Aggregation behavior of the template-removed 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin chiral array directed by poly(ethylene glycol)-block-poly(L-lysine).

Complexation between 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and poly(ethylene glycol)-block-poly(L-lysine) (PEG-b-PLL) was performed via electrostatic interaction. Two kinds of primary arrays of TPPS with different supramolecular chirality induced by PLL were obtained in the resultant complex by inverting the mixing procedure of the two components. These arrays could be displaced by poly(sodium-p-styrenesulfonate) (PSS) from the chiral PLL template through competitive electrostatic complexation, and then PSS formed a polyion complex micelle with PEG-b-PLL. The template-removed TPPS arrays preserved their induced chirality and served as primary subunits for the secondary aggregation of TPPS. The morphology of the secondary aggregates was strongly dependent upon the asymmetric primary supramolecular arrangement of TPPS. The rodlike nanostructure that was ∼200 nm in length was composed of the primary arrays that showed opposite exciton chirality between the J- and H-bands. In contrast, the micrometer-sized fibrils observed were composed of the arrays with the same exciton chirality at the J- and H-bands.

Facile strategy for synthesis of silica/polymer hybrid hollow nanoparticles with channels.

The silica/polymer hybrid hollow nanoparticles with channels and gatekeepers were successfully fabricated with a facile strategy by using thermoresponsive complex micelles of poly(ethylene glycol)-b-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) and poly(N-isopropylacrylamide)-b-poly(4-vinylpyridine) (PNIPAM-b-P4VP) as the template. In aqueous solution, the complex micelles (PEG-b-PNIPAM/PNIPAM-b-P4VP) formed with the PNIPAM block as the core and the PEG/P4VP blocks as the mixed shell at 45 °C and pH 4.0. After shell cross-linking by 1,2-bis(2-iodoethoxyl)ethane (BIEE), tetraethylorthosilicate (TEOS) selectively well-deposited on the P4VP block and processed the sol-gel reaction. When the temperature was decreased to 4 °C, the PNIPAM block became swollen and further soluble, and the PEG-b-PNIPAM block copolymer escaped from the hybrid nanoparticles as a result of swelled PNIPAM and weak interaction between PEG and silica at pH 4.0. Therefore, the hybrid hollow silica nanoparticles with inner thermoresponsive PNIPAM as gatekeepers and channels in the silica shell were successfully obtained, which could be used for switchable controlled drug release. In the system, the complex micelles, as a template, could avoid the formation of larger aggregates during the preparation of the hybrid hollow silica nanoparticles. The thermoresponsive core (PNIPAM) could conveniently control the hollow space through the stimuli-responsive phase transition instead of calcination or chemical etching. In the meantime, the channel in the hybrid silica shell could be achieved because of the escape of PEG chains from the hybrid nanoparticles.

A porphyrin-based optical sensor membrane prepared by electrostatic self-assembled technique for online detection of cadmium(II).

An optical sensor membrane was prepared by electrostatic self-assembled technique for online detection of cadmium ion (II) (Cd(II)). The optical indicator 5,10,15,20-tetrakis(4-N-methylpyridyl) porphyrin p-toluenesulfonate (TMPyP) was adsorbed on a hydrolyzed polyacrylonitrile (PAN) membrane by electrostatic attraction and further immobilized through layer-by-layer deposition of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS) on the membrane surface. The electrostatic self-assembly of polyelectrolytes on the membrane is influenced by pH and salt concentration of polyelectrolytes. The optical sensor membrane shows distinct color and spectral response to Cd(II) under static and flow-through conditions based on the coordination of TMPyP with Cd(II). A faster detection of Cd(II) is achieved at higher feed concentration of Cd(II) or appropriate lower immobilization capacity of TMPyP on the membrane. The flow-through detection is also influenced by the flow rate; higher flow rate led to faster response to Cd(II) during filtration. Compared with the static process, the flow-through conditions are more conducive to faster analysis of ppb level concentration of Cd(II) (10-3 mg L-1) due to a promoted mass transfer and filtration enrichment. Hence, the development of the optical sensor membrane in this study demonstrated the prospect to make membranes multifunctional with advantages for online chromatic warning in addition to adsorption/rejection of heavy metal ions in the solutions that are treated.

