Self-assembly of amphiphilic glycoconjugates into lectin-adhesive nanoparticles

This work describes the synthesis and self-assembly of carbohydrate-clicked rod-coil amphiphilic systems. Copper-catalyzed Huisgen cycloaddition was efficiently employed to functionalize the hydrophilic extremity of PEG-b-tetra(p-phenylene) conjugates by lactose and N-acetyl-glucosamine ligands. The resulting amphiphilic systems spontaneously self-assembled into nanoparticles when dissolved in aqueous media, as evidenced by dynamic light scattering (DLS), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). The formation of highly monodisperse micelles having a mean diameter of 10 nm was observed for systems containing a PEG 900 core, and a decrease in the hydrophilic moiety (PEG 600) led to the formation of vesicles with a broader size distribution. The presence of carbohydrate residues on the surfaces of the micelles and their ability to establish specific interactions with wheat germ agglutinin (WGA) and peanut agglutinin (PNA) were further highlighted by light-scattering measurements, thus confirming the attractive applications of such sugar micelles in biosensor devices.     

Self-Assembling Behavior of Polyglyceryl-Modified Silicone Surfactant in Aqueous Solution

We report interesting self-assembly behavior of a polyglyceryl-modified silicone surfactant in the aqueous solution; the sample has been characterized through measurements of surface tension, transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle x-ray scattering (SAXS). Aqueous solutions of this surfactant had a low critical aggregation concentration (CAC) and surface tension (21.5 mN · m^?1), substantially lower than those reported for polyether-modified silicone surfactants with a similar molecular architecture. DLS and TEM revealed self-assembled spherical micelles with a narrow size distribution. At higher concentrations (10 wt%), linear packing of micelles was observed, while the micelle size distribution remained similar (50–90 nm). SAXS data could be fitted through the use of a core–shell model and implied that the core radius remained roughly 4.3–6.0 nm for all solutions of the surfactant analyzed. The origin of its curious aggregates behavior is attributed to hydrogen bonding, steric effects, and the directionality of bond angle from the polyglyceryl block of this novel class of silicone surfactant. This type of surfactant coupling lipophilic segments assembles the cores of the micelles in water which may find positive factors for potential applications such as microreaction compartmentalization.     

Submicrometer intermediates in the citrate synthesis of gold nanoparticles: new insights into the nucleation and crystal growth mechanisms

The reduction of tetrachloroaurate by citrate ions in aqueous solutions yielding gold nanoparticles (GNPs) has been studied using in situ tapping mode atomic force microscopy (AFM), UV-vis absorption and dynamic light scattering (DLS) spectroscopies, small-angle X-ray scattering (SAXS) along with ex situ TEM, EDX and XPS. Special attention is given to mesoscale intermediates responsible for the intense coloring of the transient solutions and their role in nucleation and crystal growth. AFM detects liquid droplet-like domains, globules 30-50 nm in diameter arranged in submicrometer aggregates in the gray and blue solutions, and well separated individual particles in the final red sols. DLS shows abrupt appearance of species about 30 nm and larger but not growing Au nanoparticles, while SAXS reveals gradually increasing nanoparticles and no aggregates. The mesoscale structures observed in TEM become looser as the reaction proceeds; they contain signatures of oxidized Au and other solutes. The results are interpreted in terms of decomposition of supersaturated solutions to afford domains ("dense droplets") enriched by gold, and then, after nucleation and coalescence of Au nuclei inside them, rather slow growth of gold nanoparticles within the associated globules; the color changes of the transient solutions are due to increasing interparticle distances.     

Influence of surfactant structure on reverse micelle size and charge for nonpolar electrophoretic inks

Electrophoretic inks, which are suspensions of colorant particles that are controllably concentrated and dispersed by applied electric fields, are the leading commercial technology for high-quality reflective displays. Extending the state of the art for high-fidelity color in these displays requires improved understanding and control of the colloidal systems. In these inks, reverse micelles in nonpolar media play key roles in media and particle charging. Here we investigate the effect of surfactant structure on reverse micelle size and charging properties by synthesizing different surfactants with variations in polyamine polar head groups. Small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) were used to determine the micelle core plus shell size and micelle hydrodynamic radius, respectively. The results from SAXS agreed with DLS and showed that increasing polyamines in the surfactant head increased the micelle size. The hydrodynamic radius was also calculated on the basis of transient current measurements and agreed well with the DLS results. The transient current technique further determined that increasing polyamines increased the charge stabilization capability of the micelles and that an analogous commercial surfactant OLOA 11000 made for a lower concentration of charge-generating ions in solution. Formulating magenta inks with the various surfactants showed that the absence of amine in the surfactant head was detrimental to particle stabilization and device performance.     

