Binyang Du

One-Pot Preparation of Hollow Silica Spheres by Using Thermosensitive Poly(N-isopropylacrylamide) as a Reversible Template

Hollow silica nanospheres with mesoporous shells were successfully fabricated with a new one-pot strategy by using a thermosensitive polymer, poly(N-isopropylacrylamide) (PNIPAm), as a reversible template without the need of further calcination or chemical etching. By simply regulating the solution temperature with respect to the lower critical solution temperature (LCST) of PNIPAm, PNIPAm chains can reversibly form aggregates or dissolve in aqueous solution. The thermosensitive character makes PNIPAm chains behave as soft templates for the formation of core-shell silica nanospheres at elevated temperature (>LCST), and they will then diffuse out of the cores at lower temperature (<LCST), leading to the formation of hollow silica nanospheres. The TEM, SEM, XRD, and N(2) adsorption-desorption results indicate that the shells of such hollow silica nanospheres also contain large quantities of irregular mesopores. This new strategy was also tested with another thermosensitive polymer, poly(vinyl methyl ether) (PVME). However, only solid silica nanospheres with a broad size distribution were obtained when PVME was used. We speculated on the possible formation mechanism of hollow silica nanospheres with PNIPAm templates. The effects of the initial concentration of PNIPAm, the molecular weight of PNIPAm, and the pretreatment of silica precursor on the morphology and size of the resultant hollow silica nanospheres were also investigated. The PNIPAm soft templates were confirmed to be recyclable.

Fabrication and Properties of Thermosensitive Organic/Inorganic Hybrid Hydrogel Thin Films

We report on a facile method for fabricating thermosensitive organic/inorganic hybrid hydrogel thin films from a cross-linkable organic/inorganic hydrid copolymer, poly[ N-isopropylacrylamide- co-3-(trimethoxysilyl)propylmethacrylate] [P(NIPAm- co-TMSPMA)]. Fourier transform infrared (FT-IR) spectra confirmed the formation of hybrid hydrogel thin films after hydrolysis of the methoxysilyl groups (Si-O-CH 3) and subsequent condensation of the silanol groups (Si-OH). Atomic force microscopy (AFM) images revealed that the surface morphology of the hydrogel thin films depended on the supporting substrates. Microdomains were observed for the hydrogel thin films on a gold surface, which can be attributed to inhomogeneous network structures. The thermoresponsive swelling-deswelling behavior and the viscoelastic properties of the hydrogel thin films were investigated as a function of temperature (25-45 degrees C) by using a quartz crystal microbalance (QCM) operated in water. The high frequency shear modulus of the P(NIPAm- co-TMPSMA) hydrogel thin films was several hundred kilopascals.

Direct measurement of plowing friction and wear of a polymer thin film using the atomic force microscope

Nanometer-scale plowing friction and wear of a polycarbonate thin film were directly measured using an atomic force microscope (AFM) with nanoscratching capabilities. During the nanoscratch tests, lateral forces caused discrepancies between the maximum forces for the initial loadings prior to the scratch and the unloading after the scratch. In the case of a nanoscratch test performed parallel to the cantilever probe axis, the plowing friction added another component to the moment acting at the cantilevered end compared to the case of nanoindentation, resulting in an increased deflection of the cantilever. Using free-body diagrams for the cases of nanoindentation and nanoscratch testing, the AFM force curves were analyzed to determine the plowing friction during nanoscratch testing. From the results of this analysis, the plowing friction was found to be proportional to the applied contact force, and the coefficient of plowing friction was measured to be 0.56 +/- 0.02. Also, by the combination of nanoscratch and nanoindentation testing, the energetic wear rate of the polycarbonate thin film was measured to be 0.94 +/- 0.05 mm(3)/(N m).

Thermosensitive Ionic Microgels via Surfactant-Free Emulsion Copolymerization and in Situ Quaternization Cross-Linking

