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Sample records for liquid delivery metalorganic

  1. Liquid Metal-Organic Frameworks: Formation Mechanism, Structure and Properties

    OpenAIRE

    Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.; Chapman, Karena W.; Keen, David A.; Bennett, Thomas D.; Coudert, François-Xavier

    2017-01-01

    Metal--organic frameworks are a novel family of chemically diverse materials, with applications in a wide field covering engineering, physics, chemistry, biology and medicine. Research so far has focused almost entirely on crystalline structures, yet a clear trend has emerged shifting the emphasis onto disordered states of MOFs, including "defective by design" crystals, as well as amorphous phases such as glasses and gels. Here we introduce a MOF liquid, a strongly associated liquid obtained ...

  2. Designing Kitaev Spin Liquids in Metal-Organic Frameworks

    Science.gov (United States)

    Yamada, Masahiko G.; Fujita, Hiroyuki; Oshikawa, Masaki

    2017-08-01

    Kitaev's honeycomb lattice spin model is a remarkable exactly solvable model, which has a particular type of spin liquid (Kitaev spin liquid) as the ground state. Although its possible realization in iridates and α -RuCl3 has been vigorously discussed recently, these materials have substantial non-Kitaev direct exchange interactions and do not have a spin liquid ground state. We propose metal-organic frameworks (MOFs) with Ru3 + (or Os3 + ), forming the honeycomb lattice as promising candidates for a more ideal realization of Kitaev-type spin models, where the direct exchange interaction is strongly suppressed. The great flexibility of MOFs allows generalization to other three-dimensional lattices for the potential realization of a variety of spin liquids, such as a Weyl spin liquid.

  3. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    Science.gov (United States)

    McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; Düren, Tina; Williams, Jennifer J.; Charrier, Cedric; Mercer, Derry K.; Teat, Simon J.; Morris, Russell E.

    2014-12-01

    The highly porous nature of metal-organic frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  4. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Alistair C. McKinlay

    2014-12-01

    Full Text Available The highly porous nature of metal-organic frameworks (MOFs offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  5. Ionic liquid accelerates the crystallization of Zr-based metal-organic frameworks.

    Science.gov (United States)

    Sang, Xinxin; Zhang, Jianling; Xiang, Junfeng; Cui, Jie; Zheng, Lirong; Zhang, Jing; Wu, Zhonghua; Li, Zhihong; Mo, Guang; Xu, Yuan; Song, Jinliang; Liu, Chengcheng; Tan, Xiuniang; Luo, Tian; Zhang, Bingxing; Han, Buxing

    2017-08-02

    The Zr-based metal-organic frameworks are generally prepared by solvothermal procedure. To overcome the slow kinetics of nucleation and crystallization of Zr-based metal-organic frameworks is of great interest and challenging. Here, we find that an ionic liquid as solvent can significantly accelerate the formation of Zr-based metal-organic frameworks at room temperature. For example, the reaction time is shortened to 0.5 h in 1-hexyl-3-methylimidazolium chloride for Zr-based metal-organic framework formation, while that in the conventional solvent N,N-dimethylformamide needs at least 120 h. The reaction mechanism was investigated in situ by (1)H nuclear magnetic resonance, spectroscopy synchrotron small angle X-ray scattering and X-ray absorption fine structure. This rapid, low-energy, and facile route produces Zr-based metal-organic framework nanoparticles with small particle size, missing-linker defects and large surface area, which can be used as heterogeneous catalysts for Meerwein-Ponndorf-Verley reaction.Crystallization kinetics of metal-organic frameworks in conventional organic solvents are usually very slow. Here, the authors show that an ionic liquid medium accelerates considerably the formation of Zr-based metal-organic frameworks that are active catalysts in the Meerwein-Ponndorf-Verley reaction.

  6. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    Science.gov (United States)

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  7. Metal-organic frameworks as host materials of confined supercooled liquids.

    Science.gov (United States)

    Fischer, J K H; Sippel, P; Denysenko, D; Lunkenheimer, P; Volkmer, D; Loidl, A

    2015-10-21

    In this work, we examine the use of metal-organic framework (MOF) systems as host materials for the investigation of glassy dynamics in confined geometry. We investigate the confinement of the molecular glass former glycerol in three MFU-type MOFs with different pore sizes (MFU stands for "Metal-Organic Framework Ulm-University") and study the dynamics of the confined liquid via dielectric spectroscopy. In accord with previous reports on confined glass formers, we find different degrees of deviations from bulk behavior depending on pore size, demonstrating that MOFs are well-suited host systems for confinement investigations.

  8. A multifunctional metal-organic framework based tumor targeting drug delivery system for cancer therapy

    Science.gov (United States)

    Wang, Xiao-Gang; Dong, Zhi-Yue; Cheng, Hong; Wan, Shuang-Shuang; Chen, Wei-Hai; Zou, Mei-Zhen; Huo, Jia-Wei; Deng, He-Xiang; Zhang, Xian-Zheng

    2015-09-01

    Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects.Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects. Electronic supplementary information (ESI) available

  9. Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide

    Science.gov (United States)

    Eubank, Jarrod F.; Wheatley, Paul S.; Lebars, Gaëlle; McKinlay, Alistair C.; Leclerc, Hervé; Horcajada, Patricia; Daturi, Marco; Vimont, Alexandre; Morris, Russell E.; Serre, Christian

    2014-12-01

    The room temperature sorption properties of the biological gas nitric oxide (NO) have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL)-100(Fe or Cr) and MIL-127(Fe). In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II) Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II) sites, providing further insights over the partial release of NO only in the presence of water at room temperature.

  10. Porous, rigid metal(III-carboxylate metal-organic frameworks for the delivery of nitric oxide

    Directory of Open Access Journals (Sweden)

    Jarrod F. Eubank

    2014-12-01

    Full Text Available The room temperature sorption properties of the biological gas nitric oxide (NO have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL-100(Fe or Cr and MIL-127(Fe. In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II sites, providing further insights over the partial release of NO only in the presence of water at room temperature.

  11. Assembly of metal-organic polyhedra into highly porous frameworks for ethene delivery.

    Science.gov (United States)

    Stoeck, Ulrich; Senkovska, Irena; Bon, Volodymyr; Krause, Simon; Kaskel, Stefan

    2015-01-21

    Two new mesoporous metal-organic frameworks (DUT-75 and DUT-76) with exceptional ethene uptake were obtained using carbazole dicarboxylate based metal-organic polyhedra as supermolecular building blocks. The compounds have a total pore volume of 1.84 and 3.25 cm(3) g(-1) and a specific BET surface area of 4081 and 6344 m(2) g(-1), respectively, and high gas uptake at room temperature and high pressure.

  12. Nanoscale metal-organic frameworks for biomedical imaging and drug delivery.

    Science.gov (United States)

    Della Rocca, Joseph; Liu, Demin; Lin, Wenbin

    2011-10-18

    Metal-organic frameworks (MOFs), a class of hybrid materials formed by the self-assembly of polydentate bridging ligands and metal-connecting points, have been studied for a variety of applications. Recently, these materials have been scaled down to nanometer sizes, and this Account details the development of nanoscale metal-organic frameworks (NMOFs) for biomedical applications. NMOFs possess several potential advantages over conventional nanomedicines such as their structural and chemical diversity, their high loading capacity, and their intrinsic biodegradability. Under relatively mild conditions, NMOFs can be obtained as either crystalline or amorphous materials. The particle composition, size, and morphology can be easily tuned to optimize the final particle properties. Researchers have employed two general strategies to deliver active agents using NMOFs: by incorporating active agents into the frameworks or by loading active agents into the pores and channels of the NMOFs. The modification of NMOF surfaces with either silica coatings or organic polymers improves NMOF stability, fine-tunes their properties, and imparts additional functionality. Preliminary biomedical applications of NMOFs have focused on their use as delivery vehicles for imaging contrast agents and molecular therapeutics. Because NMOFs can carry large amounts of paramagnetic metal ions, they have been extensively explored as magnetic resonance imaging (MRI) contrast agents. Both Gd(3+)- and Mn(2+)-containing NMOFs have shown excellent efficacy as T(1)-weighted contrast agents with large per metal- and per particle-based MR relaxivities. Fe(3+)-containing NMOFs have demonstrated excellent T(2)-weighted contrast enhancement. Upon intravenous injection of iron carboxylate NMOFs in Wistar rats, researchers observed negative signal enhancement in the liver and spleen, which dissipated over time, indicating the degradation and clearance of the NMOF. Through the incorporation of luminescent or high

  13. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

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    Wencai Zhou

    2015-06-01

    Full Text Available The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs, is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM, the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1, whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  14. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Science.gov (United States)

    Zhou, Wencai; Wöll, Christof; Heinke, Lars

    2015-01-01

    The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  15. Hybrid Glasses from Strong and Fragile Metal-Organic Framework Liquids

    DEFF Research Database (Denmark)

    Bennett, T.D.; Tan, J.C.; Yue, Yuanzheng

    2015-01-01

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between...... amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density ‘perfect’ glass, similar to those formed in ice, silicon and disaccharides. This order–order transition leads to a super-strong liquid of low fragility that dynamically......-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of ‘melt-casting’ MOF glasses....

  16. Liquid chromatographic separation in metal-organic framework MIL-101: a molecular simulation study.

    Science.gov (United States)

    Hu, Zhongqiao; Chen, Yifei; Jiang, Jianwen

    2013-02-05

    A molecular simulation study is reported to investigate liquid chromatographic separation in metal-organic framework MIL-101. Two mixtures are considered: three amino acids (Arg, Phe, and Trp) in aqueous solution and three xylene isomers (p-, m-, and o-xylene) dissolved in hexane. For the first mixture, the elution order is found to be Arg > Phe > Trp. The hydrophilic Arg has the strongest interaction with the polar mobile phase (water) and the weakest interaction with the stationary phase (MIL-101), and thus transports at the fastest velocity. Furthermore, Arg forms the largest number of hydrogen bonds with water and possesses the largest hydrophilic solvent-accessible surface area. For the second mixture, the elution order is p-xylene > m-xylene > o-xylene, consistent with available experimental observation. With the largest polarity as compared to p- and m-xylenes, o-xylene interacts the most strongly with the stationary phase and exhibits the slowest transport velocity. For both mixtures, the underlying separation mechanism is elucidated from detailed energetic and structural analysis. It is revealed that the separation can be attributed to the cooperative solute-solvent and solute-framework interactions. This simulation study, for the first time, provides molecular insight into liquid chromatographic separation in a MOF and suggests that MIL-101 might be an interesting material for the separation of industrially important liquid mixtures.

  17. Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

    Science.gov (United States)

    Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

    2017-07-01

    Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

  18. Assembling Metal-Organic Frameworks in Ionic Liquids and Supercritical CO2.

    Science.gov (United States)

    Zhang, Bingxing; Zhang, Jianling; Han, Buxing

    2016-10-06

    Ionic liquids (ILs) and supercritical carbon dioxide (scCO2 ) are both considered to be green solvents with tunable properties. Recently, studies of the synthesis of metal-organic frameworks (MOFs) in the presence of ILs and scCO2 has become a burgeoning direction in chemistry and materials science. ILs have been shown to be ideal media for the synthesis of a variety of MOFs owing to their unique properties including the ability to dissolve a wide range of organic and inorganic compounds and flexible designability. scCO2 has adjustable solvent power and excellent mass-transfer characteristics that offer the opportunity to replace organic solvents for MOF activation, MOF aerogel synthesis, and MOF construction. More interestingly, the simultaneous utilization of IL and scCO2 can combine the advantages of the two liquids, which provides novel routes for the fabrication of MOF structures. This review describes the advances in MOF synthesis in ILs, scCO2 , and IL/scCO2 systems. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Coordination polymer nanocapsules prepared using metal-organic framework templates for pH-responsive drug delivery

    Science.gov (United States)

    Tang, Lei; Shi, Jiafu; Wang, Xiaoli; Zhang, Shaohua; Wu, Hong; Sun, Hongfan; Jiang, Zhongyi

    2017-07-01

    A facile, efficient, and versatile approach is presented to synthesize pH-responsive nanocapsules (˜120 nm) by combining the advantages of metal-organic frameworks (MOFs) and metal-organic thin films. ZIF-8 nanoparticles are used as templates on which a thin film coating of iron(III)-catechol complexes is derived from the coordination between dopamine-modified alginate (AlgDA) and iron(III) ions. After the template removal, nanocapsules with a pH-responsive wall are obtained. Doxorubicin (Dox), a typical anticancer drug, is first immobilized in ZIF-8 frameworks through coprecipitation and then encapsulated in nanocapsules after the removal of ZIF-8. The structure of the iron(III)-catechol complex varies with pH value, thus conferring the Dox@Nanocapsules with tailored release behavior in vitro. Cytotoxicity tests illustrate the highly effective cytotoxicity of Dox@Nanocapsules towards cancer cells. This study provides a new method for preparing smart nanocapsules and offers more opportunities for the controlled delivery of drugs.

  20. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Metere, Alfredo, E-mail: alfredo.metere@mmk.su.se; Oleynikov, Peter [Department of Materials and Environmental Chemistry, Stockholm University, S-106 91 Stockholm (Sweden); Dzugutov, Mikhail [Department of Mathematics, Royal Institute of Technology, S-100 44 Stockholm (Sweden); O’Keeffe, Michael [Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287 (United States)

    2014-12-21

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

  1. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid.

    Science.gov (United States)

    Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail; O'Keeffe, Michael

    2014-12-21

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

  2. High internal ionic liquid phase emulsion stabilized by metal-organic frameworks.

    Science.gov (United States)

    Li, Zhihao; Zhang, Jianling; Luo, Tian; Tan, Xiuniang; Liu, Chengcheng; Sang, Xinxin; Ma, Xue; Han, Buxing; Yang, Guanying

    2016-11-04

    The emulsification of metal-organic frameworks (MOFs) for the two immiscible phases of water and ionic liquid (IL) was investigated for the first time. It was found that Ni-BDC (BDC = 1,4-dicarboxybenzene) can emulsify water and ILs and favor the formation of high internal phase emulsions (HIPEs) under certain experimental conditions. The microstructures of the HIPEs were characterized by confocal laser scanning microscopy using a fluorescent dye Rhodamine B, which proves that the HIPEs are the IL-in-water type. Further results reveal that the HIPE forms during the IL-in-water to water-in-IL emulsion inversion. The possibilities of the HIPE formation by other MOFs (Cu-BDC and Zn-BDC) were explored and the mechanism for HIPE formation was discussed. The MOF-stabilized HIPE was applied to the in situ synthesis of a MOF/polymer composite by HIPE polymerization. The macroporous MOF/polyacrylamide network and MOF/polystyrene microspheres were obtained from the HIPEs, respectively.

  3. Metal-organic frameworks for the storage and delivery of biologically active hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Allan, Phoebe K; Wheatley, Paul S; Aldous, David; Mohideen, M Infas; Tang, Chiu; Hriljac, Joseph A; Megson, Ian L; Chapman, Karena W; De Weireld, Guy; Vaesen, Sebastian; Morris, Russell E [St Andrews

    2012-04-02

    Hydrogen sulfide is an extremely toxic gas that is also of great interest for biological applications when delivered in the correct amount and at the desired rate. Here we show that the highly porous metal-organic frameworks with the CPO-27 structure can bind the hydrogen sulfide relatively strongly, allowing the storage of the gas for at least several months. Delivered gas is biologically active in preliminary vasodilation studies of porcine arteries, and the structure of the hydrogen sulfide molecules inside the framework has been elucidated using a combination of powder X-ray diffraction and pair distribution function analysis.

  4. Strategy for chemotherapeutic delivery using a nanosized porous metal-organic framework with a central composite design

    Science.gov (United States)

    Li, Yingpeng; Li, Xiuyan; Guan, Qingxia; Zhang, Chunjing; Xu, Ting; Dong, Yujing; Bai, Xinyu; Zhang, Weiping

    2017-01-01

    Background Enhancing drug delivery is an ongoing endeavor in pharmaceutics, especially when the efficacy of chemotherapy for cancer is concerned. In this study, we prepared and evaluated nanosized HKUST-1 (nanoHKUST-1), nanosized metal-organic drug delivery framework, loaded with 5-fluorouracil (5-FU) for potential use in cancer treatment. Materials and methods NanoHKUST-1 was prepared by reacting copper (II) acetate [Cu(OAc)2] and benzene-1,3,5-tricarboxylic acid (H3BTC) with benzoic acid (C6H5COOH) at room temperature (23.7°C±2.4°C). A central composite design was used to optimize 5-FU-loaded nanoHKUST-1. Contact time, ethanol concentration, and 5-FU:material ratios were the independent variables, and the entrapment efficiency of 5-FU was the response parameter measured. Powder X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption were used to determine the morphology of nanoHKUST-1. In addition, 5-FU release studies were conducted, and the in vitro cytotoxicity was evaluated. Results Entrapment efficiency and drug loading were 9.96% and 40.22%, respectively, while the small-angle X-ray diffraction patterns confirmed a regular porous structure. The SEM and TEM images of the nanoHKUST-1 confirmed the presence of round particles (diameter: approximately 100 nm) and regular polygon arrays of mesoporous channels of approximately 2–5 nm. The half-maximal lethal concentration (LC50) of the 5-FU-loaded nanoHKUST-1 was approximately 10 µg/mL. Conclusion The results indicated that nanoHKUST-1 is a potential vector worth developing as a cancer chemotherapeutic drug delivery system. PMID:28260892

  5. Mechanical downsizing of a gadolinium(III)-based metal-organic framework for anticancer drug delivery.

    Science.gov (United States)

    Kundu, Tanay; Mitra, Shouvik; Patra, Prasun; Goswami, Arunava; Díaz Díaz, David; Banerjee, Rahul

    2014-08-11

    A Gd(III) -based porous metal-organic framework (MOF), Gd-pDBI, has been synthesized using fluorescent linker pDBI (pDBI=(1,4-bis(5-carboxy-1H-benzimidazole-2-yl)benzene)), resulting in a three-dimensional interpenetrated structure with a one-dimensional open channel (1.9×1.2 nm) filled with hydrogen-bonded water assemblies. Gd-pDBI exhibits high thermal stability, porosity, excellent water stability, along with organic-solvent and mild acid and base stability with retention of crystallinity. Gd-pDBI was transformed to the nanoscale regime (ca. 140 nm) by mechanical grinding to yield MG-Gd-pDBI with excellent water dispersibility (>90 min), maintaining its porosity and crystallinity. In vitro and in vivo studies on MG-Gd-pDBI revealed its low blood toxicity and highest drug loading (12 wt %) of anticancer drug doxorubicin in MOFs reported to date with pH-responsive cancer-cell-specific drug release.

  6. Olsalazine-Based Metal-Organic Frameworks as Biocompatible Platforms for H2 Adsorption and Drug Delivery.

    Science.gov (United States)

    Levine, Dana J; Runčevski, Tomče; Kapelewski, Matthew T; Keitz, Benjamin K; Oktawiec, Julia; Reed, Douglas A; Mason, Jarad A; Jiang, Henry Z H; Colwell, Kristen A; Legendre, Christina M; FitzGerald, Stephen A; Long, Jeffrey R

    2016-08-17

    The drug olsalazine (H4olz) was employed as a ligand to synthesize a new series of mesoporous metal-organic frameworks that are expanded analogues of the well-known M2(dobdc) materials (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate; M-MOF-74). The M2(olz) frameworks (M = Mg, Fe, Co, Ni, and Zn) exhibit high surface areas with large hexagonal pore apertures that are approximately 27 Å in diameter. Variable temperature H2 adsorption isotherms revealed strong adsorption at the open metal sites, and in situ infrared spectroscopy experiments on Mg2(olz) and Ni2(olz) were used to determine site-specific H2 binding enthalpies. In addition to its capabilities for gas sorption, the highly biocompatible Mg2(olz) framework was also evaluated as a platform for the delivery of olsalazine and other encapsulated therapeutics. The Mg2(olz) material (86 wt % olsalazine) was shown to release the therapeutic linker through dissolution of the framework under simulated physiological conditions. Furthermore, Mg2(olz) was used to encapsulate phenethylamine (PEA), a model drug for a broad class of bioactive compounds. Under simulated physiological conditions, Mg2(olz)(PEA)2 disassembled to release PEA from the pores and olsalazine from the framework itself, demonstrating that multiple therapeutic components can be delivered together at different rates. The low toxicity, high surface areas, and coordinatively unsaturated metal sites make these M2(olz) materials promising for a range of potential applications, including drug delivery in the treatment of gastrointestinal diseases.

