Phthalocyanine-based nanoporous network polymers

Network polymers exhibiting large surfaces areas (450-950 m2 g-1) are prepared by the phthalocyanine-forming reaction of a bis(phthalonitrile) monomer containing a rigid spirocyclic linking group.     

Ordered nanoporous polymers from polystyrene-polylactide block copolymers

Nanoporous polystyrene monoliths were prepared from polystyrene-polylactide (PS-PLA) block copolymers that form hexagonally packed nanocylinders of PLA in a PS matrix. A morphology diagram was developed to determine the range in composition and molecular weight over which this morphology existed. Macroscopic alignment of these materials gave anisotropic monoliths that were subjected to mild degradation conditions leading to the chemical etching of the PLA. The resulting nanoporous monoliths consisted of a polystyrene matrix containing hexagonally close-packed, oriented, and continuous nanoscopic channels (pore size was tunable through synthesis or blending) lined with chemically accessible hydroxyl functional groups. Both the precursors and the porous materials were analyzed moleculary (size-exclusion chromatography and proton nuclear magnetic resonance spectroscopy) and structurally (small-angle X-ray scattering, scanning electron microscopy, and differential scanning calorimetry). In addition, the surface area and pore size distribution of the nanoporous monoliths were characterized (N2 adsorption measurements). These nanoporous materials have remarkable potential as hosts for nanomaterial synthesis, size-selective catalyst supports, and advanced separations.     

Positron lifetime spectroscopy in ordered nanoporous polymers

Positron annihilation lifetime spectroscopy (PALS) is a common technique used to characterize the porosity of polymers. Here, we expand its use to the study of ordered nanoporous polymer monoliths. Polystyrene (PS) monoliths with aligned cylindrical pores ranging in diameters from 15 to 35 nm were examined. Such large pores push the boundaries of the PALS technique. To achieve robust measurement, our system used larger detectors than those typically used for monolithic polymer samples. This was done to improve data rates while sacrificing timing resolution. Pore sizes determined using PALS were consistent with measurements made using small angle x‐ray scattering. In addition, PALS was able to detect the collapse of the pores when the monolithic sample was heated above the T_g of PS. Because PALS measurements are not sensitive to the nature of the order within the structure nor are they, sensitive to the open or closed nature of the pores this technique could be expanded to a variety of other sample types. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1157–1161     

Phosphine-based coordination cages and nanoporous coordination polymers

Recent findings in the use of multidentate phosphines to synthesise porous coordination polymers (metal-organic frameworks) and their possible precursor cages are reviewed. Additional recent investigations into using large adamantoid Age cages as polymer vertices in giant diamandoid structures are also presented. The results are discussed in terms of possible strategies for the controled synthesis of porous coordination polymers.     

Porphyrin-based switchable molecular turnstiles

The design, synthesis and structural characterisation, in solution, of two new molecular turnstiles based on Sn-porphyrin derivatives are described. The system is composed of a stator (5-(4-pyridyl)-10,15,20-triphenylporphyrin), a hinge (Sn(IV)) and a rotor (handle equipped with 2,6-pyridinedicarboxamide as a tridentate coordinating site or its Pd(II) complex). The presence of interaction sites, both on the stator and the rotor, offers the possibility of switching between an open state (free rotation of the handle around the porphyrin) and a closed state (blockage of the rotation) by either establishment of hydrogen bonds between the stator and the rotor or by the simultaneous binding of Pd by both coordinating groups.     

Hybrid azobenzene-doped nanoporous polymers derived from cubic octavinylsilsesquioxane

A series of novel hybrid porous polymers (HPPs) with high specific surface areas were first prepared by one-step ternary cross-linking copolymerization of octavinylsilsesquioxane (OVS), 1,3,5-tribromobenzene, and 4,4´-dibromoazobenzene via the Heck reaction. The porosities and the CO₂ uptake capacities of resulting azobenzene-doped porous polymers could be tuned by modulating the molar percentage of the azo units. At 273 K and 101 kPa, the sample with the specific surface area of ~700 m² g^–1 (data of Brunauer—Emmett—Teller (BET) surface area analysis) showed the highest CO₂ uptake of 5.45 wt.% (1.20 mmol g^–1) among the fabricated HPPs.