A type of thermosensitive ionic microgel was successfully prepared via the simultaneous quaternized cross-linking reaction during the surfactant-free emulsion copolymerization of N-isopropylacrylamide (NIPAm) as the main monomer and 1-vinylimidazole or 4-vinylpyridine as the comonomer. 1,4-Dibromobutane and 1,6-dibromohexane were used as the halogenated compounds to quaternize the tertiary amine in the comonomer, leading to the formation of a cross-linking network and thermosensitive ionic microgels. The sizes, morphologies, and properties of the obtained ionic microgels were systematically investigated by using transmission electron microscopy (TEM), dynamic and static light scattering (DLS and SLS), electrophoretic light scattering (ELS), thermogravimetric analyses (TGA), and UV-visible spectroscopy. The obtained ionic microgels were spherical in shape with narrow size distribution. These ionic microgels exhibited thermosensitive behavior and a unique feature of poly(ionic liquid) in aqueous solutions, of which the counteranions of the microgels could be changed by anion exchange reaction with BF4K or lithium trifluoromethyl sulfonate (PFM-Li). After the anion exchange reaction, the ionic microgels were stable in aqueous solution and could be well dispersed in the solvents with different polarities, depending on the type of counteranion. The sizes and thermosensitive behavior of the ionic microgels could be well tuned by controlling the quaternization extent, the type of comonomer, halogenated compounds, and counteranions. The ionic microgels showed superior swelling properties in aqueous solution. Furthermore, these ionic microgels also showed capabilities to encapsulate and release the anionic dyes, like methyl orange, in aqueous solutions.

Poly(N-vinylpyrrolidinone) Microgels: Preparation, Biocompatibility, and Potential Application as Drug Carriers

The biocompatible poly(N-vinylpyrrolidinone) (PNVP) microgels were synthesized via surfactant free emulsion polymerization with N-vinylpyrrolidinone (NVP) as the monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linker at 60 °C. The obtained PNVP microgels are spherical in shape with hydrodynamic diameter of approximately 200 nm and narrow size distribution. The PNVP microgels show rough surfaces due to the different reaction rates of monomer NVP and cross-linker EGDMA. The obtained PNVP microgels could well disperse in phosphate-buffered saline (PBS) solution with long-term stability, which make them candidates for bioapplications. The results of 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) tests indicated that the PNVP microgels are biocompatible with low toxicity even at a concentration of 1000 μg/mL. By labeling the PNVP microgels with fluorescein comonomer, it was demonstrated that the PNVP microgels could be uptaken by human embryonic kidney 293 (HEK-293) cells. The experimental results indicated that the release of isoniazid (INH, the hydrophilic model drug) could be well described by a Fickian release, whereas the microgels exhibited burst release for 5-fluorouracil (5-fu, the hydrophobic model drug).

Speedy fabrication of free-standing layer-by-layer multilayer films by using polyelectrolyte complex particles as building blocks

A novel method for speedy fabrication of free-standing layer-by-layer (LbL) multilayer films in salt free media, and without the need for a sacrificial sublayer is described by using two different polyelectrolyte complex (PEC) nanoparticles as LbL self-assembly building blocks. Negatively charged polyelectrolyte complex particles (PEC−) consisting of poly(diallyldimethylammonium chloride)/sodium carboxymethyl cellulose (PDDA/CMCNa), and positively charged polyelectrolyte complex particles (PEC+) consisting of PDDA/poly(sodium-p-styrenesulfonate) (PDDA/PSSNa) were prepared and characterized by FT-IR, zeta-potential (ζ potential) and transmission electron microscopy (TEM). The LbL self-assembly of PEC+/PEC− and PDDA/PEC− was followed by quartz crystal microbalance (QCM), optical transmittance, UV-vis absorption spectroscopy and atomic force microscopy (AFM). QCM results show that the thickness growth rate of the PEC+/PEC− pair is 9 times faster than that of the PDDA/PEC− pair and this result is also supported by optical transmittance and UV-vis absorption. A robust free-standing multilayer film of (PEC+/PEC−)25 can be easily peeled off from the substrate after being cross-linked in 3.5 wt% glutaraldehyde (GA) (80 °C, 50mins). Field emission electron scanning microscopy (FESEM) indicates that both the surface and cross-section of the multilayer film display layered structures. Furthermore, multiwall carbon nanotubes (MWCNTs) can also be uniformly incorporated into the free-standing LbL multilayer film by pre-incorporating MWCNTs into PEC− particles. The experimental results show that using oppositely charged PEC particles as LbL assembly components is a speedy and convenient method to fabricate free-standing LbL multilayer films either with or without nanofillers.

Convergence of dissipation and impedance analysis of quartz crystal microbalance studies.

A quartz crystal microbalance (QCM) consists of a resonator, which measures the resonance frequency of the quartz slab. When coupled with a network analyzer or coupled with impulse excitation technology, QCM gives additional impedance or dissipation information, respectively. This report provides a set of equations that bring the QCM community a convergence of the dissipation and impedance analysis. Equations derived from the complex frequency shift were applied to quantitatively analyze the dissipation data of polymer brushes obtained from QCM-D. The obtained viscoelastic properties of polymer brushes were then compared with those obtained by the Voigt model method. We believe that these equations will be useful in quantitative studies of interfacial phenomena accompanied with mass or viscoelasticity changes.

