Highly branched cyclic dextrin derivatives (CH‐CDex) that are partly substituted with cholesterol groups have been synthesized. The CH‐CDex forms monodisperse and stable nanogels with a hydrodynamic radii of ≈10 nm by the self‐assembly of 4–6 CH‐CDex macromolecules in water. The CH‐CDex nanogels spontaneously trap 10–16 molecules of fluorescein isothiocyanate‐labeled insulin (FITC‐Ins). The complex shows high colloidal stability: no dissociation of trapped insulin is observed after at least 1 month in phosphate buffer (0.1 M , pH 8.0). In the presence of bovine serum albumin (BSA, 50 mg · mL?1), which is a model blood system, the FITC‐Ins trapped in the nanogels is continuously released (≈20% at 12 h) without burst release. The high‐density nanogel structure derived from the highly branched CDex significantly affects the stability of the nanogel–protein complex.
The concentration dependent transformation of an oligopeptide nanostructure from nanovesicles to nanotubes at neutral pH is presented. The oligopeptide Acp‐Tyr‐Glu (Acp: 6‐aminohexanoic acid) forms nanovesicles at a concentration of 6.9 mg mL?1. At a concentration of 2.3 mg mL?1 these vesicular structures completely disappear and nanotubular structures are observed. We have also successfully optimized an intermediate concentration (3.4 mg mL?1) where an ordered array of fused vesicular structures are formed, which actually leads to the transition from nanovesicles to nanotubes. These vesicular structures are very much sensitive toward metal ions and pH. Biocompatible calcium ions and high pH (10.7) can trigger the rupturing of these nanovesicles. One important property of these nanovesicular structures is the encapsulation of a potent anticancer drug doxorubicin, which can also be released in the presence of calcium ions promising a future use of these nanovesicles as vehicles for carrying biologically important molecules. 相似文献
Stimuli‐responsive nanoporous membranes have attracted increasing interest in various fields due to their abrupt changes of permeation/separation in response to the external environment. Here we report ultrathin pH‐sensitive nanoporous membranes that are easily fabricated by the self‐assembly of poly(acrylic acid) (PAA) in a metal hydroxide nanostrand solution. PAA‐adsorbed nanostrands (2.5–5.0 nm) and PAA‐CuII nanogels (2.0–2.5 nm) grow competitively during self‐assembly. The PAA‐adsorbed nanostrands are deposited on a porous support to fabricate ultrathin PAA membranes. The membranes display ultrafast water permeation and good rejection as well as significant pH‐sensitivity. The 28 nm‐thick membrane has a water flux decrease from 3740 to 1350 L m?1 h?1 bar?1 (pH 2.0 to 7.0) with a sharp decrease at pH 5.0. This newly developed pH‐sensitive nanoporous membranes may find a wide range of applications such as controlled release and size‐ and charge‐selective separation. 相似文献
A nanoformulation composed of curdlan, a linear polysaccharide of 1,3‐β‐linked d ‐glucose units, hydrogen bonded to poly(γ ‐glutamic acid) (PGA), was developed to stimulate macrophage. Curdlan/PGA nanoparticles (C‐NP) are formulated by physically blending curdlan (0.2 mg mL?1 in 0.4 m NaOH) with PGA (0.8 mg mL?1). Forster resonance energy transfer (FRET) analysis demonstrates a heterospecies interpolymer complex formed between curdlan and PGA. The 1H‐NMR spectra display significant peak broadening as well as downfield chemical shifts of the hydroxyl proton resonances of curdlan, indicating potential intermolecular hydrogen bonding interactions. In addition, the cross peaks in 1H‐1H 2D‐NOESY suggest intermolecular associations between the OH‐2/OH‐4 hydroxyl groups of curdlan and the carboxylic‐/amide‐groups of PGA via hydrogen bonding. Intracellular uptake of C‐NP occurs over time in human monocyte‐derived macrophage (MDM). Furthermore, C‐NP nanoparticles dose‐dependently increase gene expression for TNF‐α, IL‐6, and IL‐8 at 24 h in MDM. C‐NP nanoparticles also stimulate the release of IL‐lβ, MCP‐1, TNF‐α, IL‐8, IL‐12p70, IL‐17, IL‐18, and IL‐23 from MDM. Overall, this is the first demonstration of a simplistic nanoformulation formed by hydrogen bonding between curdlan and PGA that modulates cytokine gene expression and release of cytokines from MDM. 相似文献
