Polymeric Nanocapsule from Silica Nanoparticle@Cross-linked Polymer Nanoparticles via One-Pot Approach

A facile strategy was developed here to prepare cross-linked polymeric nanocapsules (CP nanocapsules) with silica nanoparticles as templates. The silica nanoparticle@cross-linked polymer nanoparticles were prepared by the encapsulation of the silica nanoparticles by the one-pot approach via surface-initiated atom transfer radical polymerization of hydroxyethyl acrylate in the presence of N,N′-methylenebisacrylamide as a cross-linker from the initiator-modified silica nanoparticles. After the silica nanoparticle templates were etched with hydrofluoric acid, the CP nanocapsules with particle size of about 100 nm were obtained. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis and transmission electron microscopy.     

Hydroxyl end-functionalized poly(2-isopropyl oxazoline)s used as nano-sized colloidal templates for preparation of hollow polymeric nanocapsules

Hollow polymeric nanocapsules with a thermosensitive membrane are prepared and characterized. They reversibly change their dimensions during temperature variations below and above the transition of the membrane. The nanocapsules were prepared by three steps: (i) well-defined mesoglobules prepared from an LCST polymer (hydroxyl end functionalized poly(2-isopropyl-2-oxazoline), PiPOZ-OH) were coated with a thermo-sensitive cross-linked shell formed via seeded radical copolymerization of N-isopropylacrylamide (NIPAM) and N,N′-bis-methylene acrylamide to produce core–shell nanoparticles (ii), which were subjected to extensive dialysis below the LCSTs of both the core-forming PiPOZ-OH and shell-forming PNIPAM to remove the core (iii). The use of a core-forming polymer of low molecular weight (<8900 g mol⁻¹), narrow dispersity (<1.15) and relatively low T_g (52–68 °C) is beneficial as far as the effectiveness of the removal of the cores is concerned. The inherent immiscibility between PiPOZ-OH and PNIPAM as well as the specific raspberry-like structure of the core–shell particles also contributed for enhancement of the core removal effectiveness.     

Preparation of chitosan nanocapsules and their release properties

Chitosan nanocapsules are prepared using poly(S-co-MAA) particles as the template and cross-linked chitosan with glutaraldehyde as shell, the core templates are removed by THF. The template particles and nanocapsules are characterized by FESEM and TEM. By dissolution of ibuprofen in the chloroform droplets prepares the poly(S-co-MAA), drug-loaded nanocapsules are also fabricated. It is found that the loaded drug can be released again in a sustained manner for up to 80 h.     

Facile Preparation of Crosslinked Polymeric Nanocapsules via Combination of Surface-Initiated Atom Transfer Radical Polymerization and Ultraviolet Irradiated Crosslinking Techniques

A facile approach for the preparation of crosslinked polymeric nanocapsules was developed by the combination of the surface-initiated atom transfer radical polymerization and ultraviolet irradiation crosslinking techniques. The well-defined polystyrene grafted silica nanoparticles were prepared via the SI-ATRP of styrene from functionalized silica nanoparticles. Then the grafted polystyrene chains were crosslinked with ultraviolet irradiation. The cross-linked polystyrene nanocapsules with diameter of 20–50 nm were achieved after the etching of the silica nanoparticle templates with hydrofluoric acid. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis, and transmission electron microscopy.     

Temperature and pH dual responsive crosslinked polymeric nanocapsules via surface-initiated atom transfer radical polymerization

Novel intelligent nanocapsules with temperature-responsive crosslinked shells and pH responsive brushes on their inner walls have been designed and prepared by using the “polymerization from template” strategy via the surface-initiated atom transfer radical polymerization (SI-ATRP) technique with silica nanoparticles as the sacrificial templates. The two-steps sequential SI-ATRP procedure provided the poly(tert-butyl acrylate) (PtBA) brushes on the inner walls of the temperature-responsive crosslinked poly(N-isopropylacrylamide) (PNIPAm) shells. Then the ester groups in the nanocapsules were transformed chemically into carboxyl groups after etching the silica templates with HF. The environmental responsive characteristics of the dual responsive crosslinked hollow nanocapsules (DRCNs) were characterized with dynamic light scattering (DLS) system in aqueous solutions. The intelligent nanocapsules are expected to be used for the controlled releasing of drugs.     