Enhanced hydrolysis of cellulose by catalytic polyethersulfone membranes with straight-through catalytic channels.

The aim of this study was to prepare sulfonated graphene oxide/polyether sulfone (GO-SO3H/PES) mixed matrix membranes (GPMMMs) with high porosity and straight-through catalytic channels by segregation and used for dynamic and continuous hydrolysis of cellulose. The high porosity and segregation increased the exposure of catalysts synergistically and the formative GO-SO3H enriched, straight-through catalytic channels had higher catalytic performance, enhancing the diffusion of hydrolytic products. Dynamic hydrolysis of cellulose is more efficient than static hydrolysis due to the enhanced contact between cellulose and catalysts achieved by the extra driving forces, and the further degradation of produced saccharides was suppressed due to the high freedom of products. The TRS reached 98.18% after 1 h at 150 °C with a catalyst/cellulose mass ratio of 1:5. More importantly, the immobilization of GO-SO3H by PES improved its stability and reusability at high reaction temperature. This strategy provides guidance to the design of high-performance catalytic membranes.

J- and H-aggregates of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin and interconversion in PEG-b-P4VP micelles.

Micellization of poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG114-b-P4VP61) induced by 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) in acidic solutions were studied by dynamic and static light scattering, atomic force microscope, and UV-vis spectroscopy. The resultant complex micelles had a core-shell structure with the electrostatically complex TPPS/P4VP as the core and the soluble PEG as the shell. The anionic TPPS in the micellar core formed J-aggregates at pH 1.5-2.5 and H-aggregates at pH 3.0-4.0, respectively. Interconversion between the J-aggregates and the H-aggregates was carried out by adjusting the pH value of the micelle solutions. It is worth noting that the micelles showed strong split Cotton effect in the circular dichroism spectra although TPPS and the copolymer were all achiral. The resulting chirality sign could be selected by the hydrodynamic forces of a stirring vortex. Positive or negative chiral signals appeared when stirring clockwise or anticlockwise.

Cooperative self-assembly of porphyrins with polymers possessing bioactive functions.

Natural porphyrin derivatives possess many interesting functions in biological systems. They are integrated into proteins that are essential for biological activities. Many efforts have been dedicated to mimic the microenvironment and augment the function of porphyrin/protein scaffolds. To achieve such goals, self-assembly has become one of the popular methods to construct porphyrin/protein-mimicking materials owing to its various choices of building blocks and a simple preparation process over chemical modification. Desirable characteristics of building blocks for protein mimicking include high molecular weight, predictable conformations in solution, and appropriate functional residuals. With these aims in mind, polymers are ideal candidates due to their multiple-level hierarchies derived from their chemical and spatial structures. In this review, design strategies for the cooperative self-assembly of porphyrins with polymers and the main efforts towards the implementation of porphyrin/polymer assembly for biomimetic composites with bioactive functions will be addressed.

A strategy to modulate the electrophoretic behavior in plastic microchips using sodium polystyrene sulfonate.

Plastic microchips have been broadly used as disposable microfluidic devices, but the poorly defined surface properties limit their application. Herein, we proved that an anionic polymer could be used as the background electrolyte (BGE) to provide a strong and stable cathodic electroosmotic flow (EOF) and modulate the electrophoretic behavior for efficient separation in relative thicker microchannels (∼75µm id). A cathodic EOF of ∼3.3×10-4cm2V-1s-1 was maintained using sodium polystyrene sulfonate (PSSNa) with a molecular weight of 5×105 as the BGE, which ensured fluorescein isothiocyanate labeled biogenic amines (BAs) appeared ahead of other components in the electropherograms obtained with microchips of cyclic olefin copolymer. Four selected BAs appeared within 50s and theoretical plate numbers of 8.0×105/m were achieved. The role of PSSNa was evaluated with streaming potential, dynamic light scattering, contact angle and atomic force microscopy. Its functionalities as surface modifier, viscosity regulator and pseudostationary phase were also confirmed. The proposed electrophoretic method was applied in the fast determination of BAs in fish meat samples.

