In vitro release of protein from poly(butylcyanoacrylate) nanocapsules with an aqueous core

Factors influencing the in vitro release of bovine serum albumin (BSA) from poly(butylcyanoacrylate) (PBCA) nanocapsules, such as the pH value, BSA loading, the polymeric nanocapsule walls and protein molecular weight, were investigated in detail. The BSA release rate was affected by the degradation rate of the polymeric wall and protein loading. For low molecular weight proteins, the initial burst release was faster than that of high molecular weigh proteins and got to equilibrium quickly. Sodium dodecyl sulfate–polyacrylamide gel electrophoresis results showed that BSA encapsulated within PBCA nanocapsules did not suffer covalent aggregation or fragmentation during the initial days of in vitro incubation. For nanocapsules prepared by interfacial polymerization in water-in-oil microemulsions, these findings were useful as a foundation for the development of nanocapsules with desired properties.     

Closed-loop sol-gel transition of PEG-PEC aqueous solution

We are reporting an unusual closed-loop phase behavior of poly(ethylene glycol)-beta-poly(ethyl-2-cyanoacrylate) (PEG-PEC) aqueous solutions. As the temperature increased from 0 to 60 degrees C, the aqueous polymer solution (12 wt %) underwent sol-to-gel and gel-to-syneresis transitions. However, the polymer aqueous solution persisted as a sol phase below 4.0 wt % as well as above 16 wt % in the same temperature range, thus forming a closed-loop gel domain in the phase diagram. The closed-loop gel domain is suggested to be a result of the balance between the aggregation and the stabilization of micelles in specific temperature and concentration ranges.     

One-pot synthesis of PDMAEMA nanocapsules for controlled release of hydrophobic cargo

In this work, poly((N,N-dimethyl amino)ethyl methacrylate) (PDMAEMA) homopolymers are synthesized using RAFT technique, which is then used as stabilizers to prepare miniemulsion droplets in a toluene/hexadecane(HD)/1,2-Bis-(2-iodoethyl)ethane(BIEE)/hydrophobic molecule/water mixture. Upon the reaction between BIEE and the stabilizers of miniemulsion droplets, the polymeric nanocapsules are formed and capable of encapsulating hydrophobic molecule in their oil core in one-step reaction. The release of hydrophobic cargo from the nanocapsules can be controlled by the variation of amount of surfactant (Tween®20) in the release medium and a long duration sustained release was achieved.     

Photochemical release of nitric oxide from a regenerable, sol-gel encapsulated Ru-salen-nitrosyl complex

Light activation leads to release of NO from a silicate sol-gel material SG-RuNO prepared from the ruthenium complex, [Ru(salen)(OH2)(NO)]+ (salen = N,N'-bis-(salicylidene)ethyl-enediaminato); after photochemical NO photolabilization, SG-RuNO can be regenerated from the spent material via the subsequent reaction with aqueous nitrite.     

Critical exponents and self-similarity for sol-gel transition in aqueous alginate systems induced by in situ release of calcium cations

The sol-gel transition in aqueous alginate systems induced by in situ released calcium cations was monitored with rheology methods. Four alginate samples with different molecular weights and M/G ratios were used over the concentration C(Alg) of 2 approximately 6 wt % with different mole ratios f of Ca2+ to the alginate repeat unit. The scaling for the zero shear viscosity eta(0) before the gel point and the equilibrium modulus Ge after the gel point was described as eta(0) approximately epsilon(-k) and Ge approximately epsilon(z), respectively, where the relative distance to the gel point f(gel) was epsilon = (/f-f(gel)/)/f(gel). The relaxation critical exponent n was determined with Winter's criterion, and the critical exponents k and z estimated respectively from independent measurements of eta(0) and Ge gave n from z/(k + z). Before the gel point, the storage and loss moduli G' and G' obtained at various epsilon can be superposed fairly well to form the master curve. The critical exponents n, k, and z were also evaluated from the shift factors and the structure self-similarity was found in the critical gel. The critical exponents evaluated with different methods agreed well with each other, suggesting two categories of the gelation as growth and cross-link. For the alginate with lower molecular weight, the critical exponents were almost independent of alginate concentration and close to the percolation prediction. For the alginate with higher molecular weight, the critical exponents, however, changed with alginate sample and concentration. The relative alginate concentration C(Alg)/C(Alg)* was found to serve as a criterion to divide these two transitions.     