Mesoglobules of thermoresponsive polymers in dilute aqueous solutions above the LCST

The colloidal stability and characteristics of particles formed by homopolymers of poly(N-vinyl caprolactam), poly(N-isopropyl acrylamide) and poly(vinyl methyl ether) in dilute aqueous solutions above the lower critical solution temperature, LCST, was followed by means of dynamic and static light scattering. Depending on the solution concentration, the homopolymers precipitate or form stable dispersions of monodisperse spherical particles. To obtain colloidally stable aggregates, also called mesoglobules, no stabilising agent was added. The stability of the mesoglobules upon time and dilution at temperatures above the LCST suggests that the particle surfaces possess a hydrophilic character. The size of the formed particles depends on the concentration and the heating rate of the solutions. However, internal structure and shape of mesoglobules are affected neither by the way, how the mesoglobules were prepared, nor by molar mass of individual macromolecules. Mesoglobules of PNIPAM obey the M∝R^2.7 scaling law. Origin of stability of the dispersions vs. expected precipitation is discussed.     

Mono-dispersed Functional Polymeric Nanocapsules with Multi-lacuna via Soapless Microemulsion Polymerization with Spindle-like α-Fe2O3 Nanoparticles as Templates

The mono-dispersed crosslinked polymeric multi-lacuna nanocapsules (CP(St–OA) nanocapsules) about 40 nm with carboxylic groups on their inner and outer surfaces were fabricated in the present work. The small conglomerations of the oleic acid modified spindle-like α-Fe₂O₃ nanoparticles (OA–Fe₂O₃) were encapsulated in the facile microemulsion polymerization with styrene (St) as monomer and divinyl benzene (DVB) as crosslinker. Then the templates, small conglomerations of OA–Fe₂O₃, were etched with HCl in tetrahydrofuran (THF). The surface carboxylic groups of the crosslinked polymeric multi-lacuna nanocapsules were validated by the Zeta potential analysis.     

Bulk quantity and physical properties of boron nitride nanocapsules with a narrow size distribution

A new synthesis route for the formation of boron nitride (BN) nanocapsules by means of a substitution process using single wall carbon nanotubes as templates, with yields of >95% is presented. It is also shown that these BN nanocapsules can act as ideal reference samples for the determination of the relative sp² to sp³ configuration in BN species, a value that is crucial for the physical properties of these nanostructures.     

Thermosensitive poly(N-isopropylacrylamide) nanocapsules with controlled permeability

In this paper, novel thermosensitive poly(N-isopropylacrylamide) (PNIPAM) nanocapsules with temperature-tunable diameter and permeability are reported. Firstly, the core-shell composite microparticles were synthesized by precipitation polymerization with isothiocyanate fluorescein (FITC) entrapped SiO₂ as core and cross-linked PNIPAM as shell. Then, the SiO₂ core was etched by hydrofluoric acid at certain condition and the pre-trapped FITC molecules remained within the inner cavity. The FITC release profile and TEM studies clearly indicate that the release behavior of FITC could be controlled effectively by the external temperature. Above the LCST of PNIPAM (32 °C), the dehydrated PNIPAM shell inhibited the release of FITC from the internal cavity while below its LCST, the fluorophore could permeate the swollen shell easily.     

1H NMR study of temperature-induced phase transitions in aqueous solutions of poly(N-isopropylmethacrylamide)/poly(N-vinylcaprolactam) mixtures

¹H NMR spectroscopy was used to investigate the temperature-induced phase transitions in aqueous solutions of poly(N-isopropylmethacrylamide)/poly(N-vinylcaprolactam) (PIPMAm/PVCL) mixtures to find out if the phase transition of the given component (PIPMAm or PVCL) is affected by the presence of the second component. Our results that PVCL and PIPMAm transitions are in polymer mixtures shifted by ~2 K towards higher temperatures in comparison with neat polymers and depend on polymer concentration show that such effect exists. Spin–spin relaxation times of water (HDO) indicate that in solutions with c ≥ 1 wt% a portion of water is predominantly bound in PVCL mesoglobules even at temperatures above the LCST transition of PIPMAm component. Water is with time released from these mesoglobules without any induction period so indicating that it is mostly indirectly bound water. We assume that there is a direct connection between character of the bound water and the transition temperatures.     