Size dependent catalysis with CTAB-stabilized gold nanoparticles

CTAB-stabilized gold nanoparticles were synthesized by applying the seeding-growth approach in order to gain information about the size dependence of the catalytic reduction of p-nitrophenol to p-aminophenol with sodium borohydride. Five different colloidal solutions of stabilized gold nanoparticles have been characterized by TEM, AFM, UV-Vis, SAXS, and DLS for their particle size distributions. Gold nanoparticles (mean sizes: 3.5, 10, 13, 28, 56 nm diameter) were tested for their catalytic efficiency. Kinetic data were acquired by UV-Vis spectroscopy at different temperatures between 25 and 45 °C. By studying the p-nitrophenol to p-aminophenol reaction kinetics we determined the nanoparticle size which is needed to gain the fastest conversion under ambient conditions in the liquid phase. Unexpectedly, CTAB-stabilized gold nanoparticles with a diameter of 13 nm are most efficient.     

交联度对原位聚合法制备聚合物胶束性质的影响及相应的空心球制备

用原位聚合法成功地制备出不同响应温度的温敏性聚乳酸/聚(异丙基丙烯酰胺-co-丙烯酰胺)[P(D,L-LA)/P(NIPAM-co-AM)]核壳胶束. 实验中发现, 壳层的交联剂含量对粒子的尺寸有很大的影响, 当交联剂的摩尔分数从5%提高到15%时, 粒子在25 ℃时的流体力学直径从170.2 nm增加到886.5 nm. 通过对胶束粒子的核进行生物降解, 方便地得到了相应的空心球. 用FTIR监测核的降解过程, 用SEM和AFM检测核降解完全后粒子的外在形貌和内在结构变化. DLS结果表明, 空心球粒子同样具有良好的温度响应性, 其响应温度可通过改变原位聚合时单体AM的含量加以调节.     

Growth of silica nanoparticles in methylmethacrylate-based water-in-oil microemulsions

The mechanism of silica particle formation in monomer microemulsions is studied using dynamic light scattering (DLS), atomic force microscopy, small-angle X-ray scattering (SAXS), and conductivity measurements. The hydrolysis of tetraethylorthosilicate (TEOS) in methylmethacrylate (MMA) microemulsions (MMA = methylmethacrylate) is compared with the formation of SiO₂ particles in heptane microemulsions. Stable microemulsions without cosurfactant were found for MMA, the nonionic surfactant Marlophen NP10, and aqueous ammonia (0.75 wt%). In the one-phase region of the ternary phase diagram, the water/surfactant ratio (R _w) could be varied from 6 to 18. The DLS and SAXS measurements show that reverse micelles form in these water-in-oil (w/o) microemulsions. The minimum water-to-surfactant molar ratio required for micelle formation was determined. Particle formation is achieved from the base-catalyzed hydrolysis of TEOS. According to atomic force microscopy measurements of particles isolated from the emulsion, the particle size can be effectively tailored in between 20 and 60 nm by varying R _w from 2–6 in heptane w/o microemulsions. For MMA-based microemulsions, the particle diameter ranges from 25 to 50 nm, but the polydispersity is higher. Tailoring of the particle size is not achieved with R _w, but adjusting the particle growth period produces particles between 10 and 70 nm.     

Quantitative model for prediction of hydrodynamic size of nonionic reverse micelles

The sizes of nonionic reverse micelles were investigated as a function of the molecular structure of the surfactant, the type of oil, the total concentration of surfactant [NP], the ratio of surfactant to total surfactant (r), the water to surfactant molar ratio (omega), temperature, salt concentration, and polar phase. The basis of our investigation was a mixture of nonylphenol polyethoxylates--NP4 and NP7, various polar phases, and several oils. Micelle sizes were determined using dynamic light scattering (DLS). A central composite experimental design was used to quantitatively model micelle size as a function of omega, surfactant concentration, and r. The model has demonstrated the capability of predicting the mean diameter of micelles from 4 to 13 with a precision of +/-2 nm as measured by DLS. This quantitative correlation between the size of reverse micelles and the synthetic variables provides the foundation for choosing experimental conditions to control reverse micelle size. In turn, this allows control of the size of nanoparticles synthesized within them.     