Enhancement of the photostability and photoactivity of metallo-meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrins by polymeric micelles.

Metallo-meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrins (metallo-TPPSs), such as ZnTPPS, have been widely used as photosensitizers. However, their vulnerability to photodegradation significantly limits their applications. In this contribution, we demonstrate a method to enhance the photostability of metallo-TPPSs while retaining photoactivity via encapsulation inside cores of complex micelles. Poly(ethylene glycol)-b-poly(4-vinylpyridine) (PEG-b-P4VP) and metallo-TPPSs can form complex micelles in acidic solution through electrostatic interactions and then undergo axial coordination with the pyridine moieties of PEG-b-P4VP when the pH is adjusted to 7.4. In this way, metallo-TPPSs are entrapped in the hydrophobic, compact micellar cores, which effectively prevents photodegradation of the metallo-TPPSs that would otherwise occur in aqueous solution. In addition, the photodebromination of 2,3-dibromo-3-phenylpropionic acid (DPP) sensitized with ZnTPPS has been used as a model reaction to study the photosensitive activity of ZnTPPS entrapped in complex micelles. The entrapped ZnTPPSs exhibit pronounced activity and have much higher efficiency and faster photosensitive reaction rates than free ZnTPPS.

Stability enhancement of ZnTPPS in acidic aqueous solutions by polymeric micelles.

Poly(ethyleneglycol)-b-poly(4-vinylpyridine) (PEG-b-P4VP) and zinc meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin (ZnTPPS) form complex micelles based on electrostatic interactions. The complex micelles have a core-shell structure that can effectively prevent the demetallization and aggregation of ZnTPPS in acidic aqueous solutions (pH < 4.0).

A valid way of quasi-quantificationally controlling the self-assembly of block copolymers in confined space.

To mimic nanostructures assembled by biomolecules in organic cells and achieve precise self-assembly of block copolymers, a simple but valid way is introduced to quasi-quantificationally control the aggregation numbers (N(agg)) of polymeric micelles. A three-dimensional and closed microconfinement similar to a cell is constructed by W/O inverse emulsion as the spot for self-assembly of the pH-responsive block copolymer poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG-b-P4VP). The N(agg) values of the resulting polymeric micelles are effectively controlled by tuning the number of polymer chains encapsulated in isolated water pools. Micelles with different N(agg) values are successfully prepared and characterized by atomic force microscopy, transmission electron microscopy, and dynamic light scattering. When the number of polymer chains enclosed in a water pool (N(chain)) is less than the average N(agg) of normal micelles generated in bulk aqueous solution, the resultant aggregates formed in the confined spaces always have lower N(agg) as well as smaller sizes than the normal micelles do, while normal micelles predominantly form when N(chain) > N(agg) (normal micelle).

Fabrication of complex micelles with tunable shell for application in controlled drug release.

At room temperature, diblock copolymers of PLA-b-PNIPAM and PEG-b-PLA self-assembled into complex micelles with a PLA core and a mixed PEG/PNIPAM shell. By increasing the temperature, these complex micelles could be converted into a core-shell-corona structure composed of a PLA core, a collapsed PNIPAM shell and a soluble PEG corona, and the PEG chains stretched from the inner core to outside, leading to the formation of PEG channels. The PEG channels could be used for the exchange of substance between the core and the external environment. Compared with core-shell micelles, complex micelles with a core-shell-corona structure could avoid the burst diffusion in the release of ibuprofen and inhibit the degradation of PLA by lipase to a certain extent.