Effect of time on the hydration and temperature-induced phase separation in aqueous polymer solutions. H NMR study

Dehydration during temperature-induced phase separation in D₂O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm) and poly(N-isopropylacrylamide) (PIPAAm) was followed from time dependences of NMR spin-spin relaxation times T₂ of HDO. Both the time characterizing the exclusion of the water from mesoglobules (manifested by the increase in T₂ values) and the induction period which precedes the increase in T₂ values, increased in the order PVME < PIPMAm < PIPAAm. For D₂O solutions of PIPMAm/PVME (or PIPMAm/PIPAAm) mixtures a direct connection between the state of the mesoglobules (hydrated or dehydrated) formed by the component with lower LCST (PVME, PIPAAm) and the temperatures of the phase transition of the PIPMAm component was established by NMR spectroscopy.     

Labeling the oily core of nanocapsules and lipid-core nanocapsules with a triglyceride conjugated to a fluorescent dye as a strategy to particle tracking in biological studies

The synthesis of novel fluorescent materials represents a very important step to obtain labeled nanoformulations in order to evaluate their biological behavior. The strategy of conjugating a fluorescent dye with triacylglycerol allows that either particles differing regarding supramolecular structure, i.e., nanoemulsions, nanocapsules, lipid-core nanocapsules, or surface charge, i.e., cationic nanocapsules and anionic nanocapsules, can be tracked using the same labeled material. In this way, a rhodamine B-conjugated triglyceride was obtained to prepare fluorescent polymeric nanocapsules. Different formulations were obtained, nanocapsules (NC) or lipid-core nanocapsules (LNC), using the labeled oil and Eudragit RS100, Eudragit S100, or poly(caprolactone) (PCL), respectively. The rhodamine B was coupled with the ricinolein by activating the carboxylic function using a carbodiimide derivative. Thin layer chromatography, proton nuclear magnetic resonance (¹H-NMR), Fourier transform infrared spectroscopy (FTIR), UV-vis, and fluorescence spectroscopy were used to identify the new product. Fluorescent nanocapsule aqueous suspensions were prepared by the solvent displacement method. Their pH values were 4.6 (NC-RS100), 3.5 (NC-S100), and 5.0 (LNC-PCL). The volume-weighted mean diameter (D_4.3) and polydispersity values were 150 nm and 1.05 (NC-RS100), 350 nm and 2.28 (NC-S100), and 270 nm and 1.67 (LNC-PCL). The mean diameters determined by photon correlation spectroscopy (PCS) (z-average) were around 200 nm. The zeta potential values were +5.85 mV (NC-RS100), -21.12 mV (NC-S100), and -19.25 mV (LNC-PCL). The wavelengths of maximum fluorescence emission were 567 nm (NC-RS100 and LNC-PCL) and 574 nm (NC-S100). Fluorescence microscopy was used to evaluate the cell uptake (human macrophage cell line) of the fluorescent nanocapsules in order to show the applicability of the approach. When the cells were treated with the fluorescent nanocapsules, red emission was detected around the cell nucleus. We demonstrated that the rhodamine B-conjugated triglyceride is a promising new material to obtain versatile dye-labeled nanocarriers presenting different chemical nature in their surfaces.     

Hydrogels containing redispersible spray-dried melatonin-loaded nanocapsules: a formulation for transdermal-controlled delivery

The aim of the present study was to develop a transdermal system for controlled delivery of melatonin combining three strategies: nanoencapsulation of melatonin, drying of melatonin-loaded nanocapsules, and incorporation of nanocapsules in a hydrophilic gel. Nanocapsules were prepared by interfacial deposition of the polymer and were spray-dried using water-soluble excipients. In vitro drug release profiles were evaluated by the dialysis bag method, and skin permeation studies were carried out using Franz cells with porcine skin as the membrane. The use of 10% (w/v) water-soluble excipients (lactose or maltodextrin) as spray-drying adjuvants furnished redispersible powders (redispersibility index approximately 1.0) suitable for incorporation into hydrogels. All formulations showed a better controlled in vitro release of melatonin compared with the melatonin solution. The best controlled release results were achieved with hydrogels prepared with dried nanocapsules (hydrogels > redispersed dried nanocapsules > nanocapsule suspension > melatonin solution). The skin permeation studies demonstrated a significant modulation of the transdermal melatonin permeation for hydrogels prepared with redispersible nanocapsules. In this way, the additive effect of the different approaches used in this study (nanoencapsulation, spray-drying, and preparation of semisolid dosage forms) allows not only the control of melatonin release, but also transdermal permeation.     