  7. Strategy for chemotherapeutic delivery using a nanosized porous metal-organic framework with a central composite design

    Directory of Open Access Journals (Sweden)

    Li YP

    2017-02-01

    Full Text Available Yingpeng Li,1 Xiuyan Li,2 Qingxia Guan,2 Chunjing Zhang,2 Ting Xu,2 Yujing Dong,2 Xinyu Bai,2 Weiping Zhang3 1College of Pharmacy, Tianjin University of Traditional Chinese Medicine, Tianjin, 2College of Pharmacy, Heilongjiang University of Traditional Chinese Medicine, Harbin, People’s Republic of China; 3Pope John XXIII High School, Everett, MA, USA Background: Enhancing drug delivery is an ongoing endeavor in pharmaceutics, especially when the efficacy of chemotherapy for cancer is concerned. In this study, we prepared and evaluated nanosized HKUST-1 (nanoHKUST-1, nanosized metal-organic drug delivery framework, loaded with 5-fluorouracil (5-FU for potential use in cancer treatment.Materials and methods: NanoHKUST-1 was prepared by reacting copper (II acetate [Cu(OAc2] and benzene-1,3,5-tricarboxylic acid (H3BTC with benzoic acid (C6H5COOH at room temperature (23.7°C±2.4°C. A central composite design was used to optimize 5-FU-loaded nanoHKUST-1. Contact time, ethanol concentration, and 5-FU:material ratios were the independent variables, and the entrapment efficiency of 5-FU was the response parameter measured. Powder X-ray diffraction, scanning electron microscopy (SEM, transmission electron microscopy (TEM, and nitrogen adsorption were used to determine the morphology of nanoHKUST-1. In addition, 5-FU release studies were conducted, and the in vitro cytotoxicity was evaluated.Results: Entrapment efficiency and drug loading were 9.96% and 40.22%, respectively, while the small-angle X-ray diffraction patterns confirmed a regular porous structure. The SEM and TEM images of the nanoHKUST-1 confirmed the presence of round particles (diameter: approximately 100 nm and regular polygon arrays of mesoporous channels of approximately 2–5 nm. The half-maximal lethal concentration (LC50 of the 5-FU-loaded nanoHKUST-1 was approximately 10 µg/mL.Conclusion: The results indicated that nanoHKUST-1 is a potential vector worth developing as a

  8. Pneumatically Modulated Liquid Delivery System for Nebulizers

    Science.gov (United States)

    2011-12-02

    spectrometry (OES). Nebulizers generate a fine aerosol, or mist, of liquid droplets that are subsequently vaporized. The aerosol is generated by...Elemental Scientific, Omaha, NE USA) at 30 μL min-1 liquid flow and 1000 mL min-1 gas flow. The small droplets of the aerosol are clearly visible. Gas...PMLDS can easily be extended to microfluidic applications and nanoliter per minute to milliliter per minute flow rate ranges. The PMLDS is a flexible

  9. Observing the Growth of Metal-Organic Frameworks by In-Situ Liquid Cell Transmission Electron Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Patterson, Joseph P.; Abellan Baeza, Patricia; Denny, Michael S.; Park, Chiwoo; Browning, Nigel D.; Cohen, Seth M.; Evans, James E.; Gianneschi, Nathan C.

    2015-06-17

    Liquid Cell Transmission Electron Microscopy (LCTEM) can provide direct observations of solution phase nanoscale materials, and holds great promise as a tool for monitoring dynamic self assembly processes. Control over particle behavior within the liquid cell, and under electron beam irradiation, is of paramount importance for this technique to contribute to our understanding of chemistry and materials science at the nanoscale. However, this type of control has not been demonstrated for complex, organic macromolecular materials, which form the basis for all biological systems, all of polymer science, and encompass important classes of advanced porous materials. Here we show that by controlling the liquid cell surface chemistry and electron beam effects, the dynamics and self-assembly of metal-organic frameworks (MOFs) can be observed. Our results demonstrate that hybrid organic/inorganic beam sensitive materials can be analyzed with LCTEM and at least in the case of Zif-8 dynamics, the results correlate with observations from bulk growth or other standard synthetic conditions. We anticipate that direct, nanoscale imaging by LCTEM of MOF nucleation and growth mechanisms, may provide insight into controlled MOF crystal morphology, domain composition, and processes influencing defect formation.

  10. Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction of herbicides in peanuts.

    Science.gov (United States)

    Li, Na; Wang, Zhibing; Zhang, Liyuan; Nian, Li; Lei, Lei; Yang, Xiao; Zhang, Hanqi; Yu, Aimin

    2014-10-01

    Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction was developed and applied to the extraction of pesticides in high fatty matrices. The herbicides were ultrasonically extracted from peanut using ethyl acetate as extraction solvent. The separation of the analytes from a large amount of co-extractive fat was achieved by dispersive solid-phase extraction using MIL-101(Cr) as sorbent. In this step, the analytes were adsorbed on MIL-101(Cr) and the fat remained in bulk. The herbicides were separated and determined by high-performance liquid chromatography. The experimental parameters, including type and volume of extraction solvent, ultrasonication time, volume of hexane and eluting solvent, amount of MIL-101(Cr) and dispersive solid phase extraction time, were optimized. The limits of detection for herbicides range from 0.98 to 1.9 μg/kg. The recoveries of the herbicides are in the range of 89.5-102.7% and relative standard deviations are equal or lower than 7.0%. The proposed method is simple, effective and suitable for treatment of the samples containing high content of fat.

  11. Simple and reusable picoinjector for liquid delivery via nanofluidics approach

    KAUST Repository

    Li, Shunbo

    2014-03-25

    Precise control of sample volume is one of the most important functions in lab-on-a-chip (LOC) systems, especially for chemical and biological reactions. The common approach used for liquid delivery involves the employment of capillaries and microstructures for generating a droplet which has a volume in the nanoliter or picoliter range. Here, we report a novel approach for constructing a picoinjector which is based on well-controlled electroosmotic (EO) flow to electrokinetically drive sample solutions. This picoinjector comprises an array of interconnected nanochannels for liquid delivery. Such technique for liquid delivery has the advantages of well-controlled sample volume and reusable nanofluidic chip, and it was reported for the first time. In the study of the pumping process for this picoinjector, the EO flow rate was determined by the intensity of the fluorescent probe. The influence of ion concentration in electrolyte solutions over the EO flow rate was also investigated and discussed. The application of this EO-driven picoinjector for chemical reactions was demonstrated by the reaction between Fluo-4 and calcium chloride with the reaction cycle controlled by the applied square waves of different duty cycles. The precision of our device can reach down to picoliter per second, which is much smaller than that of most existing technologies. This new approach, thus, opens further possibilities of adopting nanofluidics for well-controlled chemical reactions with particular applications in nanoparticle synthesis, bimolecular synthesis, drug delivery, and diagnostic testing.

  12. Bicontinuous cubic liquid crystalline nanoparticles for oral delivery of Doxorubicin

    DEFF Research Database (Denmark)

    Swarnakar, Nitin K; Thanki, Kaushik; Jain, Sanyog

    2014-01-01

    PURPOSE: The present study explores the potential of bicontinous cubic liquid crystalline nanoparticles (LCNPs) for improving therapeutic potential of doxorubicin. METHODS: Phytantriol based Dox-LCNPs were prepared using hydrotrope method, optimized for various formulation components, process...... variables and lyophilized. Structural elucidation of the reconstituted formulation was performed using HR-TEM and SAXS analysis. The developed formulation was subjected to exhaustive cell culture experiments for delivery potential (Caco-2 cells) and efficacy (MCF-7 cells). Finally, in vivo pharmacokinetics...

  13. Shadowing and mask opening effects during selective-area vapor-liquid-solid growth of InP nanowires by metalorganic molecular beam epitaxy.

    Science.gov (United States)

    Kelrich, A; Calahorra, Y; Greenberg, Y; Gavrilov, A; Cohen, S; Ritter, D

    2013-11-29

    Indium phosphide nanowires were grown by metalorganic molecular beam epitaxy using the selective-area vapor-liquid-solid method. We show experimentally and theoretically that the size of the annular opening around the nanowire has a major impact on nanowire growth rate. In addition, we observed a considerable reduction of the growth rate in dense two-dimensional arrays, in agreement with a calculation of the shadowing of the scattered precursors. Due to the impact of these effects on growth, they should be considered during selective-area vapor-liquid-solid nanowire epitaxy.

  14. Single liquid-source plasma enhanced metalorganic chemical vapor deposition of YBa sub 2 Cu sub 3 O sub 7-x thin films. Technical report

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, J.; Gardiner, R.; Kirlin, P.S.; Boerstler, R.W.; Steinbeck, J.

    1992-07-29

    High quality YBa2Cu3O7-x films were grown in-situ on LaAlO3 (100) by a novel single liquid source plasma-enhanced metalorganic chemical vapor deposition process. The metalorganic complexes M(thd)n, (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate; M = Y, Ba, Cu) were dissolved in an organic solution and injected into a vaporizer immediately upstream of the reactor inlet The single liquid source technique dramatically simplifies current CVD processing and can significantly improve the process reproducibility. X-ray diffraction. measurements indicated that single phase, highly c-axis oriented YBa2Cu3O7-x was formed in-situ at a substrate temperature 680 degC. The as-deposited films exhibited a mirror-like surface, had transition temperature Tc = 89 K, Delta Tc < 1K, and Jc(77K) = 106 A/cm2. Plasma enhanced metalorganic chemical vapor deposition, YBCO, superconductors.

  15. Characterization of Pb(Zr, Ti)O sub 3 thin films prepared by metal-organic chemical-vapor deposition using a solid delivery system

    CERN Document Server

    Shin, J C; Hwang, C S; Kim, H J; Lee, J M

    1999-01-01

    Pb(Zr, Ti)O sub 3 (PZT) thin films were deposited on Pt/SiO sub 2 /Si substrates by metal-organic chemical-vapor deposition technique using a solid delivery system to improve the reproducibility of the deposition. The self-regulation mechanism, controlling the Pb-content of the film, was observed to work above a substrate temperature of 620 .deg. C. Even with the self-regulation mechanism, PZT films having low leakage current were obtained only when the molar mixing ratio of the input precursors was 1

  16. A simple and powerful co-delivery system based on pH-responsive metal-organic frameworks for enhanced cancer immunotherapy.

    Science.gov (United States)

    Duan, Fei; Feng, Xiaochen; Yang, Xinjian; Sun, Wentong; Jin, Yi; Liu, Huifang; Ge, Kun; Li, Zhenhua; Zhang, Jinchao

    2017-04-01

    Tumor-associated antigens (TAAs)-loaded nanoparticles are able to be actively internalized by antigen-presenting cells (APCs) and have shown promising potential in cancer immunotherapy. However, current TAAs delivery strategy exhibits limitations of complicated synthesis process, low loading efficiency and inefficient CD8(+) cytotoxic T lymphocyte activation leading to unsatisfactory therapeutic effect. Thus, the construction of novel TAAs-delivery systems for enhanced cancer therapy is highly desirable. In this work, we fabricated a very simple yet powerful antigens-delivery system for cancer immunotherapy based-on pH-responsive metal-organic frameworks (MOFs) with size about 30 nm. TAAs can be loaded into MOFs in the one-pot synthesis process and released with the degradation of MOFs in the acidic environment of endo/lysosome as the result of relatively labile metal-ligand bonds. The endosomolytic nanoparticles would facilitate protein antigens escape from endo/lysosome and optimal for enhancing antigen cross-presentation. Furthermore, the introduction of immunostimulatory unmethylated cytosine-phosphate-guanine oligonucleotide (CpG) through Watson-Crick base pairing would further enhance CD8(+) cytotoxic T lymphocyte responses. We demonstrated that the method to co-delivery antigens and immunostimulatory molecules was very simple, convenient and effective and showed no obvious toxicity both in vitro and in vivo. This method gave a high antigens-loading capacity and the maximal antigen encapsulating efficiency was about 55% (w/w). Additionally, the pH-responsive co-delivery system exerted enhanced antitumor outcome (about 100% survival) in B16-OVA melanoma cancers in vivo. Furthermore, we confirmed that this high rating of therapeutic effect was attributed to the recruitment of tumor-killing immunocyte. This work demonstrates the ability of pH-responsive, endosomolytic MOFs to induce strong cellular immune responses for cancer therapy by co-delivery of CpG ODN

  17. Recent advances in porous nanoparticles for drug delivery in antitumoral applications: inorganic nanoparticles and nanoscale metal-organic frameworks.

    Science.gov (United States)

    Baeza, Alejandro; Ruiz-Molina, Daniel; Vallet-Regí, María

    2017-06-01

    Nanotechnology has provided new tools for addressing unmet clinical situations, especially in the oncology field. The development of smart nanocarriers able to deliver chemotherapeutic agents specifically to the diseased cells and to release them in a controlled way has offered a paramount advantage over conventional therapy. Areas covered: Among the different types of nanoparticle that can be employed for this purpose, inorganic porous materials have received significant attention in the last decade due to their unique properties such as high loading capacity, chemical and physical robustness, low toxicity and easy and cheap production in the laboratory. This review discuss the recent advances performed in the application of porous inorganic and metal-organic materials for antitumoral therapy, paying special attention to the application of mesoporous silica, porous silicon and metal-organic nanoparticles. Expert opinion: The use of porous inorganic nanoparticles as drug carriers for cancer therapy has the potential to improve the life expectancy of the patients affected by this disease. However, much work is needed to overcome their drawbacks, which are aggravated by their hard nature, exploiting the advantages offered by highly the ordered pore network of these materials.

  18. Adsorptive separation on metal-organic frameworks in the liquid phase.

    Science.gov (United States)

    Van de Voorde, Ben; Bueken, Bart; Denayer, Joeri; De Vos, Dirk

    2014-08-21

    While much attention of the MOF community has been devoted to adsorption and purification of gases, there is now also a vast body of data on the capability of MOFs to separate and purify liquid mixtures. Initial studies focused on separation of petrochemicals in apolar backgrounds, but the attention has moved now to the separation of complex, e.g. chiral compounds, and to the isolation of biobased compounds from aqueous media. We here give an overview of most of the existing literature, with an accent on separation mechanisms and structure-selectivity relationships.

  19. Chitosan capped nanoscale Fe-MIL-88B-NH2 metal-organic framework as drug carrier material for the pH responsive delivery of doxorubicin

    Science.gov (United States)

    Sivakumar, P.; Priyatharshni, S.; Nagashanmugam, K. B.; Thanigaivelan, A.; Kumar, K.

    2017-08-01

    In recent years nanoscale metal-organic frameworks (NMOFs) are contributing as an effective material for use in drug delivery and imaging applications due to their porous surfaces and easy surface modifications. In this work, Fe-MIL-88B-NH2 NMOFs were successfully synthesized on facile hydrothermal route and 2-aminoterephthalic acid (NH2-BDC) was employed as a bridging ligand to activate amine functional groups on the surface. Amine functional groups not only serve as a structure stabilizing agent but also enhance the loading efficiency of the doxorubicin (DOX) anticancer drug. A pH responsive DOX release was realized by introducing a positively charged chitosan (Chi) capping layer. Upon Chi-coating, cleavage was observed in the Fe-MIL-88B-NH2 structure at acidic pH, while gel-like insoluble structure was formed at basic pH. By utilizing this phenomenon, a pH responsive DOX release system was developed by using Chi capped Fe-MIL-88B-NH2 NMOFs under the designed pH (4.0-8.0). The results suggest the Chi capped Fe-MIL-88B-NH2 can be a promising candidate for future pH responsive drug delivery systems.

  20. Single liquid source plasma-enhanced metalorganic chemical vapor deposition of high-quality YBa2Cu3O(7-x) thin films

    Science.gov (United States)

    Zhang, Jiming; Gardiner, Robin A.; Kirlin, Peter S.; Boerstler, Robert W.; Steinbeck, John

    1992-01-01

    High quality YBa2Cu3O(7-x) films were grown in-situ on LaAlO3 (100) by a novel single liquid source plasma-enhanced metalorganic chemical vapor deposition process. The metalorganic complexes M(thd) (sub n), (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate; M = Y, Ba, Cu) were dissolved in an organic solution and injected into a vaporizer immediately upstream of the reactor inlet. The single liquid source technique dramatically simplifies current CVD processing and can significantly improve the process reproducibility. X-ray diffraction measurements indicated that single phase, highly c-axis oriented YBa2Cu3O(7-x) was formed in-situ at substrate temperature 680 C. The as-deposited films exhibited a mirror-like surface, had transition temperature T(sub cO) approximately equal to 89 K, Delta T(sub c) less than 1 K, and Jc (77 K) = 10(exp 6) A/sq cm.

  1. Single liquid source plasma-enhanced metalorganic chemical vapor deposition of high-quality YBa2Cu3O(7-x) thin films

    Science.gov (United States)

    Zhang, Jiming; Gardiner, Robin A.; Kirlin, Peter S.; Boerstler, Robert W.; Steinbeck, John

    1992-01-01

    High quality YBa2Cu3O(7-x) films were grown in-situ on LaAlO3 (100) by a novel single liquid source plasma-enhanced metalorganic chemical vapor deposition process. The metalorganic complexes M(thd) (sub n), (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate; M = Y, Ba, Cu) were dissolved in an organic solution and injected into a vaporizer immediately upstream of the reactor inlet. The single liquid source technique dramatically simplifies current CVD processing and can significantly improve the process reproducibility. X-ray diffraction measurements indicated that single phase, highly c-axis oriented YBa2Cu3O(7-x) was formed in-situ at substrate temperature 680 C. The as-deposited films exhibited a mirror-like surface, had transition temperature T(sub cO) approximately equal to 89 K, Delta T(sub c) less than 1 K, and Jc (77 K) = 10(exp 6) A/sq cm.

  2. AFM fluid delivery/liquid extraction surface sampling/electrostatic spray cantilever probe

    Science.gov (United States)

    Van Berkel, Gary J.

    2015-06-23

    An electrospray system comprises a liquid extraction surface sampling probe. The probe comprises a probe body having a liquid inlet and a liquid outlet, and having a liquid extraction tip. A solvent delivery conduit is provided for receiving solvent liquid from the liquid inlet and delivering the solvent liquid to the liquid extraction tip. An open liquid extraction channel extends across an exterior surface of the probe body from the liquid extraction tip to the liquid outlet. An electrospray emitter tip is in liquid communication with the liquid outlet of the liquid extraction surface sampling probe. A system for analyzing samples, a liquid junction surface sampling system, and a method of analyzing samples are also disclosed.

  3. Metal-organic framework supported ionic liquid membranes for CO2 capture: anion effects.

    Science.gov (United States)

    Gupta, Krishna M; Chen, Yifei; Hu, Zhongqiao; Jiang, Jianwen

    2012-04-28

    IRMOF-1 supported ionic liquid (IL) membranes are investigated for CO(2) capture by atomistic simulation. The ILs consist of identical cation 1-n-butyl-3-methylimidazolium [BMIM](+), but four different anions, namely hexafluorophosphate [PF(6)](-), tetrafluoroborate [BF(4)](-), bis(trifluoromethylsulfonyl)imide [Tf(2)N](-), and thiocyanate [SCN](-). As compared with the cation, the anion has a stronger interaction with IRMOF-1 and a more ordered structure in IRMOF-1. The small anions [PF(6)](-), [BF(4)](-), and [SCN](-) prefer to locate near to the metal-cluster, particularly the quasi-spherical [PF(6)](-) and [BF(4)](-). In contrast, the bulky and chain-like [BMIM](+) and [Tf(2)N](-) reside near the phenyl ring. Among the four anions, [Tf(2)N](-) has the weakest interaction with IRMOF-1 and thus the strongest interaction with [BMIM](+). With increasing the weight ratio of IL to IRMOF-1 (W(IL/IRMOF-1)), the selectivity of CO(2)/N(2) at infinite dilution is enhanced. At a given W(IL/IRMOF-1), the selectivity increases as [Tf(2)N](-) membrane with W(IL/IRMOF-1) = 1, [SCN](-) is identified to be the most favorable site for CO(2) adsorption. [BMIM][SCN]/IRMOF-1 outperforms polymer membranes and polymer-supported ILs in CO(2) permeability, and its performance surpasses Robeson's upper bound. This simulation study reveals that the anion has strong effects on the microscopic properties of ILs and suggests that MOF-supported ILs are potentially intriguing for CO(2) capture.

  4. In situ solvothermal growth of metal-organic framework-ionic liquid functionalized graphene nanocomposite for highly efficient enrichment of chloramphenicol and thiamphenicol.

    Science.gov (United States)

    Wu, Mian; Ai, Youhong; Zeng, Baizhao; Zhao, Faqiong

    2016-01-04

    Here we report a facile in situ solvothermal growth method for immobilization of metal-organic framework-ionic liquid functionalized graphene (MOF-5/ILG) composite on etched stainless steel wire. The X-ray diffraction spectra, scanning electron microscopy and transmission electron microscopy images showed that the metal organic framework possessed good crystal shape and its structure was not disturbed by the introduction of ILG. Moreover, the covalent bond established between the amino group of ILG and the carboxylic group of the metal organic framework improved the mechanical stability and structure uniformity of the microcrystals. The obtained material combined the favorable attributes of both metal-organic framework and ILG, having high surface area (820 m(2)/g) and good adsorption capability. Its adsorption properties were explored by preconcentrating chloramphenicol and thiamphenicol from aqueous solutions prior to gas chromatography-flame ionization detection. The MOF-5/ILG exhibited high enrichment capacity for the analytes as they could interact through π-π and H-bonding interaction. Under the optimum conditions, good linearity (correlation coefficients higher than 0.9981), low limits of detection (14.8-19.5 ng/L), and good precision (relative standard deviations less than 6.0% (n=5)) were achieved. The MOF-5/ILG composite displayed durable property. The method was applied to the determination of two antibiotics in milk, honey, urine and serum samples with acceptable relative recoveries of 82.3-103.2%.

  5. Deposition of Metal-Organic Frameworks by Liquid-Phase Epitaxy: The Influence of Substrate Functional Group Density on Film Orientation

    Science.gov (United States)

    Liu, Jinxuan; Shekhah, Osama; Stammer, Xia; Arslan, Hasan K.; Liu, Bo; Schüpbach, Björn; Terfort, Andreas; Wöll, Christof

    2012-01-01

    The liquid phase epitaxy (LPE) of the metal-organic framework (MOF) HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs) on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA), 4’-carboxyterphenyl-4-methanethiol (TPMTA) and 9-carboxy-10-(mercaptomethyl)triptycene (CMMT). The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100) direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111) direction.

  6. Deposition of Metal-Organic Frameworks by Liquid-Phase Epitaxy: The Influence of Substrate Functional Group Density on Film Orientation

    Directory of Open Access Journals (Sweden)

    Christof Wöll

    2012-09-01

    Full Text Available The liquid phase epitaxy (LPE of the metal-organic framework (MOF HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA, 4’-carboxyterphenyl-4-methanethiol (TPMTA and 9-carboxy-10-(mercaptomethyltriptycene (CMMT. The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100 direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111 direction.

