微量钛掺杂的纳米二氧化锆相变过程中的光学性质

微量钛掺杂的纳米氧化锆由于纳米“小尺寸效应”的影响,在材料中产生了过量的氧空位缺陷,这些氧空位缺陷使得氧化锆在室温下呈现出高温的四方相。这种晶相的变化对氧化锆的光学性质产生了很大的影响。在氧化锆从四方相向单斜相的转变过程中,位于470 nm位置的Ti发光中心的宽带发光以及相同位置的余辉发光得到了增强。     

Rheological properties of multisticker associative polyelectrolytes in semidilute aqueous solutions

Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (N_H). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (N_H = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the N_H value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (N_H = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004     

Sol–Gel-Derived Corrosion-Protection Coatings

There is a current need for alternative coatings that can provide corrosion resistance to metals or alloy surfaces due to the environmental hazards posed by conventional coatings. Herein, we report on novel organically-modified sol–gel coatings for the protection of metal and alloy surfaces. The basic concept of chemical conversion of metal surfaces is based on deposition of a hydrophobic, nonporous sol–gel barrier layer for surface protection and corrosion prevention. The properties of these organosilica coatings can be tuned by varying the composition of precursors. The evaluation of hydrophobicity, adhesive strength, and anticorrosion properties of organically-modified sol–gel derived coatings suggests their potential utility as technologically-compatible alternatives to conventional coatings.     

Hydrogels Incorporating GdDOTA: Towards Highly Efficient Dual T(1) /T(2) MRI Contrast Agents

Do not tumble dry: Gadolinium-DOTA encapsulated into polysaccharide nanoparticles (GdDOTA?NPs) exhibited high relaxivity (r(1) =101.7?s(-1) mM(-1) per Gd(3+) ion at 37?°C and 20?MHz). This high relaxation rate is due to efficient Gd loading, reduced tumbling of the Gd complex, and the hydrogel nature of the nanoparticles. The efficacy of the nanoparticles as a T(1) /T(2) dual-mode contrast agent was studied in C6 cells.     

Superfast Responsive Ionic Hydrogels: Effect of the Monomer Concentration

A series of strong polyelectrolyte gels were prepared in aqueous solution, using the sodium salt of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) as the monomer and N,N'‐methylene(bis)acrylamide (BAAm) as a crosslinker. The gels were both prepared below (?22°C) and above (25°C) the bulk freezing temperature of the water, producing cryogels and hydrogels, respectively. The crosslinker (BAAm) content was set at 17 mol%, while the initial monomer concentration C_o was varied over a wide range. It was found that, at ?22°C, a macroscopic network starts to form at an initial monomer concentration of as low as 0.1 w/v%. In contrast to the conventional hydrogels formed at 25°C, the cryogels have a discontinuous morphology consisting of polyhedral pores of sizes 10⁰–10² μm. The cryogels exhibit superfast swelling properties, as well as reversible swelling–deswelling cycles in water and acetone. An increase in the initial monomer concentration from 2.5 to 10% further increases the response rate of the cryogels due to the simultaneous increase of the porosity of the networks.     

Fibrous Networks with Incorporated Macrocycles: A Chiral Stimuli‐Responsive Supramolecular Supergelator and Its Application to Biocatalysis in Organic Media

A new and versatile, crown ether appended, chiral supergelator has been designed and synthesized based on the bis‐urea motif. The introduction of a stereogenic center improved its gelation ability significantly relative to its achiral analogue. This low‐molecular‐weight gelator forms supramolecular gels in a variety of organic solvents. It is sensitive to multiple chemical stimuli and the sol–gel phase transitions can be reversibly triggered by host–guest interactions. The gel can be used to trap enzymes and release them on demand by chemical stimuli. It stabilizes the microparticles in Pickering emulsions so that enzyme‐catalyzed organic reactions can take place in the polar phase inside the microparticles, the organic reactants diffusing through the biphasic interface from the surrounding organic phase. Because of the higher interface area between the organic and polar phases, enzyme activity is enhanced in comparison with simple biphasic systems.     

From Nongelating to Gelating: Synthesis and Structural Self‐Assembling Property Relationships of a Homologous Series of Oligo(amide–triazole)s

A homologous series of oligo(amide–triazole)s (OAT) [ OAT‐CO₂H‐2 n and OAT‐COPrg‐(2 n +1) ] with an increasing number of primary amide (CONH) and triazole hydrogen‐bonding functionalities was prepared by an iterative synthetic procedure. It was found that their self‐assembly and thermoreversible gelation strength had a strong correlation to the number of hydrogen‐bonding moieties in the oligomers. There also existed a threshold value of the number of CONH units, above which all the oligomers became organogelators. Hence, oligomers with ≤4 CONH units are devoid of intermolecular hydrogen bonding and also non‐organogelating, whereas those that contain >4 CONH units show intermolecular association and organogelating properties. For the organogelators, the T_gel value increases monotonically with increasing number of CONH units. On the basis of FTIR measurements, both the CONH and triazole C? H groups were involved in the hydrogen‐bonding process. A mixed xerogel that consisted of a 1:1 weight ratio of two oligomers of different lengths ( OAT‐CO₂H‐6 and OAT‐CO₂H‐12 ) was found to show microphase segregation according to differential scanning calorimetry, thus indicating that oligomers that bear a different number of hydrogen‐bonding units exhibited self‐sorting to maximize the extent of intermolecular hydrogen bonding in the xerogel state.     

An Amino‐Acid‐Based Self‐Healing Hydrogel: Modulation of the Self‐Healing Properties by Incorporating Carbon‐Based Nanomaterials

An amino‐acid‐based (11‐(4‐(pyrene‐1‐yl)butanamido)undecanoic acid) self‐repairing hydrogel is reported. The native hydrogel, as well as hybrid hydrogels, have been thoroughly characterized by using various microscopic techniques, including transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman spectroscopy, fluorescence spectroscopy, FTIR spectroscopy, X‐ray diffraction, and by using rheological experiments. The native hydrogel exhibited interesting fluorescence properties, as well as a self‐healing property. Interestingly, the self‐healing, thixotropy, and stiffness of the native hydrogel can be successfully modulated by incorporating carbon‐based nanomaterials, including graphene, pristine single‐walled carbon nanotubes (Pr‐SWCNTs), and both graphene and Pr‐SWCNTs, within the native gel system. The self‐recovery time of the gel was shortened by the inclusion of reduced graphene oxide (RGO), Pr‐SWCNTs, or both RGO and Pr‐SWCNTs. Moreover, hybrid gels that contained RGO and/or Pr‐SWCNTs exhibited interesting semiconducting behavior.