A poly(4‐vinylpridine‐co‐ethylene glycol dimethacrylate) monolith was synthesized in a capillary and constructed as a concentrator for the in‐line polymeric monolith microextraction coupling with capillary electrophoresis. The integrated system was then used for the simultaneous determination of five trace phenols (2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2‐chlorophenol, and 2,4‐dichlorophenol) in water samples. The experimental parameters for in‐line solid‐phase extraction, such as composition and volume of the elution plug, pH of sample solution, and the time for sample loading were optimized. The sensitivity for the mixture of phenols (2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2‐chlorophenol, and 2,4‐dichlorophenol) enhanced to 615–2222 folds at the optimum condition was compared to the sensitivity for a normal hydrodynamic injection in capillary electrophoresis. Linearity ranged from concentration of 10–500 ng mL?1(R2 > 0.999) for all five phenols with the detection limits of 1.3–3.3 ng mL?1. In tap, snow and Yangtze River water spiked with 20 ng mL?1 and 200 ng mL?1, respectively, the recoveries of 84–105% were obtained. It has been demonstrated that this work has great potential for the analysis of phenols in genuine water samples. 相似文献
A novel pH‐responsive magnetic nanogels were developed with the aim of targeted delivering and simultaneously releasing of newly synthesized Au(III)‐based anticancer drug, Au(1,7‐Phen)Br3. The obtained nanogels were characterized by FT‐IR, DLS, EDAX, TEM, XRD, ICP‐Ms and MRI. The TEM images showed that the nanogels had a spherical shape with a mean diameter of 20 nm. The in vitro release studies of Au (III)‐loaded nanogels showed a pH‐triggered controlled release of drugs. The in vitro cytotoxicity assay of samples to human cervical cancer HeLa cell lines indicated that the Au(III)‐loaded magnetic nanogels exert higher cytotoxicity in comparison with free Au(III) complex. Fluorescent microscope images indicated that these magnetic nanogels possessed notable cell specific targeting in vitro in the presence of an external magnetic field. The results show that this superparamagnetic nanocarrier is a promising candidate for inhibiting growth of tumor cells. 相似文献
Summary: We report novel organic‐inorganic hybrid nanomaterials that consist of polymer hydrogel nanoparticles (nanogels) and calcium phosphate. Hybrid nanoparticles that measure ca. 40 nm are synthesized from a dilute solution of hydroxyapatite using nanogels as templates for calcium phosphate mineralization. These nanoparticles show a narrow size distribution and high colloidal stability. Nanogel‐adsorbed liposomes act as templates for hierarchical hybrid nanostructures. These nanohybrids can potentially be used as biocompatible drug carriers with controlled‐release properties.
TEM images of calcium phosphate nanoparticles formed in the presence of CHP nanogels (0.5 mg · mL−1) (left) and nanogel‐liposomes (CHP 0.05 mg · mL−1, DPPC 0.08 mg · mL−1)(right). 相似文献
Poly(amidoamine)s with amino pendant groups were prepared by hydrogen‐transfer polyaddition of primary and secondary amines to bis‐acrylamines. Dansyl cadaverine (DC) doxorubicin (Dox) were bound to the polymers via a cis‐aconityl spacer to give conjugates containing 3 µg of DC per mg of polymer and 28 to 35 µg of Dox per mg of polymer. Release of DC and Dox at physiological and acidic pH varied from 0 to 35% over 48 h and was pH dependent. Although the ISA1Dox conjugate (IC50 = 6 µg Dox · mL?1) presented similar toxicity as the parent polymer without Dox, ISA23Dox showed increased toxicity (IC50 = 10 µg Dox · mL?1). These results suggest that ISA23Dox is able to release biologically active Dox in vitro and that this conjugate might be suitable for further development.