     

Porphyrin-based photocatalytic lithography

Photocatalytic lithography couples light with photoreactive coated mask materials to pattern surface chemistry. We excite porphyrins to create radical species that photocatalytically oxidize, and thereby pattern, chemistries in the local vicinity. The technique advantageously is suited for use with a wide variety of substrates. It is fast and robust, and the wavelength of light does not limit the resolution of patterned features. We have patterned proteins and cells to demonstrate the utility of photocatalytic lithography in life science applications.     

Electrochemically controlled release based on nanoporous conducting polymers

An electrochemically controlled drug release system based on nanoporous polypyrrole (PPy) films was developed. Pyrrole and a model drug, fluorescein, were electrochemically copolymerized on glassy carbon (GC) electrodes modified with self-assembled multilayer polystyrene (PS) nanobeads, and PPy films incorporated with fluorescein as dopants were formed among the interstitial spaces of the tightly packed PS nanobead template. After the removal of the PS hard template, nanoporous PPy films incorporated with the drug fluorescein were obtained. Due to the porous morphology and huge surface area, the efficiency of the prepared PPy films in electrochemically releasing incorporated fluorescein was about nine times higher than that of conventional PPy films.     

Glass transition of polymers confined to nanoporous glasses

The glassy dynamics of poly(propylene glycol) (PPG) and poly(methyl phenyl siloxane) (PMPS) confined to nanoporous glasses (pore sizes 2.5–20 nm) investigated by dielectric spectroscopy, temperature modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature modulated DSC agree quantitatively indicating that both experiments sense the glass transition.For PPG the glassy dynamics in nanopores is determined by a counterbalance of an adsorption and a confinement effect where the temperature dependence of the relaxation times obeys the Vogel/Fulcher/Tammann (VFT-) equation. The former effect results from an interaction of the confined macromolecules with the internal surfaces which in general slows down the molecular dynamics. A confinement effect leads to an acceleration of the segmental dynamics compared to the bulk state and points to an inherent length scale on which the glassy dynamics takes place. The step of the specific heat capacity c_p at the glass transition vanishes at a finite length scale of 1.8 nm. This result supports further the conception that a characteristic length scale is relevant for glassy dynamics.For PMPS down to a pore size of 7.5 nm the temperature dependence of the relaxation times follows the VFT-dependence and a confinement effect is observed like for PPG. At a pore size of 5 nm this changes to an Arrhenius-like behavior with a low activation energy. At the same pore size c_p vanishes for PMPS. This points to a dramatic change in the character of molecular motions responsible for glassy dynamics and supports further the relevance of a characteristic length scale on which it takes place.Quasielastic neutron scattering experiments on PMPS reveal that the microscopic dynamics characterized by the mean square displacement depends on confinement above the glass transition. The diffusive character of the relevant molecular motions seems to disappear at a length scale of about 1.6 nm.     

卟啉类化合物分子光电器件研究进展

分子电子器件是未来分子电路的微电子元件,已成为有机功能纳米材料研究的热点。 卟啉类化合物的π共轭体系表现出的独特光电性能和良好的热稳定性,使其作为光电器件、模拟生物酶、分子识别和传感材料在材料化学、医学、生物化学和分析化学等领域展现出良好的应用前景,由于卟啉分子平面结构的易修饰性,常用卟啉化合物组装单元来构建功能化的卟啉光电器件。 本文综述了卟啉类化合物的特点及其在光电器件中的应用进展。     

A Novel Porphyrin-based Hydrogen-bonded Organic Framework

A novel hydrogen-bonded organic framework, HOF-TCPP(HOF = hydrogen bonded organic framework, TCPP = tetrakis(4-carboxyphenyl) porphyrin), has been synthesized via solvothermal reaction in ethylene glycol. Crystal structure was well determined by single-crystal X-ray diffraction and powder X-ray diffraction(PXRD). Topological analysis reveals that HOF-TCPP exhibits sql 2 D layer and features 2 D → 3 D polycatenation. Fluorescence investigation shows that HOF-TCPP displays much higher photoluminescence(PL) intensity than the amorphous ligands TCPP, which can be ascribed to the crystalline structure and hydrogen bonds existing in the structure.     