Micelles of poly(styrene-b-2-vinylpyridine-b-ethylene oxide) with blended polystyrene core and their application to the synthesis of hollow silica nanospheres

Core-shell-corona (CSC) micelles of asymmetric triblock copolymer, poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-PVP-PEO), containing polystyrene homopolymer (homo-PS) in the core were successfully prepared in aqueous media. The influence of homo-PS contents over the formation of the micelles was investigated thoroughly by various techniques such as dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fluorescence spectroscopy. It was found that the size of the PS core of the micelle was increased by the addition of homo-PS as observed by DLS and TEM techniques. The SEM and TEM measurements confirm the spherical morphology of the micelles and enlargement of PS core over the addition of homo-PS. The increase in the PS core volume of the PS-PVP-PEO micelles is attributed to the insertion of homo-PS in the PS core. The micelles have also been demonstrated as facile soft templates for synthesis of hollow silica nanospheres. The average diameter of the spherical hollow particles could be tuned between 30.6 and 38.8 nm with cavity sizes ranging from 20.7 to 28.5 nm using tetramethoxysilane as silica precursors under mild acidic conditions. The facile synthesis of hollow silica using the CSC micelles with different homo-PS contents indicates that the hollow void size can be controlled within a range of several nanometers.     

Formation of gold nanoparticles in diblock copolymer micelles with various reducing agents

Gold nanoparticles (Au NPs) were prepared by the reduction of HAuCl₄ acid incorporated into the polar core of poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymer micelles dissolved in toluene. The formation of Au NPs was controlled using three reducing agents with different strengths: hydrazine (HA), triethylsilane (TES), and potassium triethylborohydride (PTB). The formation of Au NPs was followed by transmission electron microscopy, UV–Vis spectroscopy, isothermal titration calorimetry (ITC), and dynamic light scattering (DLS). It was found that the strength of the reducing agent determined both the size and the rate of formation of the Au NPs. The average diameters of the Au NPs prepared by reduction with HA, TES, and PTB were 1.7, 2.6, and 8 nm, respectively. The reduction of Au(III) was rapid with HA and PTB. TES proved to be a mild reducing agent for the synthesis of Au NPs. DLS measurements demonstrated swelling of the PS-b-P2VP micelles due to the incorporation of HAuCl₄ and the reducing agents. The original micellar structure rearranged during the reduction with PTB. ITC measurements revealed that some chemical reactions besides Au NPs formation also occurred in the course of the reduction process. The enthalpy of formation of Au NPs in PS-b-P2VP micelles reduced by HA was determined.     

Nanosilica-supported polyethoxyamines as low-cost, reversible carbon dioxide sorbents

Nanoparticles capped with amine ligands with different steric properties, dodecylamine and oleylamine, respectively, are investigated in the solid state as well as in solution. A combined X-ray diffraction, small angle X-ray scattering and electron microscopy investigation showed that the nanoparticles exhibit the sphalerite modification of ZnS as crystal phase with a diameter of 3-5 nm. A close packing of the monocrystalline nanoparticles in the solid state is observed. However, in the dodecylamine sample, besides spherical particles, a fraction of the nanoparticles is elongated. The nanoparticles are readily resoluble in apolar solvents like hexane. Dynamic light scattering (DLS) and SAXS investigations of the solutions reveal that the nanoparticles are dissolved as singular particles. In the case of oleylamine-capped ZnS, a defined core-shell structure with a ZnS core with a diameter of 4 nm and an organic shell with a thickness of approximately 2 nm have been found. Dodecylamine-capped nanoparticles slightly tend to form agglomerates with a diameter of approximately 40 nm.     

Creation of highly stable selenium nanoparticles capped with hyperbranched polysaccharide in water

Water-dispersible selenium nanoparticles (SeNPs) were created by using natural hyperbranched polysaccharide (HBP) as the stabilizer and capping agent under extremely safe conditions. The structure, morphology, size, and stability of the nanocomposites were investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and static and dynamic light scattering (DLS) measurements. The results revealed that the spherical selenium nanoparticles (mean particle size of about 24 nm) were ligated with HBP to form nanocomposites (Se-HBP) in aqueous solution and were stable for over one month. In our findings, supported by the results of FTIR, TEM, AFM, and DLS, SeNPs were capped with the HBP macromolecules, as a result of strong physical adsorption of OH groups on Se surfaces, leading to a highly stable structure of Se nanoparticles in water. This work provided reaction sites for the complexation between HBP and Se to fabricate well-dispersed Se nanoparticles in aqueous system with potential bioapplications.     