  7. Deposition of metal-organic frameworks by liquid-phase epitaxy: The influence of substrate functional group density on film orientation

    KAUST Repository

    Liu, J.

    2012-09-05

    The liquid phase epitaxy (LPE) of the metal-organic framework (MOF) HKUST-1 has been studied for three different COOH-terminated templating organic surfaces prepared by the adsorption of self-assembled monolayers (SAMs) on gold substrates. Three different SAMs were used, mercaptohexadecanoic acid (MHDA), 4\\'-carboxyterphenyl-4-methanethiol (TPMTA) and 9-carboxy-10-(mercaptomethyl)triptycene (CMMT). The XRD data demonstrate that highly oriented HKUST-1 SURMOFs with an orientation along the (100) direction was obtained on MHDA-SAMs. In the case of the TPMTA-SAM, the quality of the deposited SURMOF films was found to be substantially inferior. Surprisingly, for the CMMT-SAMs, a different growth direction was obtained; XRD data reveal the deposition of highly oriented HKUST-1 SURMOFs grown along the (111) direction.

  8. Effect of Microstructure and Wettability on Liquid Delivery in Structured Surfaces

    Science.gov (United States)

    Zong, Diyuan; Rokoni, Arif; Duan, Yuanyuan; Sun, Ying

    2016-11-01

    Liquid delivery rate in structured surfaces contributes greatly to the enhancement in critical heat flux during boiling and thin film evaporation. In the present study, the effect of microstructure and wettability on the liquid delivery rate has been investigated using molecular dynamics (MD) simulations for droplet spreading on nanostructured surfaces and liquid infiltration in nanopores. The wicked volume flux, a measure of the liquid delivery rate during droplet spreading, is found to increase with Wenzel roughness ratio regardless of the microstructure and this finding is supported by existing experiments. In addition, the effects of long-range intermolecular interactions and external electric field on liquid delivery rate are investigated. Long-range intermolecular interaction has been found to have negligible effect on liquid delivery rate. Both the wicking length in droplet spreading and the infiltration length of liquid infiltration in nanopores scale with t (1 / 2) , consistent with the classic theory. The effects of the nanostructure depth, width-to-spacing ratio, wettability, and external electric field on the wicking coefficient have been studied and the results can be used to guide structured surface designs for enhanced liquid delivery.

  9. A novel liquid effervescent floating delivery system for sustained drug delivery.

    Science.gov (United States)

    Ibrahim, H K

    2009-08-01

    An effervescent floating liquid formulation with in situ gelling properties has been assessed for its potential for sustaining drug delivery and targeting. The formulation consisted of sodium alginate and glyceryl monooleate (GMO). The developed formulation met all pre-requisites to become an in situ gelling floating system and it gelled and floated instantaneously in the pH conditions of the stomach. Moreover, the gels formed in situ remained intact for more than 48 h to facilitate sustained release of drugs. Increasing the mannuronic acid ratio of sodium alginate and the GMO concentration significantly retarded the release rate and extent. The in vitro release of both hydrophilic and hydrophobic drugs from the prepared formulations followed root-time kinetics during the sustained release period. Replacing the free drug with drug encapsulated microspheres enabled tailoring of the release profile and achieved zero-order release kinetics. The system retained its appearance and rheological properties for 12 months at ambient conditions. The values of the similarity factor Sd proved the absence of any significant difference in the release profile upon storage.

  10. 49 CFR 174.204 - Tank car delivery of gases, including cryogenic liquids.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Tank car delivery of gases, including cryogenic..., including cryogenic liquids. (a) A tank car containing Class 2 (gases) material may not be unloaded unless... Division 2.1 (flammable gas) material that is a cryogenic liquid; or (ii) A tank car, except for a DOT-106A...

  11. 76 FR 25696 - Guidance for Industry on Dosage Delivery Devices for Orally Ingested OTC Liquid Drug Products...

    Science.gov (United States)

    2011-05-05

    ... HUMAN SERVICES Food and Drug Administration Guidance for Industry on Dosage Delivery Devices for Orally... entitled ``Dosage Delivery Devices for Orally Ingested OTC Liquid Drug Products.'' This document is... over-the-counter (OTC) liquid drug products packaged with dosage delivery devices (e.g.,...

  12. Liquid-phase oxidation of alkylaromatics to aromatic ketones with molecular oxygen over a Mn-based metal-organic framework.

    Science.gov (United States)

    Kuwahara, Yasutaka; Yoshimura, Yukihiro; Yamashita, Hiromi

    2017-07-04

    Liquid-phase oxidation of alkylaromatics with molecular O2 was examined using a microporous Mn-based metal-organic framework (Mn-MOF-74). Mn-MOF-74 consisting of trimeric Mn clusters and 2,5-dihydroxyterephthalate (dhtp) linkers exhibits superior catalytic activity with good ketone selectivity compared to conventional oxide-supported Mn catalysts without showing any lengthy induction period. Combined analyses by means of XRD, FE-SEM, N2 physisorption and Mn K-edge XAFS reveal that the superior catalytic performance is attributed to the inherently-formed Mn(iii)2(dhtp) moieties embedded in the Mn-MOF-74 framework rather than structural factors associated with the MOF. The catalyst is reusable over multiple catalytic runs along with retaining its original catalytic activity due to the ability of the dhtp ligand to stabilize active Mn(iii) atoms. Owing to high activity, reusability and nontoxicity, Mn-MOF-74 can offer a simple, inexpensive and efficient protocol for the oxidation of some important alkylaromatics, such as ethylbenzene and diphenylmethane to produce the corresponding aromatic ketones.

  13. Monolithic metal-organic framework MIL-53(Al)-polymethacrylate composite column for the reversed-phase capillary liquid chromatography separation of small aromatics.

    Science.gov (United States)

    Yusuf, Kareem; Badjah-Hadj-Ahmed, Ahmed Yacine; Aqel, Ahmad; ALOthman, Zeid Abdullah

    2016-03-01

    A monolithic capillary column containing a composite of metal-organic framework MIL-53(Al) incorporated into hexyl methacrylate-co-ethylene dimethacrylate was prepared to enhance the separation of mixtures of small aromatic compounds by using capillary liquid chromatography. The addition of 10 mg/mL MIL-53(Al) microparticles increased the micropore content in the monolithic matrix and increased the Brunauer-Emmett-Teller surface area from 26.92 to 85.12 m(2) /g. The presence of 1,4-benzenedicarboxylate moieties within the structure of MIL-53(Al) as an organic linker greatly influenced the separation of aromatic mixtures through π-π interactions. High-resolution separation was obtained for a series of alkylbenzenes (with resolution factors in the range 0.96-1.75) in less than 8 min, with 14 710 plates/m efficiency for propylbenzene, using a binary polar mobile phase of water/acetonitrile in isocratic mode. A reversed-phase separation mechanism was indicated by the increased retention factor and resolution as the water percentage in the mobile phase increased. A stability study on the composite column showed excellent mechanical stability under various conditions. The higher resolution and faster separation observed at increased temperature indicated an exothermic separation, whereas the negative values for the free energy change of transfer indicated a spontaneous process.

  14. Oriented circular dichroism analysis of chiral surface-anchored metal-organic frameworks grown by liquid-phase epitaxy and upon loading with chiral guest compounds

    KAUST Repository

    Gu, Zhigang

    2014-06-17

    Oriented circular dichroism (OCD) is explored and successfully applied to investigate chiral surface-anchored metal-organic frameworks (SURMOFs) based on camphoric acid (D- and Lcam) with the composition [Cu2(Dcam) 2x(Lcam)2-2x(dabco)]n (dabco=1,4-diazabicyclo- [2.2.2]-octane). The three-dimensional chiral SURMOFs with high-quality orientation were grown on quartz glass plates by using a layer-by-layer liquid-phase epitaxy method. The growth orientation, as determined by X-ray diffraction (XRD), could be switched between the [001] and [110] direction by using either OH- or COOH-terminated substrates. These SURMOFs were characterized by using OCD, which confirmed the ratio as well as the orientation of the enantiomeric linker molecules. Theoretical computations demonstrate that the OCD band intensities of the enantiopure [Cu2(Dcam)2(dabco)] n grown in different orientations are a direct result of the anisotropic nature of the chiral SURMOFs. Finally, the enantiopure [Cu 2(Dcam)2(dabco)]n and [Cu2(Lcam) 2(dabco)]n SURMOFs were loaded with the two chiral forms of ethyl lactate [(+)-ethyl-D-lactate and (-)-ethyl-L-lactate)]. An enantioselective enrichment of >60 % was observed by OCD when the chiral host scaffold was loaded from the racemic mixture. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Dielectric relaxation dynamics and AC conductivity scaling of metal-organic framework (MOF-5) based polymer electrolyte nanocomposites incorporated with ionic liquid

    Science.gov (United States)

    Dutta, Rituraj; Kumar, A.

    2017-10-01

    Dielectric relaxation dynamics and AC conductivity scaling of a metal-organic framework (MOF-5) based poly (vinylidene fluoride-co-hexafluoropropylene) (PVdf-HFP) incorporated with 1-Butyl-3-methylimidazolium hexafluorophosphate have been studied over a frequency range of 40 Hz–5 MHz and in the temperature range of 300 K–380 K. High values of dielectric permittivity (~{{\\varepsilon }\\prime} ) having strong dispersion are obtained at low frequency because of interfacial polarization. The real part of the dielectric modulus spectra (M‧) shows no prominent peak, whereas the imaginary part (M″) shows certain peaks, with a reduction in relaxation time (τ) that can be attributed to a non-Debye relaxation mechanism. The spectra also depict both concentration- and temperature-independent scaling behavior. The power law dependent variation of AC conductivity follows the jump relaxation model and reveals activated ion hopping over diffusion barriers. The value of the frequency exponent is observed to decrease with increasing concentration of ionic liquid, indicating the forward hopping of ions in the relaxation process. The AC conductivity scaling curves at different temperatures also depict the temperature-independent relaxation dynamics.

  16. Understanding the interfacial properties of nanostructured liquid crystalline materials for surface-specific delivery applications.

    Science.gov (United States)

    Dong, Yao-Da; Larson, Ian; Barnes, Timothy J; Prestidge, Clive A; Allen, Stephanie; Chen, Xinyong; Roberts, Clive J; Boyd, Ben J

    2012-09-18

    Nonlamellar liquid crystalline dispersions such as cubosomes and hexosomes have great potential as novel surface-targeted active delivery systems. In this study, the influence of internal nanostructure, chemical composition, and the presence of Pluronic F127 as a stabilizer, on the surface and interfacial properties of different liquid crystalline particles and surfaces, was investigated. The interfacial properties of the bulk liquid crystalline systems with coexisting excess water were dependent on the internal liquid crystalline nanostructure. In particular, the surfaces of the inverse cubic systems were more hydrophilic than that of the inverse hexagonal phase. The interaction between F127 and the bulk liquid crystalline systems depended on the internal liquid crystalline structure and chemical composition. For example, F127 adsorbed to the surface of the bulk phytantriol cubic phase, while for monoolein cubic phase, F127 was integrated into the liquid crystalline structure. Last, the interfacial adsorption behavior of the dispersed liquid crystalline particles also depended on both the internal nanostructure and the chemical composition, despite the dispersions all being stabilized using F127. The findings highlight the need to understand the specific surface characteristics and the nature of the interaction with colloidal stabilizer for understanding and optimizing the behavior of nonlamellar liquid crystalline systems in surface delivery applications.

  17. High performance liquid chromatography of substituted aromatics with the metal-organic framework MIL-100(Fe): Mechanism analysis and model-based prediction.

    Science.gov (United States)

    Qin, Weiwei; Silvestre, Martin Eduardo; Li, Yongli; Franzreb, Matthias

    2016-02-05

    Metal-organic framework (MOF) MIL-100(Fe) with well-defined thickness was homogenously coated onto the outer surface of magnetic microparticles via a liquid-phase epitaxy method. The as-synthesized MIL-100(Fe) was used as stationary phase for high-performance liquid chromatography (HPLC) and separations of two groups of mixed aromatic hydrocarbons (toluene, styrene and p-xylene; acetanilide, 2-nirtoaniline and 1-naphthylamine) using methanol/water as mobile phase were performed to evaluate its performance. Increasing water content of the mobile phase composition can greatly improve the separations on the expense of a longer elution time. Stepwise elution significantly shortens the elution time of acetanilide, 2-nirtoaniline and 1-naphthylamine mixtures, while still achieving a baseline separation. Combining the experimental results and in-depth modeling using a recently developed chromatographic software (ChromX), adsorption equilibrium parameters, including the affinities and maximum capacities, for each analyte toward the MIL-100(Fe) are obtained. In addition, the pore diffusivity of aromatic hydrocarbons within MIL-100(Fe) was determined to be 5×10(-12)m(2)s(-1). While the affinities of MIL-100(Fe) toward the analyte molecules differs much, the maximum capacities of the analytes are in a narrow range with q*MOFmax,toluene=3.55molL(-1), q*MOFmax,styrene or p-xylene=3.53molL(-1), and q*MOFmax,anilines=3.12molL(-1) corresponding to approximately 842 toluene and 838 styrene or p-xylene, and 740 aniline molecules per MIL-100(Fe) unit cell, respectively.

  18. Uptake of liquid alcohols by the flexible Fe(III) metal-organic framework MIL-53 observed by time-resolved in situ X-ray diffraction.

    Science.gov (United States)

    Walton, Richard I; Munn, Alexis S; Guillou, Nathalie; Millange, Franck

    2011-06-14

    A comprehensive, time-resolved, energy-dispersive X-ray diffraction study of the uptake of liquid alcohols (methanol, ethanol, propan-1-ol and propan-2-ol) by the flexible metal-organic framework solid MIL-53(Fe)[H(2)O] is reported. In the case of the primary alcohols, a fluorinated version of the MIL-53(Fe) host (C2/c symmetry V ca. 1000 Å(3)), in which a fraction of framework hydroxides are replaced by fluoride, shows uptake of alcohols to give initially a partially expanded phase (C2/c symmetry, V ca. 1200 Å(3)) followed by an expanded form of the material (either Imcm or Pnam symmetry, V ca. 1600 Å(3)). In the case of methanol-water mixtures, the EDXRD data show that the partially open intermediate phase undergoes volume expansion during its existence, before switching to a fully open structure if concentrated methanol is used; analogous behaviour is seen if the initial guest is propan-2-ol, which then is replaced by pyridine, where a continuous shift of Bragg peaks within C2/c symmetry is observed. In contrast to the partially fluorinated materials, the purely hydroxylated host materials show little tendency to stabilise partially open forms of MIL-53(Fe) with primary alcohols and the kinetics of guest introduction are markedly slower without the framework fluorination: this is exemplified by the exchange of water by propan-2-ol, where a partially open C2/c phase is formed in a step-wise manner. Our study defines the various possible pathways of liquid-phase uptake of molecular guests by flexible solid MIL-53(Fe).

  19. Oral and transdermal drug delivery systems: role of lipid-based lyotropic liquid crystals

    OpenAIRE

    Rajabalaya, Rajan; Musa,Muhammad Nuh; Kifli, Nurolaini; Sheba R. David

    2017-01-01

    Rajan Rajabalaya, Muhammad Nuh Musa, Nurolaini Kifli, Sheba R David PAPRSB Institute of Health Sciences, Universiti Brunei Darussalam, Brunei Darussalam Abstract: Liquid crystal (LC) dosage forms, particularly those using lipid-based lyotropic LCs (LLCs), have generated considerable interest as potential drug delivery systems. LCs have the physical properties of liquids but retain some of the structural characteristics of crystalline solids. They are compatible with hydrophobic and hydrophi...

  20. Liquid sample delivery techniques for serial femtosecond crystallography.

    Science.gov (United States)

    Weierstall, Uwe

    2014-07-17

    X-ray free-electron lasers overcome the problem of radiation damage in protein crystallography and allow structure determination from micro- and nanocrystals at room temperature. To ensure that consecutive X-ray pulses do not probe previously exposed crystals, the sample needs to be replaced with the X-ray repetition rate, which ranges from 120 Hz at warm linac-based free-electron lasers to 1 MHz at superconducting linacs. Liquid injectors are therefore an essential part of a serial femtosecond crystallography experiment at an X-ray free-electron laser. Here, we compare different techniques of injecting microcrystals in solution into the pulsed X-ray beam in vacuum. Sample waste due to mismatch of the liquid flow rate to the X-ray repetition rate can be addressed through various techniques.

  1. SiC coatings grown by liquid injection chemical vapor deposition using single source metal-organic precursors

    OpenAIRE

    Boisselier, Guilhaume; Maury, Francis; Schuster, Frédéric

    2013-01-01

    International audience; SiC coatings have been grown by direct liquid injection of organosilanes in a hot-wall chemical vapor depositionreactor (DLICVD). 1,3-disilabutane (DSB) and polysilaethylene (PSE) were used as single-source precursors. Amorphous and stoichiometric SiC coatings were deposited under low pressure on various substrates in the temperature range of 923–1073 K. Thickness gradients due to the temperature profiles and the precursor depletion were observed along the reactor axis...

  2. Liquid crystalline systems for transdermal delivery of celecoxib: in vitro drug release and skin permeation studies.

    Science.gov (United States)

    Estracanholli, Eder André; Praça, Fabíola Silva Garcia; Cintra, Ana Beatriz; Pierre, Maria Bernadete Riemma; Lara, Marilisa Guimarães

    2014-12-01

    Liquid crystalline systems of monoolein/water could be a promising approach for the delivery of celecoxib (CXB) to the skin because these systems can sustain drug release, improve drug penetration into the skin layers and minimize side effects. This study evaluated the potential of these systems for the delivery of CXB into the skin based on in vitro drug release and skin permeation studies. The amount of CXB that permeated into and/or was retained in the skin was assayed using an HPLC method. Polarizing light microscopy studies showed that liquid crystalline systems of monoolein/water were formed in the presence of CXB, without any changes in the mesophases. The liquid crystalline systems decreased drug release when compared to control solution. Drug release was independent of the initial water content of the systems and CXB was released from cubic phase systems, irrespective of the initial water content. The systems released the CXB following zero-order release kinetics. In vitro drug permeation studies showed that cubic phase systems allowed drug permeation and retention in the skin layers. Cubic phase systems of monoolein/water may be promising vehicles for the delivery of CXB in/through the skin because it improved CXB skin permeation compared with the control solution.

  3. Oral and transdermal drug delivery systems: role of lipid-based lyotropic liquid crystals.

    Science.gov (United States)

    Rajabalaya, Rajan; Musa, Muhammad Nuh; Kifli, Nurolaini; David, Sheba R

    2017-01-01

    Liquid crystal (LC) dosage forms, particularly those using lipid-based lyotropic LCs (LLCs), have generated considerable interest as potential drug delivery systems. LCs have the physical properties of liquids but retain some of the structural characteristics of crystalline solids. They are compatible with hydrophobic and hydrophilic compounds of many different classes and can protect even biologicals and nucleic acids from degradation. This review, focused on research conducted over the past 5 years, discusses the structural evaluation of LCs and their effects in drug formulations. The structural classification of LLCs into lamellar, hexagonal and micellar cubic phases is described. The structures of these phases are influenced by the addition of surfactants, which include a variety of nontoxic, biodegradable lipids; these also enhance drug solubility. LLC structure influences drug localization, particle size and viscosity, which, in turn, determine drug delivery properties. Through several specific examples, we describe the applications of LLCs in oral and topical drug formulations, the latter including transdermal and ocular delivery. In oral LLC formulations, micelle compositions and the resulting LLC structures can determine drug solubilization and stability as well as intestinal transport and absorption. Similarly, in topical LLC formulations, composition can influence whether the drug is retained in the skin or delivered transdermally. Owing to their enhancement of drug stability and promotion of controlled drug delivery, LLCs are becoming increasingly popular in pharmaceutical formulations.

  4. Oral and transdermal drug delivery systems: role of lipid-based lyotropic liquid crystals

    Science.gov (United States)

    Rajabalaya, Rajan; Musa, Muhammad Nuh; Kifli, Nurolaini; David, Sheba R

    2017-01-01

    Liquid crystal (LC) dosage forms, particularly those using lipid-based lyotropic LCs (LLCs), have generated considerable interest as potential drug delivery systems. LCs have the physical properties of liquids but retain some of the structural characteristics of crystalline solids. They are compatible with hydrophobic and hydrophilic compounds of many different classes and can protect even biologicals and nucleic acids from degradation. This review, focused on research conducted over the past 5 years, discusses the structural evaluation of LCs and their effects in drug formulations. The structural classification of LLCs into lamellar, hexagonal and micellar cubic phases is described. The structures of these phases are influenced by the addition of surfactants, which include a variety of nontoxic, biodegradable lipids; these also enhance drug solubility. LLC structure influences drug localization, particle size and viscosity, which, in turn, determine drug delivery properties. Through several specific examples, we describe the applications of LLCs in oral and topical drug formulations, the latter including transdermal and ocular delivery. In oral LLC formulations, micelle compositions and the resulting LLC structures can determine drug solubilization and stability as well as intestinal transport and absorption. Similarly, in topical LLC formulations, composition can influence whether the drug is retained in the skin or delivered transdermally. Owing to their enhancement of drug stability and promotion of controlled drug delivery, LLCs are becoming increasingly popular in pharmaceutical formulations. PMID:28243062

  5. Development and Evaluation of Liquid and Solid Self-Emulsifying Drug Delivery Systems for Atorvastatin

    Directory of Open Access Journals (Sweden)

    Anna Czajkowska-Kośnik

    2015-11-01

    Full Text Available The objective of this work was to design and characterize liquid and solid self-emulsifying drug delivery systems (SEDDS for poorly soluble atorvastatin. To optimize the composition of liquid atorvastatin-SEDDS, solubility tests, pseudoternary phase diagrams, emulsification studies and other in vitro examinations (thermodynamic stability, droplet size and zeta potential analysis were performed. Due to the disadvantages of liquid SEDDS (few choices for dosage forms, low stability and portability during the manufacturing process, attempts were also made to obtain solid SEDDS. Solid SEDDS were successfully obtained using the spray drying technique from two optimized liquid formulations, CF3 and OF2. Despite liquid SEDDS formulation, CF3 was characterized by lower turbidity, higher percentage transmittance and better self-emulsifying properties, and based on the in vitro dissolution study it can be concluded that better solubilization properties were exhibited by solid formulation OF2. Overall, the studies demonstrated the possibility of formulating liquid and solid SEEDS as promising carriers of atorvastatin. SEDDS, with their unique solubilization properties, provide the opportunity to deliver lipophilic drugs to the gastrointestinal tract in a solubilized state, avoiding dissolution—a restricting factor in absorption rate of BCS Class 2 drugs, including atorvastatin.

