Gas Transport in a Polymer of Intrinsic Microporosity (PIM-1) Substituted with Pseudo-Ionic Liquid Tetrazole-Type Structures.

We report a side group modification strategy to tailor the structure of a polymer of intrinsic microporosity (PIM-1). PIM-1 with an average of ∼50% of the repeat units converted to tetrazole is prepared, and a subsequent reaction then introduces three types of pseudo-ionic liquid tetrazole-like structures (PIM-1-ILx). The presence of pseudo-ionic liquid functional groups in the PIM-1 structure increases gas selectivities for O2/N2 and CO2/N2, while it decreases pure-gas permeabilities. The overall gas separation performance of PIM-1-ILx is close to the 2008 Robeson upper bound. Since the tetrazoles are versatile groups for building a wide variety of ionic liquids, the modification method can be expanded to explore a broad spectrum of functional groups.

Polymer nanosieve membranes for CO2-capture applications.

Microporous organic polymers (MOPs) are of potential significance for gas storage, gas separation and low-dielectric applications. Among many approaches for obtaining such materials, solution-processable MOPs derived from rigid and contorted macromolecular structures are promising because of their excellent mass transport and mass exchange capability. Here we show a class of amorphous MOP, prepared by [2+3] cycloaddition modification of a polymer containing an aromatic nitrile group with an azide compound, showing super-permeable characteristics and outstanding CO(2) separation performance, even under polymer plasticization conditions such as CO(2)/light gas mixtures. This unprecedented result arises from the introduction of tetrazole groups into highly microporous polymeric frameworks, leading to more favourable CO(2) sorption with superior affinity in gas mixtures, and selective CO(2) transport by presorbed CO(2) molecules that limit access by other light gas molecules. This strategy provides a direction in the design of MOP membrane materials for economic CO(2) capture processes.

Azide-based cross-linking of polymers of intrinsic microporosity (PIMs) for condensable gas separation.

Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O(2) /N(2) and CO(2) /N(2) gas pairs, as well as for condensable gases, such as CO(2) /CH(4) , propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO(2) plasticization up to 20 atm pressure of pure CO(2) and CO(2) /CH(4) mixtures.

Copolymers of Intrinsic Microporosity Based on 2,2',3,3'-Tetrahydroxy-1,1'-dinaphthyl.

A series of new copolymers with high molecular weight and low polydispersity, prepared from tetrahydroxydinaphthyl, tetrahydroxyspirobisindane, and tetrafluoroterephthalonitrile monomers, prevent efficient space packing of the stiff polymer chains and consequently show intrinsic microporosity. One copolymer, DNPIM-33, has an excellent combination of properties with good film-forming characteristics and gas transport performance, and exhibits higher selectivity than the corresponding spirobisindane-based homopolymer PIM-1 for gas pairs, such as O(2) /N(2) , with a corresponding small decrease in permeability. This work demonstrates that significant improvements in properties may be obtained through development of copolymers with intrinsic microporosity (CoPIMs) that extends the spectrum of high-molecular-weight ladder structures of poly(dibenzodioxane)s.

Comparative study of ruthenium(II) tris(bipyridine) derivatives for electrochemiluminescence application.

Several [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine and its derivatives) complexes were synthesized and compared electrochemically and spectroscopically in the search for better luminophores for electrochemiluminescence (ECL)-based analytical applications. ECL measurement in [Ru(bpy)3]2+/tripropylamine (TPA) aqueous buffer solutions has led to a conclusion that due to the complexity of the ECL generation process, the photoluminescence efficiency cannot be used to predict ECL intensity and there is no obvious relationship between the photoluminescence quantum yield and the ECL intensity. Under the present experimental condition, when compared with the pristine [Ru(bpy)3]2+, the ethoxycarbonyl-substituted derivative, [Ru(bpy-COOEt)3]2+, one of the most efficient luminophores under photoexcitation, did not generate reasonably intense ECL, whereas luminophores with lower photoluminescence quantum yields demonstrated higher ECL. These findings are useful for further efforts in the search for more efficient ECL luminophores.

Multilabeling biomolecules at a single site. 1. Synthesis and characterization of a dendritic label for electrochemiluminescence assays.

Ultrasensitive bioanalytical assays are of great value for early detection of human diseases and pathogens. The sensitivities of immunoassays and DNA probing can be enhanced by multilabeling the biorecognition partner used for affinity-based assays. However, the bioreactivity of biomolecules is affected by a high degree of multilabeling at multiple functional sites. It is proposed that dendritic scaffoldings be used to link multiple signal-generating units to a single site with potentially minimum impact on the bioaffinity. A prototype label, a zeroth-generation dendron, bearing three [Ru(bpy)(3)](2+) units for electrochemiluminescence (ECL) assays was synthesized and characterized preliminarily by spectroscopic, electrochemical, and ECL methods. No evidence of interaction between the neighboring [Ru(bpy)(3)](2+) units in the label molecule was found from these characterizations. Both the photoluminescence and ECL of the prototype label have features very similar to those of mononuclear [Ru(bpy)(3)](2+) compounds. Labeling a model protein with a triad of [Ru(bpy)(3)](2+) at one NH(2) position was demonstrated. The results reported here provide support to applying the proposed multilabeling strategy to affinity-based bioanalytical assays.