Modifying the adsorption behavior of polyamidoamine dendrimers at silica surfaces investigated by total internal reflection fluorescence correlation spectroscopy

Polyamidoamine (PAMAM) dendrimers were modified and tested for use as solution-phase diffusion probes in silica nanostructures. In order for the successful application of dendrimers as solution-phase probes, their interactions with silica surfaces must be understood and controlled, so that the motion of the probe is not influenced by adsorption. Adsorption/desorption kinetics of PAMAM dendrimers and their diffusion in solution near silica surfaces were investigated with total internal reflection fluorescence correlation spectroscopy (TIR-FCS). Dendrimers of generations 3, 5, and 7 were dye-labeled with carboxyrhodamine 6G. Because PAMAM dendrimers are positively charged in solution (having primary amines as end groups), significant adsorption of these molecules to the negatively charged silica surface was observed. Adsorption/desorption rates and the equilibrium constant for adsorption were determined by fitting the autocorrelation functions to a kinetic model. The desorption rate decreases and the absorption equilibrium constant increases with higher dendrimer generation. To reduce the adsorption of these probes to silica surfaces, the labeled dendrimers were reacted with succinic anhydride, converting the primary amine end groups to negatively charged carboxylic acid groups. These carboxylated dendrimers did not detectably adsorb to silica from aqueous solution. TIR-FCS was used to determine their free-solution diffusion constants near silica surfaces, and the corresponding hydrodynamic radii compare favorably with values reported from forced Rayleigh scattering measurements.     

CdS／PAMAM纳米复合材料的制备及光学性能

以聚酰胺－胺（PAMAM）树形分子为模板，原位合成CdS，AMAM树形分子纳米复合材料，探索不同负载比对其性能的影响及量子点表面的功能性。通过荧光光谱技术，分析Cu^2＋和Mn^2＋重金属离子对其光致发光性能的影响，利用光学性质变化、材料分析稳定度考察其反应机制。     

Infrared method for in situ studies of polymer/surfactant adsorption on silica powders from aqueous solution

This article presents a general infrared spectroscopic method that enables the monitoring of the adsorption of surfactants and polyelectrolytes on high surface area silica particles from aqueous solution. The method is based on the use of a ZnSe internal reflection element (IRE) coated with a layer of titania particles. The titania surface is the converted to silica using atomic layer deposition with sequential addition of an amine catalyst, gaseous SiCl4, and water vapor. A minimum of three cycles is needed to produce a surface that mimics silica, as evidenced by the reaction of hexamethyldisilazane and zeta potential measurements. It is shown that the silicacoated titania particles on the ZnSe crystals are stable to flowing aqueous solutions below pH = 8 and can be used to study the dynamics of polymer/surfactant adsorption on silica.     

Morphologies and Superhydrophobicity of Hybrid Film Surfaces Based on Silica and Fluoropolymer

Fluoropolymer and different kinds of silica particles were used for controlling surface chemistry and morphology, respectively. A superhydrophobic surface originated from strawberry-like or quincunx-shaped composite silica particles was obtained. The dual size particles are obtained by utilizing the graft of different modified silica particles with epoxy functional group and amine functional group, This makes the surface of film form a composite interface to have irregular binary structure which plays an essential role in trapping air between the substrate surface and the liquid droplets to be necessary for high contact angle and low contact angle hysteresis. The maximum contact angle for water on the hybrid film is about 174±2° and the contact angle hysteresis is less than 2°. The surface morphologies, roughness and the wettability on the surface of films containing different structural silica particles were compared. It was shown that the hierarchical irregularly structure with a low roughness factor and high air-trapped ratio is indispensable for superhydrophobic surface. Although this structural surfaces based on composite silica particles play a vital role in governing the surface wettability, it is necessary to combine with a low surface energy to make the surface superhydrophobic.     

Grafting electrosprayed silica microspheres on cellulosic textile via cyanuric chloride reactive groups

A novel method of covalently grafting solid or hollow microcapsules on cellulosic textiles was developed by surface functionalisation of capsules with reactive triazine moieties. Demonstrative silica microspheres, with 454 nm average particle size, were developed by electrospraying silica sol prepared via sol–gel process. The chemical–physical properties of submicron particles were characterised by Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TGA) and scanning (SEM) and transmission electron microscopy (TEM). As a potential process towards functional textiles, the micro/nanosphere surface was modified with chlorotriazine ligands in a two-step procedure to react with the hydroxyl groups in cellulose under mild conditions. The first amine functionalisation was demonstrated by evaluation with FTIR and silicon-29 nuclear magnetic resonance (²⁹Si-NMR), as well as using TGA. Subsequent chemical functionalisation of an amine–silica surface with triazine moieties was analysed by FTIR, proton solid-state NMR spectroscopy (¹H-NMR) and TEM coupled to an X-ray detector. Finally, the covalent bonding of silica nanoparticles to cellulose was performed under simulated dying conditions and it was evaluated by SEM in combination to energy dispersive X-ray spectroscopy.     