Surface-localized release of nitric oxide via sol-gel chemistry

The release of nitric oxide (NO) from polymers has proven to be highly effective at inhibiting platelet adhesion and thus enhancing the blood compatibility of medical implants. Micropatterning techniques were used to design surfaces that release NO while preserving the underlying substrate for other applications (e.g., sensors). Micropatterned NO-releasing substrates based on aminosilane-containing methyltrimethoxysilane sol-gels were prepared and characterized in terms of stability, NO surface flux, and resistance to in vitro platelet adhesion. We have found that surface-localized NO release from substrates modified with sol-gel micropatterns exhibit enhanced blood compatibility relative to controls.     

Ion imprinted sol-gel nanotubes membrane for selective separation of copper ion from aqueous solution

Selective separation of Cu(II) ions from aqueous solution was accomplished with a new type of ion-imprinted silica nanotube membrane. A study on its capability for adsorption and selective recognition showed that best selectivity coefficient over Zn(II) ion was over 150, which is much higher than those of control silica nanotube membranes. The largest relative selectivity coefficient over Zn(II) was >200. The new membrane also possess a fast kinetics for the removal of Cu(II) from aqueous solution, an equilibrium period of <30 min, and suitability for repeated use. Hence, the new membrane acts as an effective material for highly selective preconcentration and separation of Cu(II) ion.     

Synergistic co-entrapment and triggered release in hollow nanocapsules with uniform nanopores

We describe a new co-entrapment and release motif based on the combination of noncovalent and steric interactions in materials with well-defined nanopores. Individual components enter hollow nanocapsules through nanopores in the capsule shell. Their complex, larger than the pore size, remains entrapped. The dissociation of the complex upon external stimulus releases entrapped components. Reversible formation of complexes between diaza-18-crown-6 and metal ions was used to demonstrate the feasibility of new approach to co-entrapment and triggered release.     

Encapsulation and release of aqueous components from sonochemically produced protein microspheres

Aqueous solutions of salts or dyes have been contained in sonochemically produced lysozyme microspheres by encapsulating an inverse emulsion in tetradecane. Release can be triggered by chemically disrupting crosslinking in the protein shell or by mechanical disruption using high intensity ultrasound.     

Stimuli-responsive supramolecular nanocapsules from amphiphilic calixarene assembly

We synthesized tetrameric amphiphilic molecules based on a calixarene building block that self-assembles into a tunable and stable aggregation structure in aqueous solution. The amphiphilic calixarene molecules with a small hydrophilic part were observed to assemble into a vesicular structure that decreases significantly in diameter with only small increases in the hydrophilic chain length. Further increasing the chain length induced the collapse of the vesicles into spherical micelles. Remarkably, the vesicles were also observed to transform into small globular micelles at lower pH, which can be used to trigger the release of the encapsulated hydrophilic guest molecules.     

Spectrally tunable uncaging of biological stimuli from nanocapsules

This communication describes the first uncaging of stimuli in the far red, wavelengths that have much less of an adverse affect on cellular systems, via photolysis of photosensitized nanocapsules.     

L-asparaginase release from Escherichia coli cells with aqueous two-phase micellar systems

A method was proposed to release and separate L-asparaginase (EC 3.5.1.1) from Escherichia coli ATCC 11303 cells with aqueous two-phase micellar systems. The systems were composed of K2HPO4 and Triton X-100. The method combines enzyme release with enzyme purification. The influence of Triton X-100 concentration, K2HPO4 concentration, and pH on the release and partition of L-asparaginase was investigated. Experimental results showed that E. coli cells treated with 9.4% (w/v) K2HPO4 and 15% (w/v) Triton X-100 at 25 degrees C for 15-20 h released nearly 80% of the enzyme. Most of the released enzyme was partitioned to the bottom phase (phosphate-rich phase). The effects of Triton X-100 concentration, K2HPO4 concentration, and pH on cloud point were also studied. Electron micrography indicated that the chemical treatment altered the inner structure of E. coli cells significantly.     