  6. A Densified Liquid Methane Delivery System for the Altair Ascent Stage

    Science.gov (United States)

    Tomsik, Thomas M.; Johnson, Wesley L.; Smudde, Todd D.; Femminineo, Mark F.; Schnell, Andrew R.

    2010-01-01

    The Altair Lunar Lander is currently carrying options for both cryogenic and hypergolic ascent stage propulsion modules. The cryogenic option uses liquid methane and liquid oxygen to propel Altair from the lunar surface back to rendezvous with the Orion command module. Recent studies have determined that the liquid methane should be densified by subcooling it to 93 K in order to prevent over-pressurization of the propellant tanks during the 210 day stay on the lunar surface. A trade study has been conducted to determine the preferred method of producing; loading, and maintaining the subcooled, densified liquid methane onboard Altair from a ground operations perspective. The trade study took into account the limitations in mass for the launch vehicle and the mobile launch platform as well as the historical reliability of various components and their thermal efficiencies. Several unique problems were encountered, namely delivering a small amount of a cryogenic propellant to a flight tank that is positioned over 350 ft above the launch pad as well as generating the desired delivery temperature of the methane at 93 K which is only 2.3 K above the methane triple point of 90.7 K. Over 20 methods of subcooled liquid methane production and delivery along with the associated system architectures were investigated to determine the best solutions to the problem. The top four cryogenic processing solutions were selected for further evaluation and detailed thermal modeling. This paper describes the results of the preliminary trade analysis of the 20 plus methane densification methods considered. The results of the detailed analysis will be briefed to the Altair Project Office and their propulsion team as well as the Ground Operations Project Office before the down-select is made between cryogenic and hypergolic ascent stages in August 2010.

  7. Development and characterization of liquid and solid self-microemulsifying drug delivery system of Tacrolimus

    Directory of Open Access Journals (Sweden)

    Hitesh K Patel

    2012-01-01

    Full Text Available Tacrolimus is an immunosuppressant agent for the prevention and treatment of graft rejection in solid organ transplantation patients. Tacrolimus is a poorly water-soluble drug. Its absorption is further limited due to the involvement of an efflux transporter P-glycoprotein and metabolism via cytochrome P450. The objective of present investigation was to develop and characterize a liquid self-microemulsifying drug delivery system (SMEDDS and a solid SMEDDS by using bioenhancer excipients like Tween 20 and Tween 80, which are known for their inhibiting action on CYP 450 and P-glycoprotein efflux pump. Solubility of Tacrolimus was determined in various vehicles, including oils, surfactants and cosolvents. Pseudoternary phase diagrams were constructed to identify the most efficient self-emulsification region. The optimized formulations were characterized by differential scanning calorimetry (DSC, X-ray diffraction (XRD and globule size analysis. The optimized liquid SMEDDS formulation contained 20% Phosal 53 MCT as oil, 60% Tween 20 as surfactant and 20% ethanol as cosolvent. Liquid SMEDDS was converted to solid SMEDDS by using Aerosil-200 and Florite-RE as inert solid adsorbents. The optimized liquid and solid SMEDDS showed higher drug release than the marketed capsule and pure API powder. For optimized liquid SMEDDS and solid SMEDDS, the globule sizes were found to be 140.9 nm and 304.6 nm, respectively. DSC and XRD results of solid SMEDDS confirmed that the drug present in the formulation was in an amorphous state. Shelf-lives for liquid SMEDDS and solid SMEDDS were found to be 1.76 and 2.27 years, respectively. The prepared liquid SMEDDS and solid SMEDDS containing bioenhancer excipients increase the in vitro dissolution rate of lipophilic Tacrolimus.

  8. Liquid crystalline systems containing Vitamin E TPGS for the controlled transdermal nicotine delivery

    Directory of Open Access Journals (Sweden)

    Lívia Neves Borgheti-Cardoso

    Full Text Available ABSTRACT Transdermal nicotine patches have been used in smoking cessation therapy, suggested for the treatment of skin disorders with eosinophilic infiltration and have been found to improve attention performance in patients with Alzheimer's disease and age-associated memory impairment. However, skin irritation with extended patch use is still a problem. The aim of this work was to develop a simple to prepare liquid crystalline system containing vitamin E TPGS that would be able to control nicotine delivery and reduce irritation and sensitization problems. The liquid crystalline phases were macroscopically characterized by visual analysis and examined microscopically under a polarized light microscope. Topical and transdermal delivery of nicotine were investigated in vitro using porcine ear skin mounted on a Franz diffusion cell. Nicotine skin permeation from the developed cubic phase followed zero-order kinetics (r = 0.993 and was significantly enhanced after 12 h when compared to the control formulation (nicotine solution (p < 0.05 (138.86 ± 20.44 and 64.91 ± 4.06 μg/cm2, respectively. Cubic phase was also able to target viable skin layers in comparison to control solution (8.18 ± 1.89 and 2.63 ± 2.51 μg/cm2, respectively. Further studies to evaluate skin sensitization and irritation are now necessary.

  9. Cubic liquid crystalline nanoparticles: optimization and evaluation for ocular delivery of tropicamide.

    Science.gov (United States)

    Verma, Purnima; Ahuja, Munish

    2016-10-01

    The purpose of this study was to investigate the potential of cubic liquid crystalline nanoparticles for ocular delivery of tropicamide. Ultrasound-assisted fragmentation of cubic liquid crystalline bulk phases resulted in cubic liquid crystalline nanoparticles employing Pluronic F127 as dispersant. The effects of process variables such as sonication time, sonication amplitude, sonication depth, and pre-mixing time on particle size and polydispersity index was investigated using central composite design. The morphology of tropicamide-loaded nanoparticles was found to be nearly cubical in shape by transmission electron microscopy observation. Further, small angle X-ray scattering experiment confirmed the presence of D and P phase cubic structures in coexistence. The optimized tropicamide-loaded cubic nanoparticles showed in vitro corneal permeation of tropicamide across isolated porcine cornea comparable to its commercial preparation, Tropicacyl®. Ocular tolerance was evaluated by Hen's egg-chorioallantoic membrane test and histological studies. The results of in vivo mydriatic response study demonstrated a remarkably higher area under mydriatic response curve (AUC0→1440 min) values of cubic nanoparticles over Tropicacyl® indicating better therapeutic value of cubic nanoparticles. Furthermore, tropicamide-loaded cubic nanoparticles exhibited prolonged mydriatic effect on rabbits as compared to commercial conventional aqueous ophthalmic solution.

  10. Pyroelectric Adaptive Nanodispenser (PYRANA) microrobot for liquid delivery on a target.

    Science.gov (United States)

    Vespini, Veronica; Coppola, Sara; Grilli, Simonetta; Paturzo, Melania; Ferraro, Pietro

    2011-09-21

    Manipulation of micro-sized objects in lab-on-a-chip and microfluidic environments is essential for different experiments and procedures ranging from chemical to biological applications and for experimental biotechnologies. For example polymeric particles, useful as targets for encapsulating or for being covered by drug vaccines, can be manipulated and controlled with the aim of releasing them to specific sites. Here we show a novel ElectroHydroDynamic tool able to control and manipulate dielectric micro-targets by a touch-less approach. This approach allows one to manipulate liquids and nano-particles simultaneously for specific delivery applications (i.e. decoration and coating). Thus a sort of EHD micro-robot is proposed. This flexible tool provides a new and powerful way to operate various tasks as demonstrated by the experiments reported here. This journal is © The Royal Society of Chemistry 2011

  11. Metal-organic frameworks constructed from d-camphor acid: bifunctional properties related to luminescence sensing and liquid-phase separation.

    Science.gov (United States)

    Wen, Lili; Xu, Xiaoyue; Lv, Kangle; Huang, Yumei; Zheng, Xiaofang; Zhou, Li; Sun, Renqiang; Li, Dongfeng

    2015-02-25

    Three metal-organic frameworks (MOFs) [M2(d-cam)2(bimb)2]n · 3.5nH2O (M = Mn for 1, Co for 2) and [Cd8(d-cam)8(bimb)4]n (3) (d-H2cam = d-camphor acid, bimb = 4,4'-bis(1-imidazolyl)biphenyl), solvothermally synthesized, exhibit structural diversity. The charming aspect of these frameworks is that compound 3 is the very first MOF-based sensor for quantitatively detecting three different types of analytes (metal ions, aromatic molecules, and pesticides). And also, both compounds 2 and 3 show rapid uptake and ready regeneration for methyl orange (MO) and can selectively bind MO over methylene blue (MB) with high MO/MB separation ratio.

  12. Personal electronics printing via tapping mode composite liquid metal ink delivery and adhesion mechanism.

    Science.gov (United States)

    Zheng, Yi; He, Zhi-Zhu; Yang, Jun; Liu, Jing

    2014-04-04

    Printed electronics is becoming increasingly important in a variety of newly emerging areas. However, restricted to the rather limited conductive inks and available printing strategies, the current electronics manufacture is usually confined to industry level. Here, we show a highly cost-effective and entirely automatic printing way towards personal electronics making, through introducing a tapping-mode composite fluid delivery system. Fundamental mechanisms regarding the reliable printing, transfer and adhesion of the liquid metal inks on the substrate were disclosed through systematic theoretical interpretation and experimental measurements. With this liquid metal printer, a series of representative electronic patterns spanning from single wires to desired complex configurations such as integrated circuit (IC), printed-circuits-on-board (PCB), electronic paintings, or more do-it-yourself (DIY) devices, were demonstrated to be printed out with high precision in a moment. And the total machine cost already reached personally affordable price. This is hard to achieve by a conventional PCB technology which generally takes long time and is material, water and energy consuming, while the existing printed electronics is still far away from the real direct printing goal. The present work opens the way for large scale personal electronics manufacture and is expected to generate important value for the coming society.

  13. Personal electronics printing via tapping mode composite liquid metal ink delivery and adhesion mechanism

    Science.gov (United States)

    Zheng, Yi; He, Zhi-Zhu; Yang, Jun; Liu, Jing

    2014-04-01

    Printed electronics is becoming increasingly important in a variety of newly emerging areas. However, restricted to the rather limited conductive inks and available printing strategies, the current electronics manufacture is usually confined to industry level. Here, we show a highly cost-effective and entirely automatic printing way towards personal electronics making, through introducing a tapping-mode composite fluid delivery system. Fundamental mechanisms regarding the reliable printing, transfer and adhesion of the liquid metal inks on the substrate were disclosed through systematic theoretical interpretation and experimental measurements. With this liquid metal printer, a series of representative electronic patterns spanning from single wires to desired complex configurations such as integrated circuit (IC), printed-circuits-on-board (PCB), electronic paintings, or more do-it-yourself (DIY) devices, were demonstrated to be printed out with high precision in a moment. And the total machine cost already reached personally affordable price. This is hard to achieve by a conventional PCB technology which generally takes long time and is material, water and energy consuming, while the existing printed electronics is still far away from the real direct printing goal. The present work opens the way for large scale personal electronics manufacture and is expected to generate important value for the coming society.

  14. Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

    OpenAIRE

    Friščić, Tomislav; Halasz, Ivan; Štrukil, Vjekoslav; Maksić, Mirjana; Dinnebier, Robert E

    2012-01-01

    This review briefly discusses recent advances and future prospects in the mechanochemical synthesis of coordination compounds by ball milling and grinding, and highlights our contributions to the mechanosynthesis of porous metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs), metal-organic pharmaceutical derivatives and metallodrugs using the recently developed mechanochemical methods of liquid-assisted grinding (LAG) and ion- and liquid-assisted grinding (ILAG). The...

  15. Multilayer-Coated Liquid Crystalline Nanoparticles for Effective Sorafenib Delivery to Hepatocellular Carcinoma.

    Science.gov (United States)

    Thapa, Raj Kumar; Choi, Ju Yeon; Poudel, Bijay K; Hiep, Tran Tuan; Pathak, Shiva; Gupta, Biki; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

    2015-09-16

    Hepatocellular carcinoma is one of the most common cancers in adults and develops due to activation of oncogenes and inactivation of tumor suppressor genes. Sorafenib (SF) is a U.S. Food and Drug Administration (FDA) approved drug for the treatment of hepatocellular carcinoma. However, its clinical use is limited by its poor aqueous solubility and undesirable side effects. Monoolein-based liquid crystalline nanoparticles (LCN) are self-assembled structures that have been determined as promising drug-delivery vehicles. Therefore, the main aim of this study was to prepare layer-by-layer (LbL) polymer-assembled SF-loaded LCNs (LbL-LCN/SF) for effective delivery of SF to hepatocellular carcinoma. Results revealed that LbL-LCN/SF presented optimum particle size (∼165 nm) and polydispersity index (PDI, ∼0.14) with appropriate polymer layer assembly confirmed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Furthermore, LbL-LCN/SF effectively controlled burst release and exhibited pH-sensitive release of SF, thereby increasing drug release in the acidic microenvironment of tumor cells. Compared to free SF and bare LCN, the hemolytic activity of LbL-LCN/SF was significantly reduced (p<0.01). Interestingly, LbL-LCN/SF was more cytotoxic to HepG2 cells than the free drug was. Additionally, high cellular uptake and greater apoptotic effects of LbL-LCN/SF in HepG2 cells indicates superior antitumor effects. Therefore, LbL-LCN/SF is a potentially effective formulation for hepatocellular carcinoma.

  16. Interactions of biomacromolecules with reverse hexagonal liquid crystals: drug delivery and crystallization applications.

    Science.gov (United States)

    Libster, Dima; Aserin, Abraham; Garti, Nissim

    2011-04-15

    Recently, self-assembled lyotropic liquid crystals (LLCs) of lipids and water have attracted the attention of both scientific and applied research communities, due to their remarkable structural complexity and practical potential in diverse applications. The phase behavior of mixtures of glycerol monooleate (monoolein, GMO) was particularly well studied due to the potential utilization of these systems in drug delivery systems, food products, and encapsulation and crystallization of proteins. Among the studied lyotropic mesophases, reverse hexagonal LLC (H(II)) of monoolein/water were not widely subjected to practical applications since these were stable only at elevated temperatures. Lately, we obtained stable H(II) mesophases at room temperature by incorporating triacylglycerol (TAG) molecules into the GMO/water mixtures and explored the physical properties of these structures. The present feature article summarizes recent systematic efforts in our laboratory to utilize the H(II) mesophases for solubilization, and potential release and crystallization of biomacromolecules. Such a concept was demonstrated in the case of two therapeutic peptides-cyclosporin A (CSA) and desmopressin, as well as RALA peptide, which is a model skin penetration enhancer, and eventually a larger macromolecule-lysozyme (LSZ). In the course of the study we tried to elucidate relationships between the different levels of organization of LLCs (from the microstructural level, through mesoscale, to macroscopic level) and find feasible correlations between them. Since the structural properties of the mesophase systems are a key factor in drug release applications, we investigated the effects of these guest molecules on their conformations and the way these molecules partition within the domains of the mesophases. The examined H(II) mesophases exhibited great potential as transdermal delivery vehicles for bioactive peptides, enabling tuning the release properties according to their chemical

  17. Macroscopically Oriented Porous Materials with Periodic Ordered Structures: From Zeolites and Metal-Organic Frameworks to Liquid-Crystal-Templated Mesoporous Materials.

    Science.gov (United States)

    Cho, Joonil; Ishida, Yasuhiro

    2017-07-01

    Porous materials with molecular-sized periodic structures, as exemplified by zeolites, metal-organic frameworks, or mesoporous silica, have attracted increasing attention due to their range of applications in storage, sensing, separation, and transformation of small molecules. Although the components of such porous materials have a tendency to pack in unidirectionally oriented periodic structures, such ideal types of packing cannot continue indefinitely, generally ceasing when they reach a micrometer scale. Consequently, most porous materials are composed of multiple randomly oriented domains, and overall behave as isotropic materials from a macroscopic viewpoint. However, if their channels could be unidirectionally oriented over a macroscopic scale, the resultant porous materials might serve as powerful tools for manipulating molecules. Guest molecules captured in macroscopically oriented channels would have their positions and directions well-defined, so that molecular events in the channels would proceed in a highly controlled manner. To realize such an ideal situation, numerous efforts have been made to develop various porous materials with macroscopically oriented channels. An overview of recent studies on the synthesis, properties, and applications of macroscopically oriented porous materials is presented. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Perfluorochemical Liquid-Adenovirus Suspensions Enhance Gene Delivery to the Distal Lung

    Directory of Open Access Journals (Sweden)

    Jeffrey A. Kazzaz

    2011-01-01

    Full Text Available We compared lung delivery methods of recombinant adenovirus (rAd: (1 rAd suspended in saline, (2 rAd suspended in saline followed by a pulse-chase of a perfluorochemical (PFC liquid mixture, and (3 a PFC-rAd suspension. Cell uptake, distribution, and temporal expression of rAd were examined using A549 cells, a murine model using luciferase bioluminescence, and histological analyses. Relative to saline, a 4X increase in transduction efficiency was observed in A549 cells exposed to PFC-rAd for 2–4 h. rAd transgene expression was improved in alveolar epithelial cells, and the level and distribution of luciferase expression when delivered in PFC-rAd suspensions consistently peaked at 24 h. These results demonstrate that PFC-rAd suspensions improve distribution and enhance rAd-mediated gene expression which has important implications in improving lung function by gene therapy.

  19. Metal-organic frameworks in chromatography.

    Science.gov (United States)

    Yusuf, Kareem; Aqel, Ahmad; ALOthman, Zeid

    2014-06-27

    Metal-organic frameworks (MOFs) emerged approximately two decades ago and are the youngest class of porous materials. Despite their short existence, MOFs are finding applications in a variety of fields because of their outstanding chemical and physical properties. This review article focuses on the applications of MOFs in chromatography, including high-performance liquid chromatography (HPLC), gas chromatography (GC), and other chromatographic techniques. The use of MOFs in chromatography has already had a significant impact; however, the utilisation of MOFs in chromatography is still less common than other applications, and the number of MOF materials explored in chromatography applications is limited.

  20. A magnetic-based dispersive micro-solid-phase extraction method using the metal-organic framework HKUST-1 and ultra-high-performance liquid chromatography with fluorescence detection for determining polycyclic aromatic hydrocarbons in waters and fruit tea infusions.

    Science.gov (United States)

    Rocío-Bautista, Priscilla; Pino, Verónica; Ayala, Juan H; Pasán, Jorge; Ruiz-Pérez, Catalina; Afonso, Ana M

    2016-03-04

    A hybrid material composed by the metal-organic framework (MOF) HKUST-1 and Fe3O4 magnetic nanoparticles (MNPs) has been synthetized in a quite simple manner, characterized, and used in a magnetic-assisted dispersive micro-solid-phase extraction (M-d-μSPE) method in combination with ultra-high-performance liquid chromatography (UHPLC) and fluorescence detection (FD). The application was devoted to the determination of 8 heavy polycyclic aromatic hydrocarbons (PAHs) in different aqueous samples, specifically tap water, wastewaters, and fruit tea infusion samples. The overall M-d-μSPE-UHPLC-FD method was optimized and validated. The method is characterized by: its simplicity in both the preparation of the hybrid material (simple mixing) and the magnetic-assisted approach (∼10min extraction time), the use of low sorbent amounts (20mg of HKUST-1 and 5mg of Fe3O4 MNPs), and the low organic solvent consumption in the overall M-d-μSPE-UHPLC-FD method (1.5mL of acetonitrile in the M-d-μSPE method and 2.8mL of acetonitrile in the UHPLC-FD run). The resulting method has high sensitivity, with LODs down to 0.8ngL(-1); adequate intermediate precision, with relative standard deviation values (RSD) always lower than 6.3% (being the range 5.9-9.0% in tap water for a spiked level of 45ngL(-1), 6.1-14% in wastewaters for a spiked level of 45ngL(-1), and 7.2-17% in fruit tea infusion samples for a spiked level of 45ngL(-1)); and adequate relative recoveries, with average values of 82% in tap water, and 94% and 75% in wastewater and fruit tea infusion samples, respectively, if using the proper matrix-matched calibration.