Fluorogenic 1,3-dipolar cycloaddition within the hydrophobic core of a shell cross-linked nanoparticle

Using either nitroxide mediated polymerization (NMP) or reversible addition fragmentation transfer (RAFT) techniques, novel block copolymers that present terminal acetylenes, in the side chain of the styrenic block, were obtained with narrow polydispersities and targeted molecular weights. For the conversion of these acetylene-functionalized polymers to amphiphilic block copolymers, RAFT techniques were preferred. Mild protection/deprotection chemistries were employed which were compatible with the incorporation of the acetylene functionality in the hydrophobic segment. These acetylene-functionalized, Click-readied amphiphilic block copolymers were then self-assembled and cross-linked to afford shell cross-linked knedel-like (SCK) nanoparticles that contained acetylene groups in the core domain. The hydrodynamic diameters (D(h)) of the block copolymer micelles and nanoparticles were determined by dynamic light scattering (DLS), and the dimensions of the nanoparticles were characterized using tapping-mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). The chemical availability of the Click functionality within the core domain of the SCKs was investigated using the copper(I)-catalyzed 1,3-dipolar fluorogenic cycloaddition with a non-fluorescent 3-azidocoumarin profluorophore to afford intensely fluorescent nanoparticles.     

Polycaprolactone-b-Poly(ethylene oxide) Biocompatible Micelles as Drug Delivery Nanocarriers: Dynamic Light Scattering and Fluorescence Experiments

Summary: Dynamic light scattering (DLS) and fluorescence experiments were carried out to study PCL₄₄-b-PEO₁₁₄ biocompatible micelles used as nanocarriers in drug delivery. Micelles prepared by a simple procedure (THF removal under nitrogen flow) exhibited a narrow size distribution with an average diameter of 100 nm. For micelles containing a hydrophobic model compound (pyrene) within the PCL core, a smaller average micellar size of 80 nm was observed, with a simultaneous broadening in the size distribution profile. In parallel to DLS results, fluorescence experiments showed evidence of pyrene encapsulation, and that the onset of the micellization process occurs at approximately 10/90 (v/v) THF/water mixtures in the case of PCL₄₄-b-PEO₁₁₄ polymer.     

Templating CdSe tetrapods at the air/water interface with POPC lipids

ZnS nanoparticles were precipitated in aqueous dispersions of cationic surfactant cetyltrimethylammonium bromide (CTAB). The sphere radii of ZnS nanoparticles calculated by using band-gap energies steeply decreased from 4.5 nm to 2.2 nm within CTAB concentrations of 0.4-1.5 mmol L(-1). Above the concentration of 1.5 mmol L(-1), the radii were stabilized at R=2.0 nm and increased up to R=2.5 nm after 24 h. The hydrodynamic diameters of CTAB-ZnS structures observed by the dynamic light scattering (DLS) method ranged from 130 nm to 23 nm depending on CTAB concentrations of 0.5-1.5 mmol L(-1). The complex structures were observed by transmission electron microscopy (TEM). At the higher CTAB concentrations, ZnS nanoparticles were surrounded by CTA(+) bilayers forming positively charged micelles with the diameter of 10nm. The positive zeta-potentials of the micelles and their agglomerates were from 16 mV to 33 mV. Wurtzite and sphalerite nanoparticles with R=2.0 nm and 2.5 nm covered by CTA(+) were modeled with and without water. Calculated sublimation energies confirmed that a bilayer arrangement of CTA(+) on the ZnS nanoparticles was preferred to a monolayer.     

Synthesis and Characterization of Thermo-responsive Poly(N-vinyl-2-pyrrolidinone)-block-poly(N-isopropylacrylamide) Micelles

A novel thermo-responsive diblock copolymer of poly(N-vinyl-2-pyrrolidinone)-block-poly(N-isopropylacrylamide) (PNVP-b-PNIPAM) was synthesized. FT-IR, ¹H-NMR and SEC results confirmed the successful synthesis of PNVP-b-PNIPAM diblock copolymer via anionic polymerization. The polymeric micelles formed from PNVP-b-PNIPAM copolymer in aqueous solution were developed and characterized as a potential thermo-responsive and biocompatible drug delivery system. Micellization of the diblock copolymer in aqueous solution was characterized by dynamic laser scattering (DLS), turbidity measurement, tension measurement and transmission electron microscopy (TEM). The thermo-responsive polymeric micelles with the size ranges of 200 to 260 nm and thickness of 30 nm are localized, selected and targeted for drug release, having a great potential in response to external-stimulus such as temperatures from 35 to 39°C. The critical micellization concentration (cmc) of PNVP-b-PNIPAM in aqueous solution is 0.0026 wt% determined by turbidity measurement. The size of micelles determined by DLS increased from 163 to 329 nm with increasing concentration of PNVP-b-PNIPAM from 0.25 to 0.5 wt% in aqueous solution at 40°C, which is determined by DLS.     