Wide varieties of cationic nanoparticles induce defects in supported lipid bilayers

Nanoparticles with widely varying physical properties and origins (spherical versus irregular, synthetic versus biological, organic versus inorganic, flexible versus rigid, small versus large) have been previously noted to translocate across the cell plasma membrane. We have employed atomic force microscopy to determine if the physical disruption of lipid membranes, formation of holes and/or thinned regions, is a common mechanism of interaction between these nanoparticles and lipids. It was found that a wide variety of nanoparticles, including a cell penetrating peptide (MSI-78), a protein (TAT), polycationic polymers (PAMAM dendrimers, pentanol-core PAMAM dendrons, polyethyleneimine, and diethylaminoethyl-dextran), and two inorganic particles (Au-NH2, SiO2-NH2), can induce disruption, including the formation of holes, membrane thinning, and/or membrane erosion, in supported lipid bilayers.     

Molecular dynamics simulation of polyamidoamine dendrimer-fullerene conjugates: generations zero through four

Previously the synthesis of the polyamidoamine (PAMAM) (G4)-C60 conjugate with a molar ratio of 1 : 30 was reported. Because PAMAM G4 has sixty-four primary amine groups, it was hypothesized that approximately two surface amine groups react with each fullerene molecule to form the conjugates. A computational energy minimization study of various G4 PAMAM-fullerene conjugates containing 1 dendrimer but different amounts of fullerenes shows excellent stability for the 1 : 30 dendrimer to fullerene product. Attempts to prepare other PAMAM dendrimer-fullerene (C60) conjugates, using generations G0-G3 of PAMAM and C60 via the same procedure in pyridine were not successful, possibly due to solubility differences. The same computational techniques used to study the G4 conjugates were then used to determine (1) the stability of the G0-G3 conjugates (with a 2 : 1 primary amine to fullerene ratio), and (2) their solubility in pyridine compared to the (G4)-C60 conjugate. The findings allow for a better understanding of structure-property relationships of these nano-hybrid materials, through investigation of the molecular shape and radius of gyration. The findings reported herein may lead to improved syntheses of fullerene-dendrimer conjugates of various sizes and a better understanding of their nanoscopic structures and topographical influences.     

Resonance energy transfer-amplifying fluorescence quenching at the surface of silica nanoparticles toward ultrasensitive detection of TNT

This paper reports a resonance energy transfer-amplifying fluorescence quenching at the surface of silica nanoparticles for the ultrasensitive detection of 2,4,6-trinitrotoluene (TNT) in solution and vapor environments. Fluorescence dye and organic amine were covalently modified onto the surface of silica nanoparticles to form a hybrid monolayer of dye fluorophores and amine ligands. The fluorescent silica particles can specifically bind TNT species by the charge-transfer complexing interaction between electron-rich amine ligands and electron-deficient aromatic rings. The resultant TNT-amine complexes bound at the silica surface can strongly suppress the fluorescence emission of the chosen dye by the fluorescence resonance energy transfer (FRET) from dye donor to the irradiative TNT-amine acceptor through intermolecular polar-polar interactions at spatial proximity. The quenching efficiency of the hybrid nanoparticles with TNT is greatly amplified by at least 10-fold that of the corresponding pure dye. The nanoparticle-assembled arrays on silicon wafer can sensitively detect down to approximately 1 nM TNT with the use of only 10 microL of solution (approximately 2 pg TNT) and several ppb of TNT vapor in air. The simple FRET-based nanoparticle sensors reported here exhibit a high and stable fluorescence brightness, strong analyte affinity, and good assembly flexibility and can thus find many applications in the detection of ultratrace analytes.     

Fumed silica/polymer hybrid nanoparticles prepared by redox-initiated graft polymerization in emulsions

Hybrid particles comprising aggregated fumed silica nanoparticles as the core and hydrophobic polymers existing around the nanoparticles were prepared by ‘grafting from’ polymerization in emulsions. The emulsion polymerization employed cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant, respectively, to stabilize the emulsion polymerization. The polymerization was initiated by the redox reaction between ceric ion Ce(IV) and the amine groups on the surfaces of aminated fumed silica nanoparticles that were modified by 3-aminopropyltriethoxysilane. Infrared spectroscopy and thermogravimetric analysis demonstrated that both poly(methyl methacrylate) (PMMA) and polystyrene (PS) were successfully grafted onto the fumed silica surface. The type of surfactant greatly affected the grafting ratio, monomer-to-polymer conversion, and morphology of the product. When CTAB was used as the surfactant, both the grafting ratio and monomer-to-polymer conversion were lower than when SDS was used, but transmission electron microscopy and light scattering analysis indicated that most of the resultant particles were sub-100 nm hybrid nanoparticles with a non-spherical shape and particles sizes of 75–90 and 57–85 nm for PMMA and PS-grafted fumed silica, respectively. Whereas, when SDS was used as the surfactant, the particles agglomerated to form large irregular clusters or even networks, possibly due to the electrostatic attractions between SDS and Ce(IV) and/or the aminated fumed silica nanoparticles in aqueous solution.     