Preparation of albumin—PAA nanocapsules and their controlled release behavior for drugs

New kinds of narrowly distributed protein‐based nanoparticles, bovine serum albumin‐Poly (acrylic acid) (BSA/PAA) nanospheres, and nanocapsules were prepared via in situ polymerization, swelling, and re‐aggregation. The structure and morphology of the nanospheres were characterized by UV‐Vis, FT‐IR, DLS, and TEM. The stability of the BSA/PAA nanospheres and nanocapsules was increased when their skeletons were fixed by cross‐linked agents. The nanospheres carried a positive charge and their size was about 80–110 nm. The protein‐based nanocapsules were stimuli‐responsive with pH value and their hydrodynamic diameter varied from 70 to 230 nm with changes of pH. In vitro release experiments of Rhodamine B and Doxorubicin hydrochloride showed that these biopolymer nanoparticles provided a controlled release of the entrapped drugs for 300 hr. Copyright © 2009 John Wiley & Sons, Ltd.     

Three-phase microemulsion/sol-gel system for aqueous catalysis with hydrophobic chemicals

A facile three-phase transport process is described that allows to carry out catalytic reactions in water, whereby all components are hydrophobic. According to this process a hydrophobic substrate is microemulsified in water and subjected to an organometallic catalyst, which is entrapped within a partially hydrophobized sol-gel matrix. The surfactant molecules, which carry the hydrophobic substrate, adsorb/desorb reversibly on the surface of the sol-gel matrix breaking the micellar structure, spilling their substrate load into the porous medium that contains the catalyst. A catalytic reaction then takes place within the ceramic material to form the desired products that are extracted by the desorbing surfactant, carrying the emulsified product back into the solution. The method is general and versatile and has been demonstrated with the catalytic hydrogenations of alkenes, alkynes, aromatic C=C bonds, and nitro and cyano groups.     

Closed-surface hexameric metal-organic nanocapsules derived from cavitand ligands

Assembly of cavitand ligands, (4-), and Zn2+ ions yields a one-dimensional polymer comprised of hexameric, closed-surface, metal-organic nanocapsules.     

Triggered release of molecules across droplet interface bilayer lipid membranes using photopolymerizable lipids

A combination of nonpolymerizable phospholipids (DPPC or DPhPC) and a smaller amount of cross-linking photopolymerizable phospholipids (23:2 DiynePC) is incorporated in an unsupported artificial lipid bilayer formed using the droplet interface bilayer (DIB) approach. The DIB is formed by contacting lipid monolayer-coated aqueous droplets against each other in a dodecane-lipid medium. Cross-linking of the photopolymerizable lipids incorporated in the DIB was obtained by exposure to UV-C radiation (254 nm), resulting in pore formation. The effect of cross-linking on the DIB properties was characterized optically by measuring the diffusion of selectively encapsulated dye molecules (calcein) from one droplet of the DIB to the other droplet. Changes in DIB conductivity due to UV-C exposure were investigated using current-voltage (I-V) measurements. The leakage of dye molecules across the DIB and the increase in DIB conductivity after UV-C exposure indicates the formation of membrane pores. The results indicate that the DIB approach offers a simple and flexible platform for studying phototriggered drug delivery systems in vitro.     

Preparation of non-spherical hollow carbon nanocapsules from nickel nanoprecursors

Hollow carbon nanocapsules (NCs) are prepared from nickel nanoplate precursors through carburizing, decomposition, and leaching steps. The carburizing step was carried out by heating the nickel nanoplates in oleylamine at 250 °C for 4 h. Decomposition was then performed in a nitrogen atmosphere at 530 °C for 3 min. Characterization of the resulting product of the first two steps shows the intermediates to be Ni₃C/Ni–C alloy and Ni/C core–shell nanostructures. Hollow carbon NCs are recovered from the products by leaching the Ni/C core–shell nanostructures in concentrated nitric acid. The NCs are found to have a high specific surface area (1081 m² g⁻¹) and a mesoporous structure (i.e., a pore volume of 2.81 cm³/g and a narrow pore size distribution of 2.9–3.4 nm). In addition, it is found that the hollow carbon NCs retained the same morphology as the original nickel precursors; demonstrating the robustness of the nickel templates and the ability of the carbon shells to maintain a non-spherical shape.     