A porous carbon designated as MOF‐5‐C was prepared by directly carbonizing a metal–organic framework (MOF‐5). The morphology and microstructure of MOF‐5‐C were characterized by scanning electron microscopy, N2 adsorption, and powder X‐ray diffraction. The MOF‐5‐C retained the original porous structures of MOF‐5, and showed a high Brunauer–Emmett–Teller surface area (1808 m2 g?1) and large pore volume (3.05 cm3 g?1). To evaluate its adsorption performance, the MOF‐5‐C was used as an adsorbent for the solid‐phase extraction of four phthalate esters from bottled water, peach juice, and soft drink samples followed by high‐performance liquid chromatographic analysis. Several parameters that could affect the extraction efficiencies were investigated. Under the optimum conditions, a good linearity was achieved in the concentration range of 0.1–50.0 ng mL?1 for bottled water sample and 0.2–50.0 ng mL?1 for peach juice and soft drink samples. The limits of detection of the method (S/N = 3) were 0.02 ng mL?1 for bottled water sample, and 0.04–0.05 ng mL?1 for peach juice and soft drink samples. The results indicated that the MOF‐5‐C exhibited an excellent adsorption capability for trace levels of phthalate esters, and it could be a promising adsorbent for the preconcentration of other organic compounds. 相似文献
Summary: Supramolecular self‐assembly of poly(methyl methacrylate)‐grafted multiwalled carbon nanotubes (MWNT‐g‐PMMA) was reported herein. The MWNT‐g‐PMMA (85 wt.‐% PMMA) dispersed in tetrahydrofuran could self‐assemble into suprastructures on surfaces such as gold, mica, silicon, quartz, or carbon films. With decreasing concentration of the MWNT‐g‐PMMA from 3 to 0.1 mg · mL−1, the assembled structures changed from cellular and basketwork‐like forms to multilayer cellular networks and individual needles. SEM, AFM, and TEM measurements confirmed the morphology of the assembled suprastructures, and revealed the assembly mechanism. Phase separation during evaporation of the solvent drives the MWNT‐g‐PMMA nanohybrids to assemble and form the suprastructures, and the rigid MWNTs stabilize the structures.
SEM images of self‐assembled suprastructures of basketwork (a), cellular network (b), and needles (c) from the THF solution of the PMMA‐grafted MWNTs on gold surface. 相似文献
We report an innovative supramolecular architecture for bienzymatic glucose biosensing based on the non‐covalently functionalization of multi‐walled carbon nanotubes (MWCNTs) with two proteins, glucose oxidase (GOx) (to recognize glucose) and avidin (to allow the specific anchoring of biotinylated horseradish peroxidase (b‐HRP)). The optimum functionalization was obtained by sonicating for 10 min 0.50 mg mL?1 MWCNTs in a solution of 2.00 mg mL?1 GOx+1.00 mg mL?1avidin prepared in 50 : 50 v/v ethanol/water. The sensitivity to glucose for glassy carbon electrodes (GCE) modified with MWCNTs‐GOx‐avidin dispersion and b‐HRP (GCE/MWCNTs‐GOx‐avidin/b‐HRP), obtained from amperometric experiments performed at ?0.100 V in the presence of 5.0×10?4 M hydroquinone, was (4.8±0.3) μA mM?1 (r2=0.9986) and the detection limit was 1.2 μM. The reproducibility for 5 electrodes using the same MWCNTs/GOx‐avidin dispersion was 4.0 %, while the reproducibility for 3 different dispersions and 9 electrodes was 6.0 %. The GCE/MWCNT‐GOx‐avidin/b‐HRP was successfully used for the quantification of glucose in a pharmaceutical product and milk. 相似文献
A new validated potentiometric method is described for batch and continuous quality control monitoring of the drug oseltamivir phosphate (Taminil) (OST). The method involves the development of a potentiometric sensor responsive to the drug based on the use of the ion‐association complex of (OST+) cation with phosphomolybdate anion (PMA?) as an electroactive material in a poly(vinyl chloride) matrix membrane plasticized with o‐nitrophenyloctyl ether (o‐NPOE). Optimization of the performance characteristics of the sensor is described. A membrane incorporating the OST‐PMA‐NPOE complex in a tubular flow through detector is used in a two channel flow injection set up for continuous monitoring of the drug at a frequency of ~30 samples h?1. The sensor shows fast near‐Nernstian response for OST over the concentration range 5.2×10?5–0.8×10?2 M (21.34 µg mL?1–3.23 mg mL?1) with a detection limit of 9.1×10?6 M (3.73 µg mL?1) over the pH range 4.6–6.1. The sensor displays good selectivity for OST drug over some basic drugs, inorganic cations, excipients and diluents commonly used in the drug formulations. Validation of the assay method is tested by measuring the lower detection limit, range, linearity, bias, trueness, accuracy, precision, and between‐day‐variability, within day reproducibility, selectivity and ruggedness (robustness). The results reveal good potentiometric performance of the proposed sensor for determination of OST in pharmaceutical capsules and in biological fluid matrices as well as for testing the dissolution profile of the drug and drug homogeneity. 相似文献