以酯端基PAMAM树形分子为模板在N，M-二甲基甲酰胺溶剂中制备金纳米粒子

用UV-vis、FT-IR光谱研究了HAuCl4和酯端基聚酰胺胺(PAMAM)树形分子在N，N-二甲基甲酰胺(DMF)溶剂中的相互作用，提出HAuCl4与树形分子之间的络合机理：[AuCl4]^-离子与质子化叔胺基团形成离子对，Au^3 离子与PAMAM树形分子上的酯基和酰胺基团形成配位作用。在DMF溶剂中酯端基PAMAM树形分子与HAuCl4配位后用柠檬酸钠还原形成金纳米粒子，UV-vis光谱和TEM图像分析表明了随树形分子代数的增加，金纳米粒子的直径减小，并提出了树形分子-金纳米复合物的结构模型：(1)较低代数的树形分子环绕在金粒子的外围；(2)在较高代数的树形分子空腔内部封装金纳米粒子。     

Real-time imaging of tunable adenosine 5-triphosphate release from an MCM-41-type mesoporous silica nanosphere-based delivery system

We studied a mesoporous silica nanosphere (MSN) material with tunable release capability for drug delivery applications. We employed luciferase chemiluminescence imaging to investigate the kinetics and mechanism of the adenosine 5-triphosphate (ATP) release with various disulfide-reducing agents as uncapping triggers. ATP molecules were encapsulated within the MSNs by immersing dry nanospheres in aqueous solutions of ATP followed by capping of the mesopores with chemically removable caps, such as cadmium sulfide (CdS) nanoparticles and poly(amido amine) dendrimers (PAMAM), via a disulfide linkage. By varying the chemical nature of the 'cap' and 'trigger' molecules in our MSN system, we discovered that the release profiles could indeed be regulated in a controllable fashion.     

Effect of the particle size of nanosilica on the performance of epoxy/silica composite coatings

Four kinds of colloidal silica particles with different size (27, 58, 79 and 173 nm, respectively) were synthesized by sol-gel process and modified with 3-glycidoxypropyltrimethoxysilicane, then homogenously dispersed into the epoxy resin and cured with alicyclic amine on aluminum alloy substrates. The results showed that the Si-O-Al bond was formed at nanocomposite coat/substrate interface, introducing nanosilica significantly enhanced the adhesive strength, scratch resistance, abrasion resistance and corrosion resistance of coats, but different particle sizes of nanosilica had various impact on these properties, which seemed to be related to the structure of the silica surface.     

Preparation and catalytic activity of Au-Pd, Au-Pt, and Pt-Pd binary metal dendrimer nanocomposites

Catalytic activity of Au-Pt, Au-Pd, and Pt-Pd dendrimer nanocomposites for reduction of p-nitrophenol was investigated in water. The bimetallic dendrimer nanocomposites were prepared by simultaneous reduction with sodium borohydride in the presence of poly(amidoamine) (PAMAM) dendrimers with amine and carboxyl terminal groups. Average diameters of the obtained particles were 2-4 nm by transmission electron microscopy. From UV-vis spectroscopy, it was found that the particles were not mixtures of monometallic particles but binary ones. X-ray photoelectron spectroscopy showed that formation of binary composite particles prevents palladium atoms from oxidation. The Au-Pd and Pt-Pd binary particles exhibited higher catalytic activity than monometallic ones. On the other hand, catalytic activity of Au-Pt binary particle was comparable to that of platinum nanoparticles.     

二代PAMAM树型高分子的荧光现象及其荧光标记应用

首次发现不含荧光团的二代poly(amido amine) (PAMAM) 树型高分子的荧光现象,研究结果表明在无荧光基团的PAMAM树型高分子中,胺类官能团是产生荧光的关键.不同酸度条件下,生成荧光中心的速度不同,而且荧光的稳定性也不相同.同时发现当反复变换酸碱性时PAMAM树型高分子的荧光强度逐渐变弱.由于低代PAMAM树型高分子的良好生物相容性和低廉价格,其有可能成为新型生物荧光标记物.     