Effects of subphase pH and temperature on the interfacial behavior of double hydrophilic diblock copolymer PDEGMA-b-PDIPAEMA

The aggregation behavior of two pH- and temperature-responsive diblock copolymers of poly[di-(ethylene glycol) methyl ether methacrylate]-block-poly[2-(diisopropylamino) ethyl methacrylate] (PDEGMA-b-PDIPAEMA) at the air/water interface and the structures of their Langmuir–Blodgett (LB) films were studied by the Langmuir monolayer technique and atomic force microscopy, respectively. At the air/water interface, PDEGMA-b-PDIPAEMA tends to form the core-shell-corona micellar structure composed of a PDIPAEMA main chain core, an amino ethyl ester shell, and a PDEGMA corona. Under acidic, neutral, and alkaline conditions, PDIPAEMA blocks are completely protonated, partially protonated, and completely non-protonated, respectively, and the protonated amino ethyl ester groups are immersed in water before monolayer compression, whereas PDEGMA coronas are adsorbed at the interface. At pH 3, 7, and 10, the limiting areas (A₀) for PDEGMA42%-PDIPAEMA58% (weight percents) and PDEGMA55%-PDIPAEMA45% are 8.2/10.2/14.0 and 6.7/8.3/8.4 nm², respectively. The A₀ values of the former copolymer are larger than those of the latter. This is because the shells in the former copolymer are denser due to the higher polymerization degree of PDIPAEMA blocks, providing greater steric hindrance for PDEGMA coronas and making the latter more extended at the interface. In contrast to other copolymer systems, the effect of temperature on the isotherms of PDEGMA-b-PDIPAEMA is less obvious.     

Formation of mesoglobules in aqueous media from thermo-sensitive poly(ethoxytriethyleneglycol acrylate)

A series of six poly(ethoxytriethyleneglycol acrylate) (PETEGA) homopolymers were synthesized by atom transfer radical polymerization, reversible addition-fragmentation transfer polymerization, and anionic polymerization in order to cover a molecular weight range from 7,000 to 40,000 Da. The polymers exhibited a lower critical solution temperature (LCST) behavior in water, which was observed by the occurrence of a cloud point (CP) at around 35 °C. The transmittance of visible light versus temperature dependence overlapped during the cooling and the heating cycles, showing almost a complete lack of hysteresis. Moreover, instead of the occurrence of an uncontrolled macroscopic phase separation, stable colloidal aggregates (mesoglobules) of narrow distribution in particle size were formed in water at temperatures above the LCST of PETEGA at 1 g L⁻¹ solutions. The dimensions of the mesoglobules ranged from 91 to 235 nm, and particle size was not influenced by the molecular weight of PETEGA. Temperature changes caused considerable variations of the mesoglobules dimensions, which were smaller at higher temperatures. The addition of an anionic surfactant simultaneously increased the CP values by 4–6 °C and lowered the dimensions of the mesoglobules.     

Characterization and magnetic properties of carbon-coated cobalt nanocapsules synthesized by the chemical vapor-condensation process

Carbon-coated cobalt nanocapsules were synthesized by the chemical vapor-condensation process with cobalt carbonyl (Co₂(CO)₈) used as precursor and carbon monoxide (CO) as carrier gas. The characterization and magnetic properties of carbon-coated cobalt nanocapsules were investigated systematically. The transmission electron microscope (TEM) images showed that the as-prepared nanoparticles consist of a metal core and an amorphous carbon shell. X-ray diffraction and TEM selected area diffraction revealed the presence of f.c.c. Co phase, h.c.p. Co phase, and minority Co₂C, Co₃C phases. The saturation magnetization at room temperature of the nanocapsules is 146.9 Am² kg⁻¹, which is 90% of the bulk ferromagnetic element counterpart. The coercive force at room temperature of the nanocapsules is 0.12 T, while the ratio of remnant to saturation magnetization M_r/M_s is about 0.4. The saturation magnetization and the coercive force increase with increasing the decomposition temperature, mainly due to the increase of the size of the magnetic particles. The decomposition of the cobalt carbonyl (Co₂(CO)₈) and CO gas can decrease efficiently the oxygen content in nanocapsules. The metallic Co nanoparticles completely coated by carbon can resist the dilute acid erosion as well as the oxidation. The thermal stability of the Co nanocapsules is also studied.     