Nanocomposite and nanoporous polyaniline conducting polymers exhibit enhanced catalysis of nitrite reduction

Nanostructured polyaniline (PANI) conducting polymer films were prepared on electrochemically pretreated glassy carbon electrodes, which were previously modified with multilayers of polystyrene (PS) nanoparticles with a diameter of 100 nm. PANI was electropolymerised and grown through the interstitial spaces between the PS nanoparticles, which formed a nanocomposite film of PANI and PS nanoparticles on the electrode surface. Furthermore, a nanoporous PANI film was fabricated through the removal of the PS nanoparticles by dissolution in toluene. As a result of their nanostructure, both of the PANI films (before and after removal of the PS nanoparticles) exhibited enhanced electrocatalytic behaviour towards the reduction of nitrite relative to bulk-PANI films; however, partial collapse or shrinkage may have occurred with the removal of the nanoparticles and could have resulted in a less enhanced response. Under optimised conditions, the nanocomposite-film-modified electrode exhibited a fast response time of 5 s and a linear range from 5.0 x 10(-7) to 1.4 x 10(-3) M for the detection of nitrite; the detection limit was 2.4 x 10(-7) M at a signal-to-noise ratio of 3.     

Cobalt Porphyrin-based Solid-Contact Electrode Sensitive to Pyridine Concentration

A solid-contact electrode based on cobalt tetraphenyl porphin, sensitive to pyridine concentration, was studied. The properties of this electrode were analyzed.     

Porphyrin-based peptide receptors: syntheses and NMR analysis

The synthesis and purification of a water-soluble host compound that contains three pyridinium units and one spacer-connected benzocrown ether unit in the meso-positions of porphyrin and of its Zn(II) or Cu(II) complexes is described. Metalation leads to small (compared to the apo-derivative) changes of selectivities with different peptides, with complexation constants in water of above 10(5)M(-1). One complex containing the tripeptide Gly-Gly-Phe is analyzed in detail by COSY, HSQC, HMBC, and NOESY NMR experiments. Temperature-dependent spectra show activation energies for a intramolecular hydrogen exchange of amide protons with valence isomerization of the porphyrin ring, in accordance with the literature. Sharp signals for the spin system are only found at elevated temperature. Vicinal coupling constants within the crown ether moiety indicate stronger puckering than that reported for benzocrowns. All NMR signals of the complexed peptide are shielded, in particular those of the terminal phenylalanine unit, in line with its stacking on the porphyrin surface. A corresponding structural model, obtained by CHARMm simulation, is also in line with the observed intermolecular NOE cross peaks.     

卟啉共价有机框架化合物的研究进展

共价有机框架化合物(COFs)是一类新兴的具有多孔结构的晶态有机聚合物,在储存与分离、催化、能量转化等领域具有广泛应用。本文介绍了一类基于卟啉单元的COFs,从框架构筑及应用开发两方面综述了这类材料的研究进展。     

Supramolecular Self-assembly and Functionalization of Porphyrin-based Systems

Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004–2012. This review gives a full summary of related studies in our group.     

Fabrication and electrochemical properties of novel nanoporous platinum network electrodes

Three-dimensional nanoporous Pt networks with a high surface area were directly grown on titanium substrates through a simple hydrothermal-assisted seed growth method.     

Porphyrin-based heterogeneous photocatalysts for solar energy conversion

In recent years, porphyrins with a similar structure to chlorophyll are often used as photosensitizers or reaction centers to improve the light absorption capacity or catalytic selectivity of existing photocatalytic systems. However, photocatalytic reactions include photoelectric conversion, photocarrier transport, and surface reaction, which requires the overall design of porphyrin-based photocatalysts. In this paper, the research work of porphyrin molecular design in heterogeneous photocatalys...     

Novel network polymers based on calixresorcinarenes

The novel network polymers 2a-2d based on calix[4]resorcinarene derivatives were obtained with yields 2a: 80%, 2b: 90%, 2c: 70%, 2d: 70%. Polymers 2a and 2b containing fragments of tetramethylcalix[4]resorcinarene or tetraphenylcalix[4]resorcinarene as a repeating units were synthesized by condensation cis-tetramethylcalix[4]resorcinarene or cis-tetraphenylcalix[4]resorcinarene with formaldehyde. Polymers 2c and 2d containing fragments of furylcalix[4]resorcinarene were obtained by condensation of formaldehyde with products of calix[4]resorcinarene and furfural interaction. The IR spectra and sorption properties of the polymers were researched. It is found out that 2a-2d can participate in the cation-exchange reaction.