Selective separation of lead from aqueous solution with a novel Pb(II) surface ion-imprinted sol-gel sorbent

A novel Pb(II) ion-imprinted mesoporous sorbent (IIMS) was synthesized by a surface imprinting technique combined with a sol-gel process and characterized by FT-IR and N₂ adsorption-desorption. Compared to the non-imprinted mesoporous sorbent (NIMS), the IIMS had a higher adsorption capacity and selectivity for Pb(II). The maximum static adsorption capacities of the IIMS and NIMS for Pb(II) were 221 and 173 mg g^?1, respectively. The relative selectivity coefficients of the sorbent for Pb(II) in the presence of Cd(II), Cu(II) and Zn(II) were 3.7, 1.9 and 3.4, respectively. Furthermore, the IIMS possessed a fast kinetics for Pb(II) sorption from aqueous solution with saturation time of <?20 min, and could be used repeatedly. The detection limit (3σ) of this method was 0.23 ng mL^?1 and relative standard deviation of 11 replicate determinations was 3.7 %. The IIMS has been applied to selectively separate and determine Pb(II) in real water samples with satisfactory results.     

Synthesis of lead-based 1212 and 3212 superconductors by an aqueous sol-gel method

The aqueous sol-gel synthesis technique for the preparation of (Pb,Sr)Sr₂(Y,Ca)Cu₂O_7±x (Pb-1212) and (Pb₂,Cu)Sr₂(Y,Ca)Cu₂O_8±x (Pb-3212) superconductors using two different complexing agents, namely 1,2-ethanediol and tartaric acid was studied. The phase transformations, composition and micro-structural features in the polycrystalline samples were studied by powder X-ray diffraction analysis (XRD), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XRD analysis of the ceramic samples obtained by calcination of Pb-Sr-Y-Ca-Cu-O acetate-glycolate precursor gels in air, for 10 hours at 800°C and at 825°C, showed the presence of homogeneous Pb-1212 and Pb-3212 crystallites as major phases. The XRD patterns of the ceramics obtained from Pb-Sr-Y-Ca-Cu-O acetate-tartrate precursor gels, however, showed multiphasic character. The critical temperature of superconductivity (T_C (onset)) observed by resistivity measurements were found to be 91 K and 75 K for Pb-1212 and Pb-3212 samples, respectively.      

Facile fabrication of thermally responsive Pluronic F127-based nanocapsules for controlled release of doxorubicin hydrochloride

Novel core–shell-structured Pluronic-based nanocapsules with thermally responsive properties were successfully prepared using a modified emulsification/solvent evaporation method. The nanocapsules were constructed through the cross-linking reaction between p-nitrophenyl-activated Pluronic F127 and hyaluronic acid (HA) (named Pluronic F127/HA) or poly(ε-lysine) (PL) (named Pluronic F127/PL) at the organic/aqueous interface. The formation, size, and thermal responsiveness of the nanocapsules were characterized by ¹H NMR, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The resultant shell-cross-linked nanocapsules exhibit a larger volume transformation (26 times change in volume for Pluronic F127/HA and 31 times for Pluronic F127/PL) over a temperature range of 4–37 °C because of the temperature-dependent dehydration of cross-linked Pluronic F127 polymer chains. The nanocapsules are about 72?±?4 nm (polydispersity index [PDI]?=?0.08) for Pluronic F127/PL (69?±?5 nm, PDI?=?0.10 for Pluronic F127/HA) at 37 °C with narrow size distribution and expand to about 226?±?23 nm (PDI?=?0.34) for Pluronic F127/PL (206?±?20 nm, PDI?=?0.3) for Pluronic F127/HA at 4 °C with broad size distribution in aqueous solutions. The nanocapsules were used to encapsulate and control the release of doxorubicin hydrochloride (DOX·HCl) in aqueous solution. DOX·HCl was physically encapsulated in the nanocapsules using a soaking–freeze-drying–heating procedure. The release curve and release kinetics disclosed that the thermally responsive hollow nanocapsules are good carries for drug delivery.