Preparation and characterization of crosslinked poly(methylmethacrylate) heat sensitive color-developing nanocapsules

The crosslinked poly(methylmethacrylate) (PMMA) heat sensitive color-developing nanocapsules were prepared by emulsion polymerization, in which leucocompound was used as a core material and methyl methacrylate and unsaturated hyperbranched poly(amide-ester) as wall-forming materials. The nanocapsules were characterized by Malvern particle size analysis, scanning electron microscopy, Fourier transform infrared spectrophotometry (FTIR), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), and densitometry. Triton X-100 was used as the emulsifier of emulsion polymerization. The effects of the emulsifier content on the particle size distribution and morphology of nanocapsules were discussed in detail. The FTIR analysis of leucocompound-containing nanocapsules demonstrated that leucocompound was successfully encapsulated in the crosslinked PMMA matrix. TGA results showed that the resultant nanocapsules had good thermal stabilities. The DSC analysis of the resultant nanocapsules indicated that the glass transition temperature of the nanocapsules was 117.9 °C. The resultant nanocapsules had narrower particle size distribution, smoother surface, and higher heat sensitive color-developing density with the percentage weight of emulsifier being 0.6 wt%.     

Thermosensitive graft copolymers of an amphiphilic macromonomer and N-vinylcaprolactam: synthesis and solution properties in dilute aqueous solutions below and above the LCST

Thermosensitive graft copolymers of N-vinylcaprolactam and poly(ethylene oxide)-alkyl methacrylate macromonomer were synthesised with different grafting densities. Association of the polymers in dilute aqueous solutions was studied below and above the LCST using static and dynamic light scattering, microcalorimetry, pressure perturbation calorimetry (PPC), and fluorescence probe experiments. Owing to the amphiphilicity of the grafts, the most densely grafted polymer forms intrapolymeric structures while the less grafted polymers build up mixtures of intra- and interpolymeric associates at temperatures below LCST. These assemblies solubilise hydrophobic substances such as pyrene. Upon heating, the graft copolymers aggregate in water and form nano-sized particles, mesoglobules. Heat induced particles are exceptionally stable against further aggregation, and the dilution of the solutions has no effect on the particle size or shape. The structure of the particles can be frozen by physically crosslinking the collapsed polymers with a phenol, e.g. 1,2-benzenediol.     

Sacrificial PSS-doped CaCO3 templates to prepare chitosan capsules and their deformation under bulk pressure

To prepare microcapsules composed of chitosan (CS), a templating method is developed using poly(styrene sulfonate) (PSS)-doped porous calcium carbonate (CaCO₃) templates as sacrificial templates. First, CS is absorbed onto PSS-doped porous CaCO₃ templates, and then the absorbed CS is covalently cross-linked with each other by using glutaraldehyde. Porous CaCO₃ templates are dissolved with disodium ethylenediaminetetraacetate dihydrate and the resultant CS capsules ranged from 2 to 5 μm in diameter. Nitrogen adsorption–desorption analysis are applied to characterize the porous CaCO₃ templates, the BET surface area and total pore volume are 220 m²/g and 0.36 cm³/g, respectively. Field-emission scanning electron microscopy and transmission electron microscopy were used to characterize the CS capsules morphology. Confocal laser scanning microscopy images reveal that the capsules have been labeled with green fluorescein isothiocyanate. The gradual deformation of capsule in response to bulk osmotic pressure created by CS solutions has also been discussed.     

Fabrication of poly(vinyl alcohol)s (PVAs) nanotubes through the fusion of nanocapsules composed of PVAs multilayer films

Poly(vinyl alcohol) (PVA) nanocapsules were fabricated by the deposition of PVA multilayer films onto the surface of silica particles followed by the removal of the silica cores. When a water dispersion of PVA nanocapsules was dried on a substrate, PVA nanotubes were formed through the one-dimensional fusion of the nanocapsules. This fusion behavior of the PVA nanocapsules was strongly affected by the molecular weights and acetylation degrees of PVA, the capsule film thickness of the PVA nanocapsules and the temperature to dry a water dispersion of the nanocapsules. When nanocapsules composed of 20 layered films of acetylated PVA with a 14% acetylation degree were used, nanotube formation via the fusion of these nanocapsules occurred effectively upon drying the water dispersion at 20 °C.