  1. Experimental characterization and modeling for the growth rate of oxide coatings from liquid solutions of metalorganic precursors by ultrasonic pulsed injection in a cold-wall low-pressure reactor

    Science.gov (United States)

    Krumdieck, Susan Pran

    Several years ago, a method for depositing ceramic coatings called the Pulsed-MOCVD system was developed by the Raj group at Cornell University in association with Dr. Harvey Berger and Sono-Tek Corporation. The process was used to produce epitaxial thin films of TiO2 on sapphire substrates under conditions of low pressure, relatively high temperature, and very low growth rate. The system came to CU-Boulder when Professor Raj moved here in 1997. It is quite a simple technique and has several advantages over typical CVD systems. The purpose of this dissertation is two-fold; (1) understand the chemical processes, thermodynamics, and kinetics of the Pulsed-MOCVD technique, and (2) determine the possible applications by studying the film structure and morphology over the entire range of deposition conditions. Polycrystalline coatings of ceramic materials were deposited on nickel in the low-pressure, cold-wall reactor from metalorganic precursors, titanium isopropoxide, and a mixture of zirconium isopropoxide and yttria isopropoxide. The process utilized pulsed liquid injection of a dilute precursor solution with atomization by ultrasonic nozzle. Thin films (less than 1mum) with fine-grained microstructure and thick coatings (up to 1mum) with columnar-microstructure were deposited on heated metal substrates by thermal decomposition of a single liquid precursor. The influence of each of the primary deposition parameters, substrate temperature, total flow rate, and precursor concentration on growth rate, conversion efficiency and morphology were investigated. The operating conditions were determined for kinetic, mass transfer, and evaporation process control regimes. Kinetic controlled deposition was found to produce equiaxed morphology while mass transfer controlled deposition produced columnar morphology. A kinetic model of the deposition process was developed and compared to data for deposition of TiO2 from Ti(OC3H7) 4 precursor. The results demonstrate that growth

  2. Floating drug delivery of a locally acting H2-antagonist: an approach using an in situ gelling liquid formulation.

    Science.gov (United States)

    Rohith, Ganapati; Sridhar, Bhimagoni Keshavamurthy; Srinatha, Anegundha

    2009-09-01

    In the present work, a gastroretentive in situ gelling liquid formulation for controlled delivery of ranitidine was formulated using sodium alginate (low, medium and high viscosity grades), calcium carbonate (source of cations) and ranitidine. Prepared formulations were evaluated for viscosity, buoyancy lag time and buoyancy duration, drug content and in vitro drug release. Formulation variables such as concentration of sodium alginate, calcium carbonate and drug significantly affected the formulation viscosity, floating behavior and in vitro drug release. Analysis of the release pattern showed that the drug release from in situ gel followed a diffusion mechanism.

  3. Synthesis of nano-bio conjugates for drug delivery systems using gas-liquid interfacial discharge plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Toshiro; Chen, Qiang; Hatakeyama, Rikizo [Tohoku University, Sendai (Japan)

    2012-03-15

    Size-controlled gold nanoparticles (AuNPs) covered with DNA are synthesized by using a pulse driven gas-liquid interfacial discharge plasma (GLIDP) to reduce an aqueous solution of chloroauric acid trihydrate with DNA. The size and the assembly of the AuNPs are found to be easily controlled by changing the DNA concentration in the aqueous solution. The synthesized AuNP-DNA conjugates are forced to be encapsulated into double-walled carbon nanotubes (DWNTs) by superimposing a positive DC voltage on the pulse voltage. The AuNP-DNA-conjugate encapsulated DWNTs can be utilized in drug delivery systems when DNA is used as a drug molecule.

  4. Development and Evaluation of Liquid and Solid Self-Emulsifying Drug Delivery Systems for Atorvastatin

    National Research Council Canada - National Science Library

    Czajkowska-Kośnik, Anna; Szekalska, Marta; Amelian, Aleksandra; Szymańska, Emilia; Winnicka, Katarzyna

    2015-01-01

    ...) for poorly soluble atorvastatin. To optimize the composition of liquid atorvastatin-SEDDS, solubility tests, pseudoternary phase diagrams, emulsification studies and other in vitro examinations...

  5. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  6. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  7. Lipid Raft-Mediated Membrane Tethering and Delivery of Hydrophobic Cargos from Liquid Crystal-Based Nanocarriers.

    Science.gov (United States)

    Nag, Okhil K; Naciri, Jawad; Oh, Eunkeu; Spillmann, Christopher M; Delehanty, James B

    2016-04-20

    A main goal of bionanotechnology and nanoparticle (NP)-mediated drug delivery (NMDD) continues to be the development of novel biomaterials that can controllably modulate the activity of the NP-associated therapeutic cargo. One of the desired subcellular locations for targeted delivery in NMDD is the plasma membrane. However, the controlled delivery of hydrophobic cargos to the membrane bilayer poses significant challenges including cargo precipitation and lack of specificity. Here, we employ a liquid crystal NP (LCNP)-based delivery system for the controlled partitioning of a model dye cargo from within the NP core into the plasma membrane bilayer. During synthesis of the NPs, the water-insoluble model dye cargo, 3,3'-dioctadecyloxacarbocyanine perchlorate (DiO), was efficiently incorporated into the hydrophobic LCNP core as confirmed by multiple spectroscopic analyses. Conjugation of a PEGylated cholesterol derivative to the NP surface (DiO-LCNP-PEG-Chol) facilitated the localization of the dye-loaded NPs to lipid raft microdomains in the plasma membrane in HEK 293T/17 cell. Analysis of DiO cellular internalization kinetics revealed that when delivered as a LCNP-PEG-Chol NP, the half-life of DiO membrane residence time (30 min) was twice that of free DiO (DiO(free)) (15 min) delivered from bulk solution. Time-resolved laser scanning confocal microscopy was employed to visualize the passive efflux of DiO from the LCNP core and its insertion into the plasma membrane bilayer as confirmed by Förster resonance energy transfer (FRET) imaging. Finally, the delivery of DiO as a LCNP-PEG-Chol complex resulted in the attenuation of its cytotoxicity; the NP form of DiO exhibited ∼30-40% less toxicity compared to DiO(free). Our data demonstrate the utility of the LCNP platform as an efficient vehicle for the combined membrane-targeted delivery and physicochemical modulation of molecular cargos using lipid raft-mediated tethering.

  8. [Progress in metal-organic frameworks].

    Science.gov (United States)

    Zhai, Rui; Jiao, Fenglong; Lin, Hongjun; Hao, Feiran; Li, Jiabin; Yan, Hui; Li, Nannan; Wang, Huanhuan; Jin, Zuyao; Zhang, Yangjun; Qian, Xiaohong

    2014-02-01

    Metal-organic frameworks (MOFs) are a class of crystalline materials built from organic binding ligands and metal ions through self-assembly. Currently, MOFs have drawn a growing interest among the scientific teams of various fields. Compared with conventional inorganic porous materials, MOFs possess larger specific surface areas, higher porosity and diversity of structures and functions, thus many potential applications have been proposed in the domains of gas adsorption and separation, sensors, drug delivery, catalysis or others. The combinations of MOFs and other materials such as graphene oxide, magnetic nanoparticles have obvious advantages in adsorption and separation. The appearance of novel materials greatly promotes interdisciplinary developments such as organic chemistry, inorganic chemistry, coordination chemistry, materials chemistry, life science and computer science. This article reviews the progress of MOFs in recent years, including the characteristics of MOFs, advances at home and abroad, applications, central issues of compound MOFs and the prospects in the future.

  9. Lox breathing system with gas permeable-liquid impermeable heat exchange and delivery hose

    Science.gov (United States)

    Hall, Mark N.

    1996-01-01

    Life support apparatus composed of: a garment (2): for completely enclosing a wearer and constructed for preventing passage of gas from the environment surrounding the garment (2); a portable receptacle (6) holding a quantity of an oxygen-containing fluid in liquid state, the fluid being in a breathable gaseous; state when at standard temperature and pressure; a fluid flow member (16) secured within the garment (2) and coupled to the receptacle (6) for conducting the fluid in liquid state from the receptacle (6) to the interior of the garment (2); and a fluid flow control device (14) connected for causing fluid to flow from the receptacle (6) to the fluid flow member (16) at a rate determined by the breathable air requirement of the wearer, wherein fluid in liquid state is conducted into the interior of the garment (2) at a rate to be vaporized and heated to a breathable temperature by body heat produced by the wearer.

  10. Optical steering of thermally generated microbubbles in a liquid for targeted metallic nanoparticle delivery

    Science.gov (United States)

    Krishnappa, Arjun; Abeywickrema, Ujitha; Banerjee, Partha

    2016-09-01

    A novel mathematical model is developed to investigate the behavior of thermally generated microbubbles in the presence of optical radiation to understand the mechanism of their steering. Forces acting on a bubble are studied in detail using a general force model. It has been proposed that these microbubbles with agglomerated metallic nanoparticles can be used for targeted drug delivery. The model can be extended to include the steering of bubbles with agglomerated silver or gold nanoparticles on their surface.

  11. Enzymatic Polymerization of Cyclic Monomers in Ionic Liquids as a Prospective Synthesis Method for Polyesters Used in Drug Delivery Systems

    Directory of Open Access Journals (Sweden)

    Urszula Piotrowska

    2014-12-01

    Full Text Available Biodegradable or bioresorbable polymers are commonly used in various pharmaceutical fields (e.g., as drug delivery systems, therapeutic systems or macromolecular drug conjugates. Polyesters are an important class of polymers widely utilized in pharmacy due to their biodegradability and biocompatibility features. In recent years, there has been increased interest in enzyme-catalyzed ring-opening polymerization (e-ROP of cyclic esters as an alternative method of preparation of biodegradable or bioresorbable polymers. Ionic liquids (ILs have been presented as green solvents in enzymatic ring-opening polymerization. The activity, stability, selectivity of enzymes in ILs and the ability to catalyze polyester synthesis under these conditions are discussed. Overall, the review demonstrates that e-ROP of lactones or lactides could be an effective method for the synthesis of useful biomedical polymers.

  12. Self-assembled nano-architecture liquid crystalline particles as a promising carrier for progesterone transdermal delivery.

    Science.gov (United States)

    Elgindy, Nazik A; Mehanna, Mohammed M; Mohyeldin, Salma M

    2016-03-30

    The study aims to elaborate novel self-assembled liquid crystalline nanoparticles (LCNPs) for management of hormonal disturbances following non-invasive progesterone transdermal delivery. Fabrication and optimization of progesteroneloaded LCNPs for transdermal delivery were assessed via a quality by design approach based on 2(3) full factorial design. The design includes the functional relationships between independent processing variables and dependent responses of particle size, polydispersity index, zeta potential, cumulative drug released after 24h and ex-vivo transdermal steady flux. The developed nanocarrier was subjected to TEM (transmission electron microscope) for morphological elucidation and stability study within a period of three months at different storage temperatures. The cubic phase of LCNPs was successfully prepared using glyceryl monooleate (GMO) via the emulsification technique. Based on the factorial design, the independent operating variables significantly affected the five dependent responses. The cubosomes hydrodynamic diameters were in the nanometric range (101-386 nm) with narrow particle size distribution, high negative zeta potential ≥-30 mV and entrapment efficiency ≥94%. The LCNPs succeeded in sustaining progesterone release for almost 24h, following a non-fickian transport of drug diffusion mechanism. Ex-vivo study revealed a significant enhancement up to 6 folds in the transdermal permeation of progesterone-loaded LCNPs compared to its aqueous suspension. The optimized LCNPs exhibited a high physical stability while retaining the cubic structure for at least three months. Quality by design approach successfully accomplished a predictable mathematical model permitting the development of novel LCNPs for transdermal delivery of progesterone with the benefit of reducing its oral route side effects.

  13. HIV-TAT enhances the transdermal delivery of NSAID drugs from liquid crystalline mesophases.

    Science.gov (United States)

    Cohen-Avrahami, Marganit; Shames, Alexander I; Ottaviani, M Francesca; Aserin, Abraham; Garti, Nissim

    2014-06-12

    Sodium diclofenac (Na-DFC) and celecoxib (CLXB) are common nonsteroidal anti-inflammatory (NSAID) drugs which suffer from poor bioavailability and severe side effects when consumed orally, and their transdermal delivery might present important advantages. In this study, the drugs were solubilized in cubic and lamellar mesophases as transdermal delivery vehicles, and a cell-penetrating peptide, HIV-TAT (TAT), was examined as a skin penetration enhancer. SD-NMR, ATR-FTIR, and EPR measurements revealed that, in the cubic mesophase (which is rich in water content), TAT populates the aqueous cores and binds water, while in the dense lamellar system (with the lower water content) TAT is bound also to the glycerol monooleate (GMO) and increases the microviscosity and the order degree. TAT secondary structure in the cubic system was found to be a random coil while once it was embedded in the closely packed lamellar system it transforms to a more ordered compact state of β-turns arranged around the GMO headgroups. TAT remarkably increased the diffusion of Na-DFC and CLXB from the cubic systems by 6- and 9-fold enhancement, respectively. TAT effect on drug diffusion from the lamellar systems was limited to an increase of 1.3- and 1.7-fold, respectively. The dense packing and strong binding in the lamellar phase led to slow diffusion rates and slower drug release in controlled pattern. These effects of the chemical composition and vehicle geometry on drug diffusion are demonstrated with the impacts of TAT which can be specifically utilized for controlling skin delivery of drugs as required.

  14. Nanoscale metal-organic materials.

    Science.gov (United States)

    Carné, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel

    2011-01-01

    Metal-organic materials are found to be a fascinating novel class of functional nanomaterials. The limitless combinations between inorganic and organic building blocks enable researchers to synthesize 0- and 1-D metal-organic discrete nanostructures with varied compositions, morphologies and sizes, fabricate 2-D metal-organic thin films and membranes, and even structure them on surfaces at the nanometre length scale. In this tutorial review, the synthetic methodologies for preparing these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chemistry, physics, medicine, nanotechnology, materials chemistry, etc., in the next years.

  15. Highly mesoporous metal-organic framework assembled in a switchable solvent

    Science.gov (United States)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  16. Iron casein succinylate-chitosan coacervate for the liquid oral delivery of iron with bioavailability and stability enhancement.

    Science.gov (United States)

    Min, Kyoung Ah; Cho, Jung-Hye; Song, Yun-Kyoung; Kim, Chong-Kook

    2016-01-01

    Iron casein succinylate (ICS) liquid oral preparation as iron supplement has uncomfortable taste after a long period of storage because of its stability, and poor bioavailability of iron compared to any other iron preparations. To improve the chemical stability of ICS and enhance the bioavailability of iron, chitosan-ICS nanoparticles (NPs) were prepared by complex coacervation method and stabilized with polyethylene glycol (PEG) 400. NPs were spherical (mean diameter of 830-1070 nm) with positive charge (+30-60 mV) depending on the composition of NPs. Addition of PEG400 (2 w/v %) increased the zeta potential (26-50 %) and physical stability of chitosan-ICS NPs suspension. Also, NPs decreased iron release compared to ICS after 7-weeks of storage at 4 °C. NPs markedly increased the permeability of iron in Caco-2 cell up to 32-38-fold compared to ICS, while physical mixture of chitosan and ICS increased the iron permeability only 2.5-fold. In summary, NPs improved the physicochemical stability and enhanced the transport of iron compared to other iron preparations in Caco-2 cell model. Thus, chitosan-ICS coacervate might be a promising candidate as a liquid oral iron delivery system for iron deficiency patients with stability and bioavailability enhancement.

  17. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis.

    Science.gov (United States)

    Liu, Jiewei; Chen, Lianfen; Cui, Hao; Zhang, Jianyong; Zhang, Li; Su, Cheng-Yong

    2014-08-21

    This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

  18. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    Science.gov (United States)

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  19. 纳米金属有机骨架化合物( NMOFs)的合成及其生物应用%Nanoscale metal-organic frameworks for biomedical imaging and drug delivery

    Institute of Scientific and Technical Information of China (English)

    秦丽洁; 丁亮; 秦长圆; 杨红; 杨仕平

    2012-01-01

    Nanoscale metal-organic frameworks (NMOFs) are a kind of coordination polymers with broad potential applications in biomedical field. This review introduced the synthesis methods of the NMOFs and the latest development of NMOFs as imaging contrast agents and molecular therapeutics. At last we put forward several aspects in this field in the future.%纳米金属有机骨架化合物是在生物医药方面具有广泛潜在应用价值的配位聚合物.从纳米金属有机骨架化合物的合成方法、药物负载、表面修饰以及生物应用等方面介绍了国内外在这一领域的最新进展,并提出了今后需要关注的几个方面,具有一定的参考价值.

  20. Evolution of form in metal-organic frameworks

    Science.gov (United States)

    Lee, Jiyoung; Kwak, Ja Hun; Choe, Wonyoung

    2017-01-01

    Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal-organic materials (MOMs), an emerging class of porous materials consisting of metal-organic frameworks (MOFs) and metal-organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF. Moreover, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs. We anticipate that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.

  1. Qualification of a sublimation tool applied to the case of metalorganic chemical vapor deposition of In₂O₃ from In(tmhd)₃ as a solid precursor.

    Science.gov (United States)

    Szkutnik, P D; Angélidès, L; Todorova, V; Jiménez, C

    2016-02-01

    A solid delivery system consisting of a source canister, a gas management, and temperature controlled enclosure designed and manufactured by Air Liquide Electronics Systems was tested in the context of gas-phase delivery of the In(tmhd)3 solid precursor. The precursor stream was delivered to a thermal metalorganic chemical vapor deposition reactor to quantify deposition yield under various conditions of carrier gas flow and sublimation temperature. The data collected allowed the determination of characteristic parameters such as the maximum precursor flow rate (18.2 mg min(-1) in specified conditions) and the critical mass (defined as the minimum amount of precursor able to attain the maximum flow rate) found to be about 2.4 g, as well as an understanding of the influence of powder distribution inside the canister. Furthermore, this qualification enabled the determination of optimal delivery conditions which allowed for stable and reproducible precursor flow rates over long deposition times (equivalent to more than 47 h of experiment). The resulting In2O3 layers was compared with those elaborated via pulsed liquid injection obtained in the same chemical vapor deposition chamber and under the same deposition conditions.

  2. Self-assembled multicompartment liquid crystalline lipid carriers for protein, peptide, and nucleic acid drug delivery.

    Science.gov (United States)

    Angelova, Angelina; Angelov, Borislav; Mutafchieva, Rada; Lesieur, Sylviane; Couvreur, Patrick

    2011-02-15

    Lipids and lipopolymers self-assembled into biocompatible nano- and mesostructured functional materials offer many potential applications in medicine and diagnostics. In this Account, we demonstrate how high-resolution structural investigations of bicontinuous cubic templates made from lyotropic thermosensitive liquid-crystalline (LC) materials have initiated the development of innovative lipidopolymeric self-assembled nanocarriers. Such structures have tunable nanochannel sizes, morphologies, and hierarchical inner organizations and provide potential vehicles for the predictable loading and release of therapeutic proteins, peptides, or nucleic acids. This Account shows that structural studies of swelling of bicontinuous cubic lipid/water phases are essential for overcoming the nanoscale constraints for encapsulation of large therapeutic molecules in multicompartment lipid carriers. For the systems described here, we have employed time-resolved small-angle X-ray scattering (SAXS) and high-resolution freeze-fracture electronic microscopy (FF-EM) to study the morphology and the dynamic topological transitions of these nanostructured multicomponent amphiphilic assemblies. Quasi-elastic light scattering and circular dichroism spectroscopy can provide additional information at the nanoscale about the behavior of lipid/protein self-assemblies under conditions that approximate physiological hydration. We wanted to generalize these findings to control the stability and the hydration of the water nanochannels in liquid-crystalline lipid nanovehicles and confine therapeutic biomolecules within these structures. Therefore we analyzed the influence of amphiphilic and soluble additives (e.g. poly(ethylene glycol)monooleate (MO-PEG), octyl glucoside (OG), proteins) on the nanochannels' size in a diamond (D)-type bicontinuous cubic phase of the lipid glycerol monooleate (MO). At body temperature, we can stabilize long-living swollen states, corresponding to a diamond cubic phase

  3. Liquid crystalline phase as a probe for crystal engineering of lactose: carrier for pulmonary drug delivery.

    Science.gov (United States)

    Patil, Sharvil S; Mahadik, Kakasaheb R; Paradkar, Anant R

    2015-02-20

    The current work was undertaken to assess suitability of liquid crystalline phase for engineering of lactose crystals and their utility as a carrier in dry powder inhalation formulations. Saturated lactose solution was poured in molten glyceryl monooleate which subsequently transformed into gel. The gel microstructure was analyzed by PPL microscopy and SAXS. Lactose particles recovered from gels after 48 h were analyzed for polymorphism using techniques such as FTIR, XRD, DSC and TGA. Particle size, morphology and aerosolisation properties of prepared lactose were analyzed using Anderson cascade impactor. In situ seeding followed by growth of lactose crystals took place in gels with cubic microstructure as revealed by PPL microscopy and SAXS. Elongated (size ∼ 71 μm) lactose particles with smooth surface containing mixture of α and β-lactose was recovered from gel, however percentage of α-lactose was more as compared to β-lactose. The aerosolisation parameters such as RD, ED, %FPF and % recovery of lactose recovered from gel (LPL) were found to be comparable to Respitose® ML001. Thus LC phase (cubic) can be used for engineering of lactose crystals so as to obtain particles with smooth surface, high elongation ratio and further they can be used as carrier in DPI formulations.

  4. Oral medication delivery in impaired swallowing: thickening liquid medications for safe swallowing alters dissolution characteristics.

    Science.gov (United States)

    Manrique, Yady J; Sparkes, Arron M; Cichero, Julie A Y; Stokes, Jason R; Nissen, Lisa M; Steadman, Kathryn J

    2016-09-01

    Acetaminophen (paracetamol) is available in a wide range of oral formulations designed to meet the needs of the population across the age-spectrum, but for people with impaired swallowing, i.e. dysphagia, both solid and liquid medications can be difficult to swallow without modification. The effect of a commercial polysaccharide thickener, designed to be added to fluids to promote safe swallowing by dysphagic patients, on rheology and acetaminophen dissolution was tested using crushed immediate-release tablets in water, effervescent tablets in water, elixir and suspension. The inclusion of the thickener, comprised of xanthan gum and maltodextrin, had a considerable impact on dissolution; acetaminophen release from modified medications reached 12-50% in 30 min, which did not reflect the pharmacopeia specification for immediate release preparations. Flow curves reflect the high zero-shear viscosity and the apparent yield stress of the thickened products. The weak gel nature, in combination with high G' values compared to G'' (viscoelasticity) and high apparent yield stress, impact drug release. The restriction on drug release from these formulations is not influenced by the theoretical state of the drug (dissolved or dispersed), and the approach typically used in clinical practice (mixing crushed tablets into pre-prepared thickened fluid) cannot be improved by altering the order of incorporation or mixing method.