Micellar aggregation in blends of linear and cyclic poly(styrene-b-isoprene) diblock copolymers

The morphology of micelles formed from blends of linear and cyclic poly(styrene-b-isoprene) (PS-b-PI) block copolymers has been investigated in solution using dynamic light scattering (DLS) and in thin solid deposits by atomic force microscopy (AFM) and transmission electron microscopy under cryogenic conditions (cryo-TEM). Micelles of the pure cyclic PS(290)-b-PI(110) copolymers are wormlike cylindrical objects built by unidirectional aggregation of 33 nm wide sunflower micelles, while the linear block copolymer having the same volume fraction and molar mass forms spherical micelles 40 nm in diameter. The DLS, AFM, and cryo-TEM results consistently show that the addition of the linear copolymer (even for amounts as low as 5% w/w) to the cyclic copolymer rather favors the formation of spherical micelles at the expense of the cylindrical aggregates. Those results clearly show that the linear block copolymer chains can be used to stabilize the thermodynamically unstable elementary sunflower micelle. The thermal stability of the micelles (from the pure copolymers and from the blends) has been examined in solid deposits with in situ AFM measurements. Coalescence starts at about 70 degrees C, and the surface roughness shows a two-step decrease toward a fully homogeneous and flat structure.     

Micellar Behavior of Polystyrene-Poly(Ethylene Oxide) Diblock Copolymers in Aqueous Media: Effect of Copolymer Composition,Temperature, Salt,and Surfactants

Formation and structure of micelles from two amphiphilic polystyrene-block-poly(ethylene oxide) (PS-PEO) diblock copolymers (PS mol.wt. 1000; PEO mol.wt. 3000 and 5000) were examined by surface tension, viscosity, steady state fluorescence, dynamic light scattering (DLS), small angle neutron scattering (SANS), and cryo-transmission electron microscopy (cryo-TEM). The critical micelle concentration (CMC) of the copolymers in aqueous solution was ca. 0.05%; micelle hydrodynamic diameter was 30–35 nm with a narrow size distribution. SANS studies show that the copolymers form ellipsoidal micelles with semi major axis ～23 nm and semi minor axis ～8 nm. No significant change in the structure was found with temperature and presence of salt. The copolymer micelles interaction with the ionic surfactants sodium dodecyl sulphate (SDS) and dodecyltrimethylammonium bromide (DTAB) was also examined by DLS and SANS.     

Sizing of Reverse Micelles in Microemulsions using NMR Measurements of Diffusion

This paper reports the size of reverse micelles (RMs) in AOT/octane/H(2)O and CTAB/hexanol/H(2)O microemulsions using magnetic resonance (MR) pulsed field gradient (PFG) measurements of diffusion. Diffusion data were measured using the pulsed gradient stimulated echo (PGSTE) experiment for surfactant molecules residing in the RM interface. Inverse Laplace transformation of these data generated diffusion coefficients for the RMs, which were converted into hydrodynamic radii using the Stokes-Einstein relation. This technique is complementary to those previously used to size RMs, such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), but also offers several advantages, which are discussed. RM sizes, determined using the PGSTE method, in the AOT (sodium bis(2-ethylhexyl) sulfosuccinate) and CTAB (cetyltrimethylammonium bromide) microemulsions were compared with previous DLS and SAXS data, showing good agreement. Methods for determining number distributions from the PGSTE data, through the use of scaling factors, were investigated.     

两亲性壳聚糖衍生物的制备及其包覆量子点

以天然壳聚糖为功能性高分子的骨架,通过西弗碱还原法,以正辛醛和端醛基聚乙二醇单甲基醚(mPEG aldehyde,mPEG-ald)修饰壳聚糖,制备了具有亲疏水性质的N-辛基化-N-mPEG化壳聚糖衍生物(N-octyl-N-mPEG-chitosan,OPEGC),并且以此两亲性壳聚糖衍生物包覆量子点制备了水溶性聚合物量子点纳米粒子.用FTIR、1H-NMR对壳聚糖衍生物进行了结构表征.制备的水溶性胶束,用动态光散射(DLS)测试其流体力学直径与分布,研究了烷基链接枝比率对粒径大小的影响,研究结果表明:烷基链接枝率越高,聚合物胶束粒径越小.以芘为分子探针,通过荧光光谱法测定了壳聚糖衍生物的临界胶束浓度(CMC)为2.032×10-2mg/mL,并对水溶性聚合物量子点纳米粒子进行了紫外、荧光及形貌表征,结果表明得到了荧光发射产率高的聚合物量子点纳米粒子,且尺寸均一、水溶性好.