Influences of Solution Property and Charge Density on the Self-Assembly Behavior of Water-Insoluble Polyelectrolyte Sulfonated Poly(sulphone) Sodium Salts

Two sulfonated poly(sulphone) sodium salts (SPSF) with different molecular weights and ionic exchange capacities in a N,N-dimethyl formamide/water (DMF-H2O) mixed solvent with various DMF contents were selected as a model system for investigating the influences of solvent composition, solution properties, and charge density of polyelectrolytes on the layer-by-layer (LbL) self-assembly of water-insoluble polyelectrolytes. Poly(dimethyldiallylammonium chloride) (PDDA) in aqueous solution was used as the counterpart. The PDDA/SPSF multilayer films grew nearly linearly with the layer numbers regardless of the volume fraction of DMF, phiDMF, in the SPSF solutions. The total absorption amount of the PDDA/SPSF multilayer films was strongly dependent on the charge density of the SPSF molecules and the phiDMF value of the SPSF solutions. Minimum values of absorption amount were observed at phiDMF = 0.6 to approximately 0.7. The surface hydrophobicity and roughness of the multilayer films can be tuned by varying phiDMF. These observations were rationalized in terms of the chain dimension and the ionization degree of the SPSF molecules as a function of phiDMF, which was characterized by the intrinsic viscosity ([eta]SPSF) and conductivity (LSPSF) of the SPSF solutions. The results indicate that the molecular structures of the DMF-H2O mixed solvent strongly affect the solution properties of SPSF, which in turn determine the growth behavior and physical properties of the PDDA/SPSF multilayer films.

Fabrication of free-standing polyelectrolyte multilayer films: a method using polysulfobetaine-containing films as sacrificial layers.

A new pH-dependent sacrificial system based on zwitterionic polysulfobetaine was proposed for the fabrication of free-standing polyelectrolyte multilayer films. The zwitterionic polysulfobetaine, poly(4-vinylpyridine propylsulfobetaine) (P4VPPS), was synthesized and its layer-by-layer (LbL) self-assembly behavior with poly(diallyldimethylammonium) (PDDA) as counterpart was investigated by using UV-vis absorption spectroscopy, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). The LbL multilayer films of PDDA/P4VPPS were successfully constructed in acid aqueous solution at pH 2 with 0.5 M NaCl. The resultant PDDA/P4VPPS multilayer films were pH-dependent and could be disintegrated in alkali aqueous solutions, especially with pH > or = 12. This disintegration property rendered such multilayer film as a sacrificial layer for further preparing free-standing polyelectrolyte multilayer films. The PDDA/poly(sodium 4-styrenesulfonate) (PSS) multilayer films deposited on the PDDA/P4VPPS sacrificial layer were confirmed to be successfully released after treated successively by alkali aqueous solution at pH 12 and ethanol. The obtained PDDA/PSS free-standing multilayer films had thicknesses of ca. 847 nm.

Layer-by-layer self-assembly, controllable disintegration of polycarboxybetaine multilayers and preparation of free-standing films at physiological conditions

The self-assembly and disintegration behavior of polyzwitterion, poly(4-vinylpyridiniomethanecarboxylate) (PVPMC), and negatively charged polyelectrolyte, poly(acrylic acid) (PAA), layer-by-layer (LbL) multilayer films were investigated in detail by using UV-vis absorption spectroscopy, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). The results indicated that the PVPMC/PAA multilayer films grew linearly with increasing bilayer number. The disintegration rate of PVPMC/PAA multilayers could be well controlled by varying the concentration of salt in aqueous solution. It was found that PVPMC/PAA multilayer films could be completely disintegrated in 0.9% normal saline solution within 15 min. Such controllable disintegration behavior rendered the PVPMC/PAA multilayer as an excellent sacrificial sublayer for fabricating free-standing LbL multilayer films. Free-standing multilayer films were then successfully fabricated by LbL self-assembly of positively charged polyelectrolyte complex (PEC), made from poly(diallyldimethylammonium) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS), and negatively charged PSS with PVPMC/PAA as a sacrificial sublayer, which was disintegrated in 0.9% normal saline solution. The obtained free-standing films had good mechanical properties with 24.1 MPa tensile strength at break and 0.56 GPa Youngs modulus.