  5. Selective anion exchange with nanogated isoreticular positive metal-organic frameworks.

    Science.gov (United States)

    Zhao, Xiang; Bu, Xianhui; Wu, Tao; Zheng, Shou-Tian; Wang, Le; Feng, Pingyun

    2013-01-01

    Crystalline porous materials, especially inorganic porous solids such as zeolites, usually have negative frameworks with extra-framework mobile cations and are widely used for cation exchange. It is highly desirable to develop new materials with positive frameworks for selective anion exchange and separation or storage and delivery. Recent advances in metal-organic framework synthesis have created new opportunities in this direction. Here we report the synthesis of a series of positive indium metal-organic frameworks and their utilization as a platform for the anion exchange-based separation process. This process is capable of size- or charge-selective ion-exchange of organic dyes and may form the basis for size-selective ion chromatography. Ion-exchange dynamics of a series of organic dyes and their selective encapsulation and release are also studied, highlighting the advantages of metal-organic framework compositions for designing host materials tailored for applications in anion separation and purification.

  6. Wild carnivore acceptance of baits for delivery of liquid rabies vaccine.

    Science.gov (United States)

    Bachmann, P; Bramwell, R N; Fraser, S J; Gilmore, D A; Johnston, D H; Lawson, K F; MacInnes, C D; Matejka, F O; Miles, H E; Pedde, M A

    1990-10-01

    A series of experiments are described on the acceptance, by red foxes (Vulpes vulpes) and other species, of two types of vaccine-baits intended to deliver liquid rabies vaccine. The baits consisted of a cube of sponge coated in a mixture of tallow and wax, or a plastic blister-pack embedded in tallow. All baits contained tetracycline as a biological marking agent: examination of thin sections of carnivore canines under an ultraviolet microscope revealed a fluorescent line of tetracycline if an individual had eaten baits. Baits were dropped from fixed-wing aircraft flying about 100 m above ground at approximately 130 km/h. Flight lines followed the edges of woodlots midway between parallel roads. Baits were dropped at one/sec, resulting in one bait/36 m on the ground, or 17 to 25 baits per km2. Crows (Corvus brachyrhynchos) removed many baits, but did not appear to lower the percent of the fox population which took bait. Dropping baits only into corn and woodland to conceal baits, to reduce depredation by crows, reduced acceptance by foxes. Acceptance by foxes ranged between 37 and 68%. Meat added as an attractant did not raise acceptance. Presence, absence, color and perforations of plastic bags did not alter bait acceptance. Dispersal by juvenile foxes probably lowered the estimates of bait acceptance. It took 7 to 17 days for 80% (n = 330) of foxes to eat their first bait. The rapidity with which foxes picked up their first bait appeared more affected by unknown characteristics of years or study areas than by experimental variables. Skunks (Mephitis mephitis) and raccoons (Procyon lotor) also ate these baits, but acceptance was lower. Small mammals contacted baits, but rarely contacted the vaccine, which had the potential for vaccine-induced rabies in some species. Aerial distribution of baits was more cost-effective than ground distribution as practiced in Europe. This system has potential for field control of rabies, although higher acceptance will be desirable.

  7. Effect of emulsifiers and their liquid crystalline structures in emulsions on dermal and transdermal delivery of hydroquinone, salicylic acid and octadecenedioic acid.

    Science.gov (United States)

    Otto, A; Wiechers, J W; Kelly, C L; Dederen, J C; Hadgraft, J; du Plessis, J

    2010-01-01

    This study investigated the effect of emulsifiers and their liquid crystalline structures on the dermal and transdermal delivery of hydroquinone (HQ), salicylic acid (SA) and octadecenedioic acid (DIOIC). Emulsions containing liquid crystalline phases were compared with an emulsion without liquid crystals. Skin permeation experiments were performed using Franz-type diffusion cells and human abdominal skin dermatomed to a thickness of 400 mum. The results indicate that emulsifiers arranging in liquid crystalline structures in the water phase of the emulsion enhanced the skin penetration of the active ingredients with the exception of SA. SA showed a different pattern of percutaneous absorption, and no difference in dermal and transdermal delivery was observed between the emulsions with and without liquid crystalline phases. The increase in skin penetration of HQ and DIOIC could be attributed to an increased partitioning of the actives into the skin. It was hypothesized that the interaction between the different emulsifiers and active ingredients in the formulations varied and, therefore, the solubilization capacities of the various emulsifiers and their association structures.

  8. Metal-Organic Heat Carrier Nanofluids

    Energy Technology Data Exchange (ETDEWEB)

    McGrail, B. Peter; Thallapally, Praveen K.; Blanchard, Jeremy; Nune, Satish K.; Jenks, Jeromy WJ; Dang, Liem X.

    2013-09-01

    Nanofluids, dispersions of metal or oxide nanoparticles in a base working fluid, are being intensively studied due to improvements they offer in thermal properties of the working fluid. However, these benefits have been erratically demonstrated and proven impacts on thermal conductivity are modest and well described from long-established effective medium theory. In this paper, we describe a new class of metal-organic heat carrier (MOHC) nanofluid that offers potential for a larger performance boost in thermal vapor-liquid compression cycles. MOHCs are nanophase porous coordination solids designed to reversibly uptake the working fluid molecules in which the MOHCs are suspended. Additional heat can be extracted in a heat exchanger or solar collector from the endothermic enthalpy of desorption, which is then released as the nanofluid transits through a power generating device such as a turboexpander. Calculations for an R123 MOHC nanofluid indicated potential for up to 15% increase in power output. Capillary tube experiments show that liquid-vapor transitions occur without nanoparticle deposition on the tube walls provided entrance Reynolds number exceeds approximately 100.

  9. An in situ gelling liquid crystalline system based on monoglycerides and polyethylenimine for local delivery of siRNAs

    NARCIS (Netherlands)

    Borgheti-Cardoso, Lívia Neves; Depieri, Lívia Vieira; Kooijmans, Sander A A; Diniz, Henrique; Calzzani, Ricardo Alexandre Junqueira; De Carvalho Vicentini, Fabiana Testa Moura; Van Der Meel, Roy; De Abreu Fantini, Márcia Carvalho; Iyomasa, Mamie Mizusaki; Schiffelers, Raymond M.; Bentley, Maria Vitória Lopes Badra; Schiffelers, Raymond

    2015-01-01

    The development of delivery systems able to complex and release siRNA into the cytosol is essential for therapeutic use of siRNA. Among the delivery systems, local delivery has advantages over systemic administration. In this study, we developed and characterized non-viral carriers to deliver siRNA

  10. An in situ gelling liquid crystalline system based on monoglycerides and polyethylenimine for local delivery of siRNAs

    NARCIS (Netherlands)

    Borgheti-Cardoso, Lívia Neves; Depieri, Lívia Vieira; Kooijmans, Sander; Diniz, Henrique; Calzzani, Ricardo Alexandre Junqueira; De Carvalho Vicentini, Fabiana Testa Moura; van der Meel, Roy; De Abreu Fantini, Márcia Carvalho; Iyomasa, Mamie Mizusaki; Schiffelers, Raymond; Bentley, Maria Vitória Lopes Badra

    2015-01-01

    The development of delivery systems able to complex and release siRNA into the cytosol is essential for therapeutic use of siRNA. Among the delivery systems, local delivery has advantages over systemic administration. In this study, we developed and characterized non-viral carriers to deliver siRNA

  11. Liquid Crystalline Nanoparticles as an Ophthalmic Delivery System for Tetrandrine: Development, Characterization, and In Vitro and In Vivo Evaluation

    Science.gov (United States)

    Liu, Rui; Wang, Shuangshuang; Fang, Shiming; Wang, Jialu; Chen, Jingjing; Huang, Xingguo; He, Xin; Liu, Changxiao

    2016-05-01

    The purpose of this study was to develop novel liquid crystalline nanoparticles (LCNPs) that display improved pre-ocular residence time and ocular bioavailability and that can be used as an ophthalmic delivery system for tetrandrine (TET). The delivery system consisted of three primary components, including glyceryl monoolein, poloxamer 407, and water, and two secondary components, including Gelucire 44/14 and amphipathic octadecyl-quaternized carboxymethyl chitosan. The amount of TET, the amount of glyceryl monoolein, and the ratio of poloxamer 407 to glyceryl monoolein were selected as the factors that were used to optimize the dependent variables, which included encapsulation efficiency and drug loading. A three-factor, five-level central composite design was constructed to optimize the formulation. TET-loaded LCNPs (TET-LCNPs) were characterized to determine their particle size, zeta potential, entrapment efficiency, drug loading capacity, particle morphology, inner crystalline structure, and in vitro drug release profile. Corneal permeation in excised rabbit corneas was evaluated. Pre-ocular retention was determined using a noninvasive fluorescence imaging system. Finally, pharmacokinetic study in the aqueous humor was performed by microdialysis technique. The optimal formulation had a mean particle size of 170.0 ± 13.34 nm, a homogeneous distribution with polydispersity index of 0.166 ± 0.02, a positive surface charge with a zeta potential of 29.3 ± 1.25 mV, a high entrapment efficiency of 95.46 ± 4.13 %, and a drug loading rate of 1.63 ± 0.07 %. Transmission electron microscopy showed spherical particles that had smooth surfaces. Small-angle X-ray scattering profiles revealed an inverted hexagonal phase. The in vitro release assays showed a sustained drug release profile. A corneal permeation study showed that the apparent permeability coefficient of the optimal formulation was 2.03-fold higher than that of the TET solution. Pre-ocular retention

  12. The preparation of metal-organic frameworks and their biomedical application.

    Science.gov (United States)

    Liu, Rong; Yu, Tian; Shi, Zheng; Wang, Zhiyong

    2016-01-01

    The development of a safe and targetable drug carrier is a major challenge. An efficient delivery system should protect cargo from degradation and cleanup, and control of drug release in the target site. Metal-organic frameworks (MOFs), consisting of metal ions and a variety of organic ligands, have been applied for drug delivery due to their distinct structure. In this review, we summarized the synthesis strategies of MOFs, especially emphasizing the methods of pore creation in frameworks, which were based on recent literatures. Subsequently, the controlled size, biocompatibility, drug releasing performances, and imaging of MOFs were discussed, which would pave the road for the application in drug-delivery systems.

  13. 2-periodic metal-organic frameworks (MOFs) as supermolecular building layers (SBLs) for making targeted 3-periodic MOFs

    KAUST Repository

    Eddaoudi, Mohamed

    2015-09-22

    Embodiments of the present disclosure provide for chemical assemblies, multidimensional metal-organic frameworks (MOFs), supermolecular building layers (SBLs), inorganic molecular building blocks (MBBs), organic MBBs (designed ligands), methods of making each, and methods of using each, and the like. In an embodiment, the composition can be used in catalysis, separations, gas storage, and drug delivery.

  14. Technical report Development of a piezoelectric inkjet dopant delivery device for an atmospheric pressure photoionization source with liquid chromatography/mass spectrometry

    KAUST Repository

    Amad, Maan H.

    2013-01-01

    This paper describes a simple robust and integrated piezoelectric actuated printhead as a dopant delivery system for atmospheric pressure photoionization with liquid chromatography/mass spectrometry The newly designed dopant delivery system avoids problems associated with traditional liquid delivery systems such as solvent immiscibility backpressure and increased post-column dead volume issues The performance of the new device was tested and evaluated using chlorobenzene as a dopant with a test mixture consisting of 18 different polycyclic aromatic hydrocarbons (PAHs) The results show that the new system works robustly at low dopant consumption level (16 uL min-1) consuming only approximately 5% of the amount used by conventional sources The low dopant consumption has resulted in up to a 20-fold reduction in signal intensity of tested PAH molecules but has led to less presence of background cluster ions and dopant trace contaminant background ions in the source area Consequently all tested PAHs were detected with excellent signal-to-noise ratio with at least two-to ten-fold improvements in the limit of detection and quantification compared to those obtained with traditional dopant assistance using a post-column addition method © IM Publications LLP 2013.

  15. Metal-organic frameworks for membrane-based separations

    Science.gov (United States)

    Denny, Michael S.; Moreton, Jessica C.; Benz, Lauren; Cohen, Seth M.

    2016-12-01

    As research into metal-organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies.

  16. Lipid-based liquid crystalline nanoparticles as oral drug delivery vehicles for poorly water-soluble drugs: cellular interaction and in vivo absorption

    Directory of Open Access Journals (Sweden)

    Zeng N

    2012-07-01

    Full Text Available Ni Zeng,1,3,* Xiaoling Gao,2,* Quanyin Hu,1 Qingxiang Song,2 Huimin Xia,1 Zhongyang Liu,1 Guangzhi Gu,1 Mengyin Jiang,1,4 Zhiqing Pang,1 Hongzhuan Chen,2 Jun Chen,1 Liang Fang3 1Key Laboratory of Smart Drug Delivery, Ministry of Education and PLA, School of Pharmacy, Fudan University, Shanghai, 2Department of Pharmacology, Institute of Medical Sciences, Shanghai Jiaotong University School of Medicine, Shanghai, 3Department of Pharmaceutical Science, School of Pharmacy, Shenyang Pharmaceutical University, Shenyang, Liaoning, 4School of Pharmacy, Shandong University of Traditional Chinese Medicine, Jinan, Shandong People's Republic of China, *These authors contributed equally to this workBackground: Lipid-based liquid crystalline nanoparticles (LCNPs have attracted growing interest as novel drug-delivery systems for improving the bioavailability of both hydrophilic and hydrophobic drugs. However, their cellular interaction and in vivo behavior have not been fully developed and characterized.Methods: In this study, self-assembled LCNPs prepared from soy phosphatidylcholine and glycerol dioleate were developed as a platform for oral delivery of paclitaxel. The particle size of empty LCNPs and paclitaxel-loaded LCNPs was around 80 nm. The phase behavior of the liquid crystalline matrix was characterized using crossed polarized light microscopy and small-angle X-ray scattering, and showed both reversed cubic and hexagonal phase in the liquid crystalline matrix. Transmission electron microscopy and cryofield emission scanning electron microscopy analysis revealed an inner winding water channel in LCNPs and a "ball-like"/"hexagonal" morphology.Results: Cellular uptake of LCNPs in Caco-2 cells was found to be concentration-dependent and time-dependent, with involvement of both clathrin and caveolae/lipid raft-mediated endocytosis. Under confocal laser scanning microscopy, soy phosphatidylcholine was observed to segregate from the internalized LCNPs and

  17. Qualification of a sublimation tool applied to the case of metalorganic chemical vapor deposition of In{sub 2}O{sub 3} from In(tmhd){sub 3} as a solid precursor

    Energy Technology Data Exchange (ETDEWEB)

    Szkutnik, P. D., E-mail: pierre.szkutnik@cea.fr; Jiménez, C. [Université Grenoble Alpes, CNRS, LMGP, 3 Parvis Louis Néel, Minatec CS 50257, 38016 Grenoble Cedex 1 (France); Angélidès, L.; Todorova, V. [Air Liquide Electronics Systems, 8 rue des Méridiens–Sud Galaxie BP 228, 38433 Échirolles Cedex (France)

    2016-02-15

    A solid delivery system consisting of a source canister, a gas management, and temperature controlled enclosure designed and manufactured by Air Liquide Electronics Systems was tested in the context of gas-phase delivery of the In(tmhd){sub 3} solid precursor. The precursor stream was delivered to a thermal metalorganic chemical vapor deposition reactor to quantify deposition yield under various conditions of carrier gas flow and sublimation temperature. The data collected allowed the determination of characteristic parameters such as the maximum precursor flow rate (18.2 mg min{sup −1} in specified conditions) and the critical mass (defined as the minimum amount of precursor able to attain the maximum flow rate) found to be about 2.4 g, as well as an understanding of the influence of powder distribution inside the canister. Furthermore, this qualification enabled the determination of optimal delivery conditions which allowed for stable and reproducible precursor flow rates over long deposition times (equivalent to more than 47 h of experiment). The resulting In{sub 2}O{sub 3} layers was compared with those elaborated via pulsed liquid injection obtained in the same chemical vapor deposition chamber and under the same deposition conditions.

  18. Characterization of gelation process and drug release profile of thermosensitive liquid lecithin/poloxamer 407 based gels as carriers for percutaneous delivery of ibuprofen.

    Science.gov (United States)

    Djekic, Ljiljana; Krajisnik, Danina; Martinovic, Martina; Djordjevic, Dragana; Primorac, Marija

    2015-07-25

    Suitability of liquid lecithin (i.e., solution of lecithin in soy bean oil with ∼ 60% w/w of phospholipids) for formation of gels, upon addition of water solution of poloxamer 407, was investigated, and formulated systems were evaluated as carriers for percutaneous delivery of ibuprofen. Formulation study of pseudo-ternary system liquid lecithin/poloxamer 407/water at constant liquid lecithin/poloxamer 407 mass ratio (2.0) revealed that minimum concentrations of liquid lecithin and poloxamer 407 required for formation of gel like systems were 15.75% w/w and 13.13% w/w, respectively, while the maximum content of water was 60.62% w/w. The systems comprising water concentrations in a range from 55 to 60.62% w/w were soft semisolids suitable for topical application, and they were selected for physicochemical and biopharmaceutical evaluation. Analysis of conductivity results and light microscopy examination revealed that investigated systems were water dilutable dispersions of spherical oligolamellar associates of phospholipids and triglyceride molecules in the copolymer water solution. Rheological behavior evaluation results indicated that the investigated gels were thermosensitive shear thinning systems. Ibuprofen (5% w/w) was incorporated by dispersing into the previously prepared carriers. Drug-loaded systems were physically stable at storage temperature from 5 ± 3°C to 40 ± 2°C, for 30 days. In vitro ibuprofen release was in accordance with the Higuchi model (rH>0.95) and sustained for 12h. The obtained results implicated that formulated LLPBGs, optimized regarding drug release and organoleptic properties, represent promising carriers for sustained percutaneous drug delivery of poorly soluble drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Planar Mn4O cluster homochiral metal-organic framework for HPLC separation of pharmaceutically important (±)-ibuprofen racemate.

    Science.gov (United States)

    Hailili, Reshalaiti; Wang, Li; Qv, Junzhang; Yao, Ruxin; Zhang, Xian-Ming; Liu, Huwei

    2015-04-20

    A planar tetracoordinated oxygen containing a homochiral metal-organic framework (MOF) has been synthesized and characterized that can be used as a new chiral stationary phase in high-performance liquid chromatography to efficiently separate racemates such as pharmaceutically important (±)-ibuprofen and (±)-1-phenyl-1,2-ethanediol.

  20. Magnetism in metal-organic capsules

    Energy Technology Data Exchange (ETDEWEB)

    Atwood, Jerry L.; Brechin, Euan K; Dalgarno, Scott J.; Inglis, Ross; Jones, Leigh F.; Mossine, Andrew; Paterson, Martin J.; Power, Nicholas P.; Teat, Simon J.

    2010-01-07

    Nickel and cobalt seamed metal-organic capsules have been isolated and studied using structural, magnetic and computational approaches. Antiferromagnetic exchange in the Ni capsule results from coordination environments enforced by the capsule framework.

  1. Magnetism in metal-organic capsules

    Energy Technology Data Exchange (ETDEWEB)

    Atwood, Jerry L.; Brechin, Euan K; Dalgarno, Scott J.; Inglis, Ross; Jones, Leigh F.; Mossine, Andrew; Paterson, Martin J.; Power, Nicholas P.; Teat, Simon J.

    2010-01-07

    Nickel and cobalt seamed metal-organic capsules have been isolated and studied using structural, magnetic and computational approaches. Antiferromagnetic exchange in the Ni capsule results from coordination environments enforced by the capsule framework.

  2. Alginate fibres containing discrete liquid filled vacuoles for controlled delivery of healing agents in fibre reinforced composites

    NARCIS (Netherlands)

    Mookhoek, S.D.; Fischer, H.R.; Zwaag, S. van der

    2012-01-01

    The work addressed involves the preparation and application of a compartmented polymer fibre, containing multiple separated domains with liquid agent for controlled release. The created fibre is a design for improvement to the existing liquid encapsulated self-healing systems such as fibre reinforce

  3. Metal-Organic Frameworks as Platforms for Functional Materials.

    Science.gov (United States)

    Cui, Yuanjing; Li, Bin; He, Huajun; Zhou, Wei; Chen, Banglin; Qian, Guodong

    2016-03-15

    Discoveries of novel functional materials have played very important roles to the development of science and technologies and thus to benefit our daily life. Among the diverse materials, metal-organic framework (MOF) materials are rapidly emerging as a unique type of porous and organic/inorganic hybrid materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers, and can be straightforwardly characterized by various analytical methods. In terms of porosity, they are superior to other well-known porous materials such as zeolites and carbon materials; exhibiting extremely high porosity with surface area up to 7000 m(2)/g, tunable pore sizes, and metrics through the interplay of both organic and inorganic components with the pore sizes ranging from 3 to 100 Å, and lowest framework density down to 0.13 g/cm(3). Such unique features have enabled metal-organic frameworks to exhibit great potentials for a broad range of applications in gas storage, gas separations, enantioselective separations, heterogeneous catalysis, chemical sensing and drug delivery. On the other hand, metal-organic frameworks can be also considered as organic/inorganic self-assembled hybrid materials, we can take advantages of the physical and chemical properties of both organic and inorganic components to develop their functional optical, photonic, and magnetic materials. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of different species of diverse functions, so a variety of functional MOF/composite materials can be readily synthesized. In this Account, we describe our recent research progress on pore and function engineering to develop functional MOF materials. We have been able to tune and optimize pore spaces, immobilize specific functional groups, and introduce chiral pore environments to target MOF materials for methane storage, light hydrocarbon separations, enantioselective recognitions

  4. Delivery of esomeprazole magnesium through nasogastric and gastrostomy tubes using an oral liquid vehicle as a suspending agent in vitro.

