nanoparticles (NPs) by photoreducing HAuCl4 in acetic acid solution in the presence of type I collagen. It was found that the collagen takes an important role in the formation of gold NPs. The introduction of collagen made the shape of the synthesized gold nanocrystals change from triangular and hexangular gold nanoplates to size-uniform NPs. On the other hand, thanks to the special characters of collagen molecules, such as its linear nanostructure, are positively charged when the pH < 7, and the excellent self-assembly ability, photoreduced gold NPs were assembled onto the collagen chains and formed gold NPs films and networks. A typical probe molecule, 4-aminothiophenol, was used to test the surface-enhanced Raman scattering activity of these gold NPs films and networks and the results indicated good Raman activity on these substrates.

Nucleic Acid-Induced Aggregation and Pyrene Excimer Formation

Nucleic acid was found to induce the aggregation of the positively charged pyrene probe (compound 1); as a result, strong pyrene excimer emission was observed. The intensity of the excimer emission was dependent on the concentration of the pyrene probe and the oligonucleotide length, sequence, and concentration. These results suggest a new strategy for label-free nucleic acid-based biosensing applications.

A novel alcohol dehydrogenase biosensor based on solid-state electrogenerated chemiluminescence by assembling dehydrogenase to Ru(bpy)(3)(2+)-Au nanoparticles aggregates

Based on electrogenerated chemiluminescence (ECL), a novel method for fabrication of alcohol dehydrogenase (ADH) biosensor by self-assembling ADH to Ru(bpy)(3)(2+) -AuNPs aggregates (Ru-AuNPs) on indium tin oxide (ITO) electrode surface has been developed. Positively charged Ru(bpy)(3)(2+) could be immobilized stably on the electrode surface with negatively charged AuNPs in the form of aggregate via electrostatic interaction. On the other hand, AuNPs are favourable candidates for the immobilization of enzymes because amine groups and cysteine residues in the enzymes are known to bind strongly with AuNPs. Moreover, AuNPs can act as tiny conduction centers to facilitate the transfer of electrons. Such biosensor combined enzymatic selectivity with the sensitivity of ECL detection for quantification of enzyme substrate, and it displayed wide linear range, high sensitivity and good stability.

Electronic structures and chemical bonding in diatomic ScX to ZnX (X = S, Se, Te)

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies, and dipole moments of the title molecules in neutral, positively, and negatively charged ions were studied using density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that, besides ionic component, covalent bonds are formed between the metal s, d orbitals, and the p orbital of S, Se, and Te. For neutral and cationic molecules, the covalent character increases from ScX to CrX and from FeX to CuX with an exception of decrease at MnX and ZnX, while for anionic molecules, the trend is not obvious. For both neutral and charged molecules, the sulfides have the shortest bond distance and largest vibrational frequency, while tellurides have the largest bond distance and smallest vibrational frequency. For neutral and anionic molecules, the dissociation energy of sulfides is the largest, that of tellurides is the smallest, while this only remains true for cationic molecules from ScX+ to FeX+.

Electronic structures and chemical bonding in 4d transition metal monohalides

Bond distances, vibrational frequencies, dipole moments, dissociation energies, electron affinities, and ionization potentials of NIX (XM = Y-Cd, X = F, Cl, Br, I) molecules in neutral, positively, and negatively charged ions were studied by density functional method, B3LYP. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the 4d transition metal s, d orbitals, and the p orbital of halogen. For both neutral and charged molecules, the fluorides have the shortest bond distance, iodides the longest. Although the opposite situation is observed for vibrational frequency, that is, fluorides have the largest value, iodides the smallest. For neutral and anionic species, the dissociation energy tends to decrease with the increasing atomic number from Y to Cd, suggesting the decreasing or weakening of the bond strength. For cationic species, the trend is observed from Y to Ag.

Density functional studies of diatomic LaO to LuO

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies and dipole moments of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the metal s, d and f orbitals and oxygen p orbitals. Contrary to the well known lanthanide contraction, the bond distance is not regular from LaO to LuO for both neutral and charged molecules. An obvious population at 5d orbital was observed through the lanthanide series. 4f electrons also participate the chemical bonding for CeO to NdO and TbO to TmO. For EuO, GdO, YbO and LuO, 4f electrons tend to be localized. The spin multiplicity is regular for neutral and charged molecules. The spin multiplicity of the charged molecules can be obtained by -1 (or +1 for TbO+, DyO+, YbO- and YbO+) compared with the corresponding neutral molecules.

Electronic structures of 4d transition metal monoxides by density functional theory

Bond distances, dissociation energies, ionization potentials and electron affinities of 4d transition metal monoxides from YO to CdO and their positive and negative ions were studied by use of density functional methods B3LYP, BLYP, B3PW91, BPW91, B3P86, BP86, SVWN, MPW1PW91 and PBE1PBE. It was found that calculated properties are highly dependent on the functionals employed, especially for dissociation energy. For most neutral species, pure density functionals BLYP, BPW91 and BP86 have good performance in predicting dissociation energy than hybrid density functionals B3LYP, B3PW91 and B3P86. In addition, BLYP gives the largest bond distance compared with other density functional methods, while SVWN gives shortest bond distance, largest dissociation energy and electron affinity. For the ground state, the spin multiplicity of the charged species can be obtained by +/- 1 of their corresponding neutral species.