Stable, dispersible surface-enhanced Raman scattering substrate capable of detecting molecules bound to silica-immobilized ligands

A stable surface-enhanced Raman scattering (SERS) substrate is developed through immobilization of gold sols onto aminated silica beads. The plasmon resonance is established by spacing of gold sols on the bead surface and remains stable over extended periods of time due to the large number of amine groups that provide stable anchoring of gold to the surface. Unlike planar supports, this substrate can be dispersed in a sample, providing high surface area for detection and efficient transport of analytes to its surface. This substrate can be used to detect the binding of a molecule to ligands on the silica surface, which avoids the stability limitations of thiol-bound ligands on gold. Chemical modification of the amine groups on the silica surface with benzoic anhydride could be readily detected in Raman scattering enhanced by the neighboring gold sols, with nearly the same sensitivity as benzylthiol bound directly to the gold surfaces. This result suggests future work involving the immobilization of other ligands through the residual amine groups to the silica, which could be used to selectively attract target analytes to the SERS-active surface.     

Fabrication of raspberry-like superhydrophobic hollow silica particles

Raspberry-like superhydrophobic hollow silica particles were prepared through a sacrificial polymer template method. The Stöber method was adopted to coat silica onto the surface of cationic polymethylmethacrylate(PMMA) particles by electrostatic interaction. The surface of the PMMA-silica composite particles exhibited raspberry-like morphology with high surface roughness. Hollow silica particles were then obtained by calcination to selectively remove the PMMA core. Subsequent modification with nonafluorohexyltriethoxysilane (NFH-silane) conferred superhydrophobicity on the hollow silica particles. The surface property of this particles were investigated by measuring their water contact angle, and the results showed that such perfluorinated raspberry-like hollow particles had unique superhydrophobic.     

High-resolution X-ray photoelectron spectroscopy of mixed silane monolayers for DNA attachment

The amine density of 3-aminopropyldimethylethoxysilane (APDMES) films on silica is controlled to determine its effect on DNA probe density and subsequent DNA hybridization. The amine density is tailored by controlling the surface reaction time of (1) APDMES, or (2) n-propyldimethylchlorosilane (PDMCS, which is not amine terminated) and then reacting it with APDMES to form a mixed monolayer. High-resolution X-ray photoelectron spectroscopy (XPS) is used to quantify silane surface coverage of both pure and mixed monolayers on silica; the XPS data demonstrate control of amine density in both pure APDMES and PDMCS/APDMES mixed monolayers. A linear correlation between the atomic concentration of N atoms from the amine and Si atoms from the APDMES in pure APDMES films allows us to calculate the PDMCS/APDMES ratio in the mixed monolayers. Fluorescence from attached DNA probes and from hybridized DNA decreases as the percentage of APDMES in the mixed monolayer is decreased by dilution with PDMCS.     

异丙醇体系中多形态氧化铝纳米粒子的制备研究

本文研究以无毒异丙醇代替苯系溶剂由醇盐水解法制备纳米氧化铝过程中,三维聚酰胺树状物(PAMAMs)及其铵盐、钠盐对氧化铝粒子形态的调控作用,同时研究了水解温度、凝胶温度对颗粒形态的影响.结果表明,在反应物中加入适当的改性剂和控制反应温度,能够使颗粒形状控制为球形、针状、棒状、纤维状及片状,其尺寸范围为3～100nm.     

热处理对二氧化钛表面二氧化硅包膜的影响

通过单流匀速滴定法在二氧化钛颗粒表面均匀包覆一层二氧化硅,系统地研究热处理温度对这层硅包覆层的形貌和相组成的影响;采用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、透射电子显微镜(TEM)和傅立叶红外光谱仪(FTIR)等手段对包硅二氧化钛颗粒进行表征。结果表明:150℃热处理形成连续致密的硅二氧化硅覆层;500℃热处理3 h后形成岛状二氧化硅膜;700℃热处理后形成不连续的硅二氧化硅覆层,并有脱落的倾向;当温度升到1 000℃时,硅二氧化硅覆层会脱落,二氧化钛的粒径增大,大约在1 000℃,二氧化硅包覆层结晶化。     

Low generation photochromic monodendrons on a solid surface

Zeroth through third generations of amphiphilic monodendrons containing a benzyl-15-crown-5 polar focal point, photochromic spacer, and alkyl tails as peripheral groups have been investigated for their ability to form photoresponsive surface monolayers. Thickness measurements, scanning probe microscopy, and molecular modeling were used to determine the microstructure of the monolayers. The tilted molecular packing of dendrons in the monolayers is proposed with bulky dendritic shell prohibiting dense packing of azobenzene groups and the aggregate formation. The two-stage trans–cis isomerization was observed for the photochromic monodendron layers composed of various generation dendrons. Fast changes within the first several minutes occurred in the azobenzene-containing monodendrons until the conversion of trans–cis isomerization reaches 13–33%. Then lateral steric hindrances in the monolayer decreases the transformation rate by three orders of magnitude. Diffusion limited intralayer reorganization is suggested to be a limiting factor in the rate of photoisomerization changes.