    Science.gov (United States)

    Shah, Sachin A; Sander, Stephen; Coleman, Craig I; White, C Michael

    2006-10-01

    The optimal delivery medium for esomeprazole magnesium enteric-coated pellets dispersed in various concentrations of Ora-Plus suspension through commonly used nasogastric and gastrostomy tubes using a previously used standardized in vitro protocol was studied. The study was conducted in two phases. In phase A, 60 size 14 French nasogastric tubes were used to compare esomeprazole pellet delivery via tap water or 30, 50, or 70% Ora-Plus concentrations (15 tubes for each). In phase B, tap water and the concentration that yielded the best pellet delivery from phase A were used with the narrower size 8 and shorter size 20 French tubes. In both phases, the appropriate volume of water was added. All capsules were assumed to have 1,240 pellets. At the end of each administration, pellet retention counts were performed. The results showed excellent delivery of esomeprazole pellets using water as a medium for tube delivery. When compared with tap water as a delivery medium, no differences in pellet retention were observed when 30% and 50% Ora-Plus were used; thus, these Ora-Plus concentrations are feasible alternatives to tap water for nasogastric tube delivery of esomeprazole pellets. Administration of esomeprazole magnesium enteric-coated pellets dispersed in tap water or Ora-Plus through size 14 French nasogastric tubes in vitro delivered over 99% of capsule contents, regardless of the Ora-Plus concentration used. For immediate bedside administration, Ora-Plus at 50% concentration is a feasible alternative to water when delivering the pellets through size 14 French tubes, while 30% Ora-Plus is an alternative to water for all tubes studied.

  5. Self-Exfoliated Metal-Organic Nanosheets through Hydrolytic Unfolding of Metal-Organic Polyhedra.

    Science.gov (United States)

    Garai, Bikash; Mallick, Arijit; Das, Anuja; Mukherjee, Rabibrata; Banerjee, Rahul

    2017-05-29

    Few-layers thick metal-organic nanosheets have been synthesized using water-assisted solid-state transformation through a combined top-down and bottom-up approach. The metal-organic polyhedra (MOPs) convert into metal-organic frameworks (MOFs) which subsequently self-exfoliate into few-layered metal-organic nanosheets. These MOP crystals experience a hydrophobicity gradient with the inner surface during contact with water because of the existence of hydrophobic spikes on their outer surface. When the amount of water available for interaction is higher, the resultant layers are not stacked to form bulk materials; instead few-layered nanosheets with high uniformity were obtained in high yield. The phenomenon has resulted high yield production of uniformly distributed layered metal-organic nanosheets from three different MOPs, showing its general adaptability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Intermolecular interaction between rare earth and manganese precursors in metalorganic chemical vapor deposition of perovskite manganite films

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, Toshihiro [Department of Engineering Science, Osaka Electro-Communication University, 18-8 Hatsu-cho, Neyagawa, Osaka 572-8530 (Japan)

    2015-07-15

    The gas-phase reaction mechanism was investigated in liquid delivery metalorganic chemical vapor deposition (MOCVD) of praseodymium and lanthanum manganite films. We studied the gas-phase behavior of praseodymium, lanthanum, and manganese precursors under actual CVD conditions by in situ infrared absorption spectroscopy. The rate of the decrease of the infrared absorbance due to Pr(DPM){sub 3} was almost constant even if Mn(DPM){sub 3} was added, indicating that the intermolecular interaction between Pr and Mn precursors in the gas phase is relatively weak in MOCVD of praseodymium manganite films. On the other hand, the temperature dependence of the infrared absorption indicates that the thermal decomposition of La(DPM){sub 3} was promoted in the presence of Mn(DPM){sub 3}. The significant intermolecular interaction occurs between La and Mn precursors in the gas phase in MOCVD of lanthanum manganite films. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Science.gov (United States)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-01

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100-1000 m2 g-1) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m2 g-1), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs.

  8. Stepwise Synthesis of Metal-Organic Frameworks.

    Science.gov (United States)

    Bosch, Mathieu; Yuan, Shuai; Rutledge, William; Zhou, Hong-Cai

    2017-04-18

    Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using

  9. Delivery of Liquid Metal to the Target Vessels as Vascular Embolic Agent to Starve Diseased Tissues or Tumors to Death

    CERN Document Server

    Wang, Qian; Liu, Jing

    2014-01-01

    Tumor growth relies heavily on the continuous blood and nutrients supply. Theoretically, it is an ideal therapeutic way of killing tumor by only vascular embolization. However, most of the existing vascular embolic agents are still rather insufficient to fulfill the real clinical need due to the reasons like: incomplete filling of target vasculature, being easily washed away by blood or body solution, or just producing toxicity to tissues. Here from an alternative way, the body temperature liquid metal, a kind of soft and highly compliant material, was proposed for the first time as blood vessel embolization agent for tumor physical therapy. With its unique capability of easy phase transition between liquid and solid state and sub-cooling behavior, such material can be fluently injected into the tiny vessels including ending capillaries and fully block them. The in vitro cytotoxicity experiments were performed which showed that treating localized diseased tissues through liquid metal embolic agent is acceptab...

  10. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    Science.gov (United States)

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-01

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  11. Structural Features and the Anti-Inflammatory Effect of Green Tea Extract-Loaded Liquid Crystalline Systems Intended for Skin Delivery

    Directory of Open Access Journals (Sweden)

    Patricia Bento da Silva

    2017-01-01

    Full Text Available Camellia sinensis, which is obtained from green tea extract (GTE, has been widely used in therapy owing to the antioxidant, chemoprotective, and anti-inflammatory activities of its chemical components. However, GTE is an unstable compound, and may undergo reactions that lead to a reduction or loss of its effectiveness and even its degradation. Hence, an attractive approach to overcome this problem to protect the GTE is its incorporation into liquid crystalline systems (LCS that are drug delivery nanostructured systems with different rheological properties, since LCS have both fluid liquid and crystalline solid properties. Therefore, the aim of this study was to develop and characterize GTE-loaded LCS composed of polyoxypropylene (5 polyoxyethylene (20 cetyl alcohol, avocado oil, and water (F25E, F29E, and F32E with different rheological properties and to determine their anti-inflammatory efficacy. Polarized light microscopy revealed that the formulations F25, F29, and F32 showed hexagonal, cubic, and lamellar liquid crystalline mesophases, respectively. Rheological studies showed that F32 is a viscous Newtonian liquid, while F25 and F29 are dilatant and pseudoplastic non-Newtonian fluids, respectively. All GTE-loaded LCS behaved as pseudoplastic with thixotropy; furthermore, the presence of GTE increased the S values and decreased the n values, especially in F29, indicating that this LCS has the most organized structure. Mechanical and bioadhesive properties of GTE-unloaded and -loaded LCS corroborated the rheological data, showing that F29 had the highest mechanical and bioadhesive values. Finally, in vivo inflammation assay revealed that the less elastic and consistent LCS, F25E and F32E presented statistically the same anti-inflammatory activity compared to the positive control, decreasing significantly the paw edema after 4 h; whereas, the most structured and elastic LCS, F29E, strongly limited the potential effects of GTE. Thereby, the

  12. Self-assembled liquid crystalline nanoparticles as an ophthalmic drug delivery system. Part II: optimization of formulation variables using experimental design.

    Science.gov (United States)

    Achouri, Djamila; Sergent, Michelle; Tonetto, Alain; Piccerelle, Philippe; Andrieu, Véronique; Hornebecq, Virginie

    2015-03-01

    In the field of keratoconus treatment, a lipid-based liquid crystal nanoparticles system has been developed to improve the preocular retention and ocular bioavailability of riboflavin, a water-soluble drug. The formulation of this ophthalmic drug delivery system was optimized by a simplex lattice experimental design. The delivery system is composed of three main components that are mono acyl glycerol (monoolein), poloxamer 407 and water and two secondary components that are riboflavin and glycerol (added to adjust the osmotic pressure). The amounts of these three main components were selected as the factors to systematically optimize the dependent variables that are the encapsulation efficiency and the particle size. In this way, 12 formulas describing experimental domain of interest were prepared. Results obtained using small angle X-rays scattering (SAXS) and cryo-transmission electron microscopy (cryo-TEM) evidenced the presence of nano-objects with either sponge or hexagonal inverted structure. In the zone of interest, the percentage of each component was determined to obtain both high encapsulation efficiency and small size of particles. Two optimized formulations were found: F7 and F1. They are very close in the ternary phase diagram as they contain 6.83% of poloxamer 407; 44.18% and 42.03% of monoolein; 46.29% and 48.44% of water for F7 and F11, respectively. These formulations displayed a good compromise between inputs and outputs investigated.

  13. Mesoporous silica nanoparticles synthesized from liquid crystal display manufacturing extracts as a potential candidate for a drug delivery carrier: evaluation of their safety and biocompatibility

    Directory of Open Access Journals (Sweden)

    Lin YC

    2013-10-01

    Full Text Available Yu-Chih Lin,1 Liang-Yi Lin,2 Ming-Yi Gao,3 Yi-Ping Fang31Department of Environmental Engineering and Health, Yuanpei University, 2Institute of Environmental Engineering, National Chiao Tung University, 3Department of Biotechnology, Yuanpei University, Hsinchu, TaiwanAbstract: Mesoporous silica nanoparticles (MSNs were synthesized as a promising drug delivery carrier due to the large surface area and porous characteristics. Our previous study successfully recycled wastes from the liquid crystal display (LCD industry as the silica precursor. In this study, we substantiated the possibility of applying this material as a drug carrier. MSNs synthesized from the extraction of wastes from the manufacture of LCD panels were characterized as having an average diameter of 100 nm, a surface area of 788 m2/g, a uniform pore size distribution of 3.8 nm, and a pore volume of up to 1.04 cm3/g. Methotrexate and camptothecin were entrapped in MSNs at about 33.88% and 75.12%, respectively. The cell viability assay demonstrated that MSNs at 1 µg/mL had no significant influence on human lung fibroblast (WI-38 cells or ovarian cancer (ES-2 cells. A lactate dehydrogenase assay also indicated no inflammation occurred. Moreover, a hemolytic erythrocyte test indicated that the dose range of <100 µg/mL showed that 5% of erythrocytes were affected. After exposure to biofluids, the ordered structure was slightly degraded. The results revealed that MSNs synthesized from extraction of wastes from the manufacture of LCD panels had a good entrapment capacity for hydrophobic drugs and controllable safety conditions; they may be applied as a drug delivery carrier.Keywords: mesoporous silica nanoparticles (MSNs, waste recycle, drug delivery carrier, safety, biocompatibility

  14. A novel in-situ-gelling liquid suppository for site-targeting delivery of anti-colorectal cancer drugs.

    Science.gov (United States)

    Lin, Hong-Ru; Tseng, Chao-Chih; Lin, Yiu-Jiuan; Ling, Ming-Hung

    2012-01-01

    In order to avoid anti-cancer drugs undergoing a first-pass effect and reduce their toxicity, and to solve conventional suppositories defects, we developed an in-situ-gelling and injectable Pluronic-poly(acrylic acid) (Pluronic-PAA) liquid suppository, which could gel fast in the physiological state and had suitable gel strength and bioadhesive force. The liquid suppositories were inserted into the rectum of rabbits without difficulty and leakage, and retained in the rectum for at least 6 h and while releasing the drug. The toxicity and cytotoxic tests indicated that Pluronic and PAA were non-toxic materials and could inhibit colon cancer cells when oxaliplatin was incorporated. C max and AUC0→12h values of oxaliplatin after rectal administration of a oxaliplatin suppository were higher than those for an oxaliplatin solution administered orally. These results suggest that an in-situ-gelling and injectable liquid suppository for humans can be further developed as a more convenient and effective rectal dosage form.

  15. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  16. Superhydrophobic perfluorinated metal-organic frameworks.

    Science.gov (United States)

    Chen, Teng-Hao; Popov, Ilya; Zenasni, Oussama; Daugulis, Olafs; Miljanić, Ognjen Š

    2013-08-07

    Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

  17. Chemically crosslinked isoreticular metal-organic frameworks.

    Science.gov (United States)

    Allen, Corinne A; Boissonnault, Jake A; Cirera, Jordi; Gulland, Ryan; Paesani, Francesco; Cohen, Seth M

    2013-04-21

    Herein we report the synthesis of canonical isoreticular metal-organic frameworks (IRMOFs) containing interligand crosslinks. Chemically crosslinking two molecules of 2-amino-1,4-benzene dicarboxylic acid (NH2-BDC) gives ligands that readily form IRMOF-1 analogs, producing crosslinked MOFs that may be designed to have novel properties.

  18. Nets, tiles, and metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Michael O’Keeffe

    2014-12-01

    Full Text Available An account is given of the basic nets that are important in the description and design of metal-organic framework (MOF structures. These are generally of minimal transitivity, a concept which is explained. Derived nets are defined and the advantages of using derived nets to describe the topology of MOF frameworks with multiple branch points are emphasized.

  19. Recent applications of metal-organic frameworks in sample pretreatment.

    Science.gov (United States)

    Wang, Yonghua; Rui, Min; Lu, Guanghua

    2017-06-19

    Metal-organic frameworks are promising materials in diverse analytical applications especially in sample pretreatment by virtue of their diverse structure topology, tunable pore size, permanent nanoscale porosity, high surface area, and good thermostability. According to hydrostability, metal-organic frameworks are divided into moisture-sensitive and water-stable types. In the actual applications, both kinds of metal-organic frameworks are usually engineered into hybrid composites containing magnetite, silicon dioxide, graphene, or directly carbonized to metal-organic frameworks derived carbon. These metal-organic frameworks based materials show good extraction performance to environmental pollutants. This review provides a critical overview of the applications of metal-organic frameworks and their composites in sample pretreatment modes, that is, solid-phase extraction, magnetic solid-phase extraction, micro-solid-phase extraction, solid-phase microextraction, and stir bar solid extraction. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A porphyrin-based metal-organic framework as a pH-responsive drug carrier

    Science.gov (United States)

    Lin, Wenxin; Hu, Quan; Jiang, Ke; Yang, Yanyu; Yang, Yu; Cui, Yuanjing; Qian, Guodong

    2016-05-01

    A low cytotoxic porphyrin-based metal-organic framework (MOF) PCN-221, which exhibited high PC12 cell viability via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay, was selected as an oral drug carrier. Methotrexate (MTX) was chosen as the model drug molecule which was absorbed into inner pores and channels of MOFs by diffusion. PCN-221 showed high drug loading and sustained release behavior under physiological environment without "burst effect". The controlled pH-responsive release of drugs by PCN-221 revealed its promising application in oral drug delivery.

  1. Stealth, biocompatible monoolein-based lyotropic liquid crystalline nanoparticles for enhanced aloe-emodin delivery to breast cancer cells: in vitro and in vivo studies.

    Science.gov (United States)

    Freag, May S; Elnaggar, Yosra Sr; Abdelmonsif, Doaa A; Abdallah, Ossama Y

    Recently, research has progressively highlighted on clues from conventional use of herbal medicines to introduce new anticancer drugs. Aloe-emodin (AE) is a herbal drug with promising anticancer activity. Nevertheless, its clinical utility is handicapped by its low solubility. For the first time, this study aims to the fabrication of surface-functionalized polyethylene glycol liquid crystalline nanoparticles (PEG-LCNPs) of AE to enhance its water solubility and enable its anticancer use. Developed AE-PEG-LCNPs were optimized via particle size and zeta potential measurements. Phase behavior, solid state characteristics, hemocompatibility, and serum stability of LCNPs were assessed. Sterile formulations were developed using various sterilization technologies. Furthermore, the potential of the formulations was investigated using cell culture, pharmacokinetics, biodistribution, and toxicity studies. AE-PEG-LCNPs showed particle size of 190 nm and zeta potential of -49.9, and PEGylation approach reduced the monoolein hemolytic tendency to 3% and increased the serum stability of the nanoparticles. Sterilization of liquid and lyophilized AE-PEG-LCNPs via autoclaving and γ-radiations, respectively, insignificantly affected the physicochemical properties of the nanoparticles. Half maximal inhibitory concentration of AE-PEG-LCNPs was 3.6-fold lower than free AE after 48 hours and their cellular uptake was threefold higher than free AE after 24-hour incubation. AE-PEG-LCNPs presented 5.4-fold increase in t1/2 compared with free AE. Biodistribution and toxicity studies showed reduced AE-PEG-LCNP uptake by reticuloendothelial system organs and good safety profile. PEGylated LCNPs could serve as a promising nanocarrier for efficient delivery of AE to cancerous cells.

  2. Ultrasonically enhanced delivery and degradation of PAHs in a polymer-liquid partitioning system by a microbial consortium.

    Science.gov (United States)

    Isaza, Pedro A; Daugulis, Andrew J

    2009-09-01

    The current study examined the effects of ultrasonic irradiation on mass transfer and degradation of PAHs, by an enriched consortium, when delivered from polymeric matrices. Rates of release into methanol under sonicated conditions, relative to unmixed cases, for phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene were increased approximately fivefold, when delivered from Desmopan 9370 A (polyurethane). Similar effects were observed in Hytrel and Kraton D4150 K polymers as well as recycled Bridgestone tires. Enhancements were also displayed as shifts to higher release equilibria under sonicated conditions, relative to non-sonicated cases, agreeing with current knowledge in sonochemistry and attributed to cavitation. Ultrasonic effects on microbial activity were also investigated and cell damage was found to be non- permanent with consortium re-growth being observed after sonic deactivation. Finally, the lumped effect of sonication on degradation of phenanthrene delivered from Desmopan was examined under the absence and presence of sonication. Rates of degradation were found to be increased by a factor of four demonstrating the possibility of using ultrasonic irradiation for improved mass transport in solid-liquid systems. Cellular inactivation effects were not evident, and this was attributed to the attenuation of sonic energy arising from the presence of solid polymer materials in the medium. The findings of the study demonstrate that sonication can be used to improve mass transport of poorly soluble compounds in microbial degradations, and alleviate limiting steps of soil remediation processes proposed in previous research.

  3. Heteroepitaxial growth of 3-5 semiconductor compounds by metal-organic chemical vapor deposition for device applications

    Science.gov (United States)

    Collis, Ward J.; Abul-Fadl, Ali

    1988-01-01

    The purpose of this research is to design, install and operate a metal-organic chemical vapor deposition system which is to be used for the epitaxial growth of 3-5 semiconductor binary compounds, and ternary and quaternary alloys. The long-term goal is to utilize this vapor phase deposition in conjunction with existing current controlled liquid phase epitaxy facilities to perform hybrid growth sequences for fabricating integrated optoelectronic devices.

  4. An Ultra-High Performance Liquid Chromatographic-Tandem Mass Spectrometric Method for the Determination of Sinomenine in Human Plasma after Transdermal Delivery of the Zhengqing Fengtongning Injection

    Directory of Open Access Journals (Sweden)

    Tingbo Chen

    2015-04-01

    Full Text Available A sensitive, precise and selective ultra-high performance liquid chromatography method coupled with triple-quadrupole mass spectrometry was developed and validated for the determination of trace amounts of sinomenine (ng/mL in minute volumes of human plasma. Fifty microliter plasma samples were precipitated using methanol to extract sinomenine. Separation was carried out on a C18 column with a water and acetonitrile mobile phase gradient with formic acid as an additive. The mass spectrometry data were obtained in the positive ion mode, and the transition of multiple reactions was monitored at m/z 330.2→181.0 for sinomenine quantification. The working assay range for sinomenine was linear from 0.1173 to 15.02 ng/mL with the lower limit of quantification of 0.1173 ng/mL. The precision and accuracy of the method was less than 15% in intra-day and inter-day experiments with a matrix effect of less than 6.5%. After validation, the quantitative method was applied to analyze sinomenine levels in human plasma after transdermal delivery of the Zhengqing Fengtongning Injection. The results showed that some samples contained sinomenine within the concentration range 0.4131–4.407 ng/mL.

  5. Minerals with metal-organic framework structures

    Science.gov (United States)

    Huskić, Igor; Pekov, Igor V.; Krivovichev, Sergey V.; Friščić, Tomislav

    2016-01-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals. PMID:27532051

  6. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  7. Metal-organic framework composites: from fundamentals to applications

    Science.gov (United States)

    Li, Shaozhou; Huo, Fengwei

    2015-04-01

    Metal-organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.

  8. Liquid Ventilation

    Directory of Open Access Journals (Sweden)

    Qutaiba A. Tawfic

    2011-01-01

    Full Text Available Mammals have lungs to breathe air and they have no gills to breath liquids. When the surface tension at the air-liquid interface of the lung increases, as in acute lung injury, scientists started to think about filling the lung with fluid instead of air to reduce the surface tension and facilitate ventilation. Liquid ventilation (LV is a technique of mechanical ventilation in which the lungs are insufflated with an oxygenated perfluorochemical liquid rather than an oxygen-containing gas mixture. The use of perfluorochemicals, rather than nitrogen, as the inert carrier of oxygen and carbon dioxide offers a number of theoretical advantages for the treatment of acute lung injury. In addition, there are non-respiratory applications with expanding potential including pulmonary drug delivery and radiographic imaging. The potential for multiple clinical applications for liquid-assisted ventilation will be clarified and optimized in future. Keywords: Liquid ventilation; perfluorochemicals; perfluorocarbon; respiratory distress; surfactant.

  9. Zeolite-like metal-organic frameworks (ZMOFs) based on the directed assembly of finite metal-organic cubes (MOCs).

    Science.gov (United States)

    Alkordi, Mohamed H; Brant, Jacilynn A; Wojtas, Lukasz; Kravtsov, Victor Ch; Cairns, Amy J; Eddaoudi, Mohamed

    2009-12-16

    Two zeolite-like metal-organic frameworks (ZMOFs) with lta- and ast- topologies, zeolitic nets that can be interpreted as augmented edge-transitive 8-connected nets, are targeted through directed self-assembly of metal-organic cubes (MOCs) as supermolecular building blocks (SBBs).

  10. Biomimicry in metal-organic materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, MW; Gu, ZY; Bosch, M; Perry, Z; Zhou, HC

    2015-06-15

    Nature has evolved a great number of biological molecules which serve as excellent constructional or functional units for metal-organic materials (MOMs). Even though the study of biomimetic MOMs is still at its embryonic stage, considerable progress has been made in the past few years. In this critical review, we will highlight the recent advances in the design, development and application of biomimetic MOMs, and illustrate how the incorporation of biological components into MOMs could further enrich their structural and functional diversity. More importantly, this review will provide a systematic overview of different methods for rational design of MOMs with biomimetic features. Published by Elsevier B.V.

  11. Hydrogen storage in metal-organic frameworks.

    Science.gov (United States)

    Hu, Yun Hang; Zhang, Lei

    2010-05-25

    Metal-organic frameworks (MOFs) are highly attractive materials because of their ultra-high surface areas, simple preparation approaches, designable structures, and potential applications. In the past several years, MOFs have attracted worldwide attention in the area of hydrogen energy, particularly for hydrogen storage. In this review, the recent progress of hydrogen storage in MOFs is presented. The relationships between hydrogen capacities and structures of MOFs are evaluated, with emphasis on the roles of surface area and pore size. The interaction mechanism between H(2) and MOFs is discussed. The challenges to obtain a high hydrogen capacity at ambient temperature are explored.

  12. Epitaxially grown metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Hartmut Gliemann

    2012-03-01

    Full Text Available The functionalization of inorganic and organic surfaces is becoming a key issue in a vast number of technical applications. The present review will focus on a particularly attractive route for surface functionalization via the coating of substrates with ordered, highly-porous, self-assembling layers of metal-organic frameworks. Loading the nm-sized pores of these molecular scaffolds with molecules, clusters, and nanoparticles creates many opportunities for using these flexible, three-dimensional shelf systems as storage material, for developing highly specific sensors, catalysts and electronic devices, as well as implementing optical metamaterials.

  13. Zeolite-like metal-organic frameworks with ana topology

    KAUST Repository

    Eddaoudi, Mohamed

    2017-04-20

    Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X(solvent)a]n wherein MIII comprises a trivalent cation of a rare earth element, X comprises an alkali metal element or alkaline earth metal element, and solvent comprises a guest molecule occupying pores. Embodiments of the present disclosure describe a method of separating paraffins comprising contacting a zeolite-like metal-organic framework with ana topology with a flow of paraffins, and separating the paraffins by size.

  14. Buccal drug delivery.

    Science.gov (United States)

    Smart, John D

    2005-05-01

    Buccal formulations have been developed to allow prolonged localised therapy and enhanced systemic delivery. The buccal mucosa, however, while avoiding first-pass effects, is a formidable barrier to drug absorption, especially for biopharmaceutical products (proteins and oligonucleotides) arising from the recent advances in genomics and proteomics. The buccal route is typically used for extended drug delivery, so formulations that can be attached to the buccal mucosa are favoured. The bioadhesive polymers used in buccal drug delivery to retain a formulation are typically hydrophilic macro-molecules containing numerous hydrogen bonding groups. Newer second-generation bioadhesives have been developed and these include modified or new polymers that allow enhanced adhesion and/or drug delivery, in addition to site-specific ligands such as lectins. Over the last 20 years a wide range of formulations has been developed for buccal drug delivery (tablet, patch, liquids and semisolids) but comparatively few have found their way onto the market. Currently, this route is restricted to the delivery of a limited number of small lipophilic molecules that readily cross the buccal mucosa. However, this route could become a significant means for the delivery of a range of active agents in the coming years, if the barriers to buccal drug delivery are overcome. In particular, patient acceptability and the successful systemic delivery of large molecules (proteins, oligonucleotides and polysaccharides) via this route remains both a significant opportunity and challenge, and new/improved technologies may be required to address these.

  15. A novel needleless liquid jet injection methodology for improving direct cardiac gene delivery: An optimization of parameters, AAV mediated therapy and investigation of host responses in ischemic heart failure

    Science.gov (United States)

    Fargnoli, Anthony Samuel

    Heart disease remains the leading cause of mortality and morbidity worldwide, with 22 million new patients diagnosed annually. Essentially, all present therapies have significant cost burden to the healthcare system, yet fail to increase survival rates. One key employed strategy is the genetic reprogramming of cells to increase contractility via gene therapy, which has advanced to Phase IIb Clinical Trials for advanced heart failure patients. It has been argued that the most significant barrier preventing FDA approval are resolving problems with safe, efficient myocardial delivery, whereby direct injection in the infarct and remote tissue areas is not clinically feasible. Here, we aim to: (1) Improve direct cardiac gene delivery through the development of a novel liquid jet device approach (2) Compare the new method against traditional IM injection with two different vector constructions and evaluate outcome (3) Evaluate the host response resulting from both modes of direct cardiac injection, then advance a drug/gene combination with controlled release nanoparticle formulations.

  16. [Metal-Organic Frameworks: A New Class of Mesoporous Materials and Potential Possibilities of Their Use in Pharmaceutical Technology].

    Science.gov (United States)

    Wyszogrodzka, Gabriela; Dorożyński, Przemysław

    2015-01-01

    Metal-organic frameworks (MOFs) belong to the new class of mesoporous, hybrid materials composed of metal ions and organic binding ligands. Their unique features: wide range of chemical building components, which enables obtaining biocompatible materials, and high surface area and loading capacity, make them promising drug delivery vehicles for therapeutic agents. The ability to tune their structures and porosities provides better adjustment for adsorbed drug molecule. Moreover, MOFs functionalized with ligands or antibodies can be used in cancer targeted therapy. Through the incorporation of paramagnetic metal ions into the structure, MOFs are suited to serve as magnetic resonance imaging (MRI) contrast agents. Combining drug delivery ability with imaging properties of MOFs indicates their potential use as theranostic agents and makes possible monitoring drug delivery within the body after administration in the real time. The aim of the present study is to characterize a new class of compounds and to present potential possibilities of their use as excipients in pharmaceutical technology .

  17. Porous materials: Lining up metal-organic frameworks

    Science.gov (United States)

    Champness, Neil R.

    2017-03-01

    A new report demonstrates an innovative approach to aligning crystallites of metal-organic frameworks such that thin films are created with oriented channels -- potentially overcoming one of the major barriers to application of these highly topical materials.

  18. Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

    Science.gov (United States)

    Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; Mattson, Eric C.; Veyan, Jean-François; Wang, Hao; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

    2016-12-01

    The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk--as is typically done to enhance adsorption--here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO2, SO2, C2H4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. These findings may provide alternative strategies for gas storage, delivery and separation.

  19. Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

    Science.gov (United States)

    Albo, Jonathan; Vallejo, Daniel; Beobide, Garikoitz; Castillo, Oscar; Castaño, Pedro; Irabien, Angel

    2017-03-22

    The electrocatalytic reduction of CO2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu3 (μ6 -C9 H3 O6 )2 ]n ; (2) CuAdeAce MOF, [Cu3 (μ3 -C5 H4 N5 )2 ]n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C2 H2 N2 S2 )]n ; and (4) CuZnDTA MOA, [Cu0.6 Zn0.4 (μ-C2 H2 N2 S2 )]n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm(-2) , an electrolyte-flow/area ratio of 3 mL min cm(-2) , and a gas-flow/area ratio of 20 mL min cm(-2) . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Substitution reactions in metal-organic frameworks and metal-organic polyhedra.

    Science.gov (United States)

    Han, Yi; Li, Jian-Rong; Xie, Yabo; Guo, Guangsheng

    2014-08-21

    Substitution reaction, as one of the most powerful and efficient chemical reactions, has been widely used in various syntheses, including those for the design and preparation of functional molecules or materials. In the past decade, a class of newly developed inorganic-organic hybrid materials, namely metal-organic materials (MOMs), has experienced a rapid development. MOMs are composed of metal-containing nodes connected by organic linkers through strong chemical bonds, and can be divided into metal-organic frameworks (MOFs) and metal-organic polygons/polyhedra (MOPs) with infinite and discrete structural features, respectively. Recent research has shown that the substitution reaction can be used as a new strategy in the synthesis and modification of MOFs and MOPs, particularly for pre-designed ones with desired structures and functions, which are usually difficult to access by a direct one-pot self-assembly synthetic approach. This review highlights the implementation of the substitution reaction in MOFs and MOPs. Examples of substitution reactions at metal ions, organic ligands, and free guest molecules of MOFs and MOPs are listed and analyzed. The changes or modifications in the structures and/or properties of these materials induced by the substitutions, as well as the nature of the associated reaction, are discussed, with the conclusion that the substitution reaction is really feasible and powerful in synthesizing and tailoring MOMs.

  1. Redox-promoted associative assembly of metal-organic materials.

    Science.gov (United States)

    Glavinović, Martin; Qi, Feng; Katsenis, Athanassios D; Friščić, Tomislav; Lumb, Jean-Philip

    2016-01-01

    We develop an associative synthesis of metal-organic materials that combines solid-state metal oxidation and coordination-driven self-assembly into a one-step, waste-free transformation. The methodology hinges on the unique reactivity of ortho-quinones, which we introduce as versatile oxidants for mechanochemical synthesis. Our strategy opens a previously unexplored route to paramagnetic metal-organic materials from elementary metals.

  2. Multi-responsive metal-organic lantern cages in solution.

    Science.gov (United States)

    Brega, Valentina; Zeller, Matthias; He, Yufan; Lu, H Peter; Klosterman, Jeremy K

    2015-03-25

    Soluble copper-based M4L4 lantern-type metal-organic cages bearing internal amines were synthesized. The solution state integrity of the paramagnetic metal-organic cages was demonstrated using NMR, DLS, MS, and AFM spectroscopy. 1D supramolecular pillars of pre-formed cages or covalent host-guest complexes selectively formed upon treatment with 4,4'-bipyridine and acetic anhydride, respectively.

  3. Metal-organic frameworks for photocatalysis.

    Science.gov (United States)

    Li, Ying; Xu, Hua; Ouyang, Shuxin; Ye, Jinhua

    2016-03-21

    Photocatalysis is a promising technology to convert solar energy into chemical energy. Recently, metal-organic frameworks (MOFs) have emerged as novel photocatalysts owing to their inherent structural characteristics of a large surface area and a well-ordered porous structure. Most importantly, via modulation of the organic linker/metal clusters or incorporation with metal/complex catalysts, not only the reactant adsorption and light absorption but also the charge separation and reactant activation will be largely promoted, leading to superior photocatalytic performance. In this article, we will first introduce the photophysical/chemical properties of MOFs; then various strategies of modification of MOFs towards better photocatalytic activity will be presented; finally, we will address the challenge and further perspective in MOF-based photocatalysis.

  4. Multifunctional Metal-Organic Frameworks for Photocatalysis.

    Science.gov (United States)

    Wang, Sibo; Wang, Xinchen

    2015-07-01

    Metal-organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO2 reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world-wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF-involved solar-to-chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co-catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.

  5. Emerging Multifunctional Metal-Organic Framework Materials.

    Science.gov (United States)

    Li, Bin; Wen, Hui-Min; Cui, Yuanjing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2016-10-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The role of metal-organic frameworks in a carbon-neutral energy cycle

    Science.gov (United States)

    Schoedel, Alexander; Ji, Zhe; Yaghi, Omar M.

    2016-04-01

    Reducing society's reliance on fossil fuels presents one of the most pressing energy and environmental challenges facing our planet. Hydrogen, methane and carbon dioxide, which are some of the smallest and simplest molecules known, may lie at the centre of solving this problem through realization of a carbon-neutral energy cycle. Potentially, this could be achieved through the deployment of hydrogen as the fuel of the long term, methane as a transitional fuel, and carbon dioxide capture and sequestration as the urgent response to ongoing climate change. Here we detail strategies and technologies developed to overcome the difficulties encountered in the capture, storage, delivery and conversion of these gas molecules. In particular, we focus on metal-organic frameworks in which metal oxide ‘hubs’ are linked with organic ‘struts’ to make materials of ultrahigh porosity, which provide a basis for addressing this challenge through materials design on the molecular level.

  7. Metal-organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials

    Science.gov (United States)

    Wang, Cheng; Liu, Demin

    2013-01-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting class of crystalline molecular materials that are synthesized by combining metal-connecting points and bridging ligands. The modular nature of and mild conditions for MOF synthesis have permitted the rational structural design of numerous MOFs and the incorporation of various functionalities via constituent building blocks. The resulting designer MOFs have shown promise for applications in a number of areas, including gas storage/separation, nonlinear optics/ferroelectricity, catalysis, energy conversion/storage, chemical sensing, biomedical imaging, and drug delivery. The structure-property relationships of MOFs can also be readily established by taking advantage of the knowledge of their detailed atomic structures, which enables fine-tuning of their functionalities for desired applications. Through the combination of molecular synthesis and crystal engineering MOFs thus present an unprecedented opportunity for the rational and precise design of functional materials. PMID:23944646

  8. Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release

    Science.gov (United States)

    Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

    2016-01-01

    Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future. PMID:27493996

  9. Anisotropic thermal expansion in a metal-organic framework.

    Science.gov (United States)

    Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-06-01

    Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

  10. Adsorptive desulfurization and denitrogenation using metal-organic frameworks.

    Science.gov (United States)

    Ahmed, Imteaz; Jhung, Sung Hwa

    2016-01-15

    With the increasing worldwide demand for energy, utilization of fossil fuels is increasing proportionally. Additionally, new and unconventional energy sources are also being utilized at an increasing rate day-by-day. These sources, along with some industrial processes, result in the exposal of several sulfur- and nitrogen-containing compounds (SCCs and NCCs, respectively) to the environment, and the exposure is one of the greatest environmental threats in the recent years. Although, several methods were established for the removal of these pollutants during the last few decades, recent advancements in adsorptive desulfurization and denitrogenation (ADS and ADN, respectively) with metal-organic frameworks (MOFs) make this the most promising and remarkable method. Therefore, many research groups are currently involved with ADS and ADN with MOFs, and the results are improving gradually by modifying the MOF adsorbents according to several specific adsorption mechanisms. In this review, ADS and ADN studies are thoroughly discussed for both liquid-phase and gas-phase adsorption. The MOF modification procedures, which are important for improved adsorption, are also described. To improve the knowledge among the scientific community, it is very important to understand the detailed chemistry and mechanism involved in a chemical process, which also creates the possibility and pathway for further developments in research and applications. Therefore, the mechanisms related to the adsorption procedures are also discussed in detail. From this review, it can be expected that the scientific community will obtain an understanding of the current state of ADS and ADN, their importance, and some encouragement and insight to take the research knowledge base to a higher level.

  11. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  12. Inelastic neutron scattering study of binding of para-hydrogen in an ultra-microporous metal-organic framework

    OpenAIRE

    Yang, Sihai; Ramirez - Cuesta, Anibal J.; Schröder, Martin

    2014-01-01

    Metal-organic framework (MOF) materials show promise for H2 storage and it is widely predicted by computational modelling that MOFs incorporating ultra-micropores are optimal for H2 binding due to enhanced overlapping potentials. We report the investigation using inelastic neutron scattering of the interaction of H2 in an ultra-microporous MOF material showing low H2 uptake capacity. The study has revealed that adsorbed H2 at 5 K has a liquid recoil motion along the channel with very little i...

  13. The Dam Bursts for Porous Liquids.

    Science.gov (United States)

    James, Stuart L

    2016-07-01

    In 2007 the idea was put forward that, through careful molecular design, it should be possible to synthesize liquids which contain permanent, well-defined molecule-sized cavities (pores). Such "porous liquids" could be a kind of liquid zeolite, or liquid MOF (metal-organic framework), exhibiting the size and shape-selective sorption (or dissolution) associated with microporous solids as well as the fluidity of liquids - a new and potentially useful combination of properties. However, these materials remained essentially hypothetical until recently. In 2014 and 2015 three papers were published which describe convincing examples of porous liquids, and studies have shown that they do exhibit some remarkable properties, such as very fast gas diffusion and high gas solubilities. The examples reported so far are almost certainly only the tip of the iceberg. Now that porous liquids are 'real', a new area of materials science may open up, with clear potential for long-term applications in chemical processes.

  14. Delivery presentations

    Science.gov (United States)

    ... passage will take place depends on how your baby is positioned during delivery. The best position for the baby to be ... possible, but labor will generally take longer. After delivery, the baby's face or brow will be swollen and may ...

  15. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Long, Jeffrey R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  16. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    Science.gov (United States)

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.

  17. Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

    Science.gov (United States)

    Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

    2014-10-10

    Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Lanthanide Metal-Organic Framework Materials

    Science.gov (United States)

    Hsieh, Ping-Yen; Green, Mark A.; Briber, Robert M.

    2009-03-01

    A series of lanthanide metal-organic framework materials (MOF) with variable organic linkages including benzene-dicarboxylic acid (BDC); 1,3,5-benzene-tricarboxylic acid (BTC); and 1,3,5-tris(4-carboxyphenyl)benzene (BTB) have been synthesized. The low density and high porosity of MOFs make them candidates molecular sieve or hydrogen storage materials. The crystal structures have been determined using a combination of single crystal X-ray diffractometer and synchrotron powder X-ray diffraction work. Holmium with the BDC ligand material (Ho-BDC) crystallizes in a monoclinic C2/c space group, with lattice parameters of a = 17.06 å, b = 10.67 å, c = 10.57 å, b = 96.12^o. The crystal structure of Ho-BTC is in tetragonal P 41 2 2 space group and Ho-BTB is in a triclinic P-1 space group. A comprehensive examination of Ho-MOF with different ligands by x-ray and thermogravimetric analysis shows that there is a stable nanoporous structure for dehydrated Ho-BTC up to 250^oC. The same phenomenon is not observed in the Ho-BDC and Ho-BTB materials. The collapsed structure with BDC and BTB indicates the stability of dehydrated samples is strongly related to the interactions between the metal and the organic linkers.

  19. Ultrahigh porosity in metal-organic frameworks.

    Science.gov (United States)

    Furukawa, Hiroyasu; Ko, Nakeun; Go, Yong Bok; Aratani, Naoki; Choi, Sang Beom; Choi, Eunwoo; Yazaydin, A Ozgür; Snurr, Randall Q; O'Keeffe, Michael; Kim, Jaheon; Yaghi, Omar M

    2010-07-23

    Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.

  20. Thermodynamics of metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Di; Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu

    2015-03-15

    Although there have been extensive studies over the past decade in the synthesis and application of metal-organic frameworks (MOFs), investigation of their thermodynamic stability and of the energetics of guest–host interactions has been much more limited. This review summarizes recent progress in experimental (calorimetric) determination of the thermodynamics of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorganic and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5–30 kJ per mole of tetrahedra in zeolites and mesoporous silicas or per mole of metal in MOFs. Thus strong thermodynamic instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small molecule–MOF interactions with defined chemical binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest–host interactions. - Graphical abstract: Energy landscape of inorganic and hybrid porous materials. - Highlights: • Thermochemical data on various MOF structures were experimentally determined. • MOFs are moderately unstable relative to their dense phase assemblage. • Overall energetic landscape of porous materials was revealed. • Guest–host interactions in MOFs were evaluated directly using calorimetry. • Confinement effect and defined chemical binding lead to strong interactions.

  1. Inorganic nanocarriers for platinum drug delivery

    Directory of Open Access Journals (Sweden)

    Ping’an Ma

    2015-12-01

    Full Text Available Nowadays platinum drugs take up almost 50% of all the clinically used anticancer drugs. Besides cisplatin, novel platinum agents including sterically hindered platinum (II drugs, chemically reductive platinum (IV drugs, photosensitive platinum (IV drugs, and multinuclear platinum drugs have been developed recently, with a few entering clinic trials. Rapid development of nanobiotechnology makes targeted delivery of anticancer platinum agents to the tumor site possible, while simultaneously minimizing toxicity and maximizing the drug efficacy. Being versatile drug carriers to deliver platinum drugs, inorganic nanovehicles such as gold nanoparticles, iron oxide nanomaterials, carbon nanotubes, mesoporous nanosilica, metal-organic frameworks (MOFs, have been extensively studied over the past decades. In contrast to conventional polymeric and lipid nanoparticles, inorganic nanoparticles based drug carriers are peculiar as they have shown excellent theranostic effects, revealing themselves an indispensable part of future nanomedicine. Here, we will elaborate recent research advances on fabrication of inorganic nanoparticles for platinum drug delivery.

  2. Recent Advances as Materials of Functional Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Xiao-Lan Tong

    2013-01-01

    Full Text Available Metal-organic frameworks (MOFs, also known as hybrid inorganic-organic materials, represent an emerging class of materials that have attracted the imagination of solid-state chemists because MOFs combine unprecedented levels of porosity with a range of other functional properties that occur through the metal moiety and/or the organic ligand. The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of functional metal-organic frameworks, including luminescence, magnetism, and porosity through presenting examples. This review will be of interest to researchers and synthetic chemists attempting to design multifunctional MOFs.

  3. Production of CNT-taxol-embedded PCL microspheres using an ammonium-based room temperature ionic liquid: as a sustained drug delivery system.

    Science.gov (United States)

    Kim, Seong Yeol; Hwang, Ji-Young; Seo, Jae-Won; Shin, Ueon Sang

    2015-03-15

    We describe a one-pot method for the mass production of polymeric microspheres containing water-soluble carbon-nanotube (w-CNT)-taxol complexes using an ammonium-based room temperature ionic liquid. Polycaprolactone (PCL), trioctylmethylammonium chloride (TOMAC; liquid state from -20 to 240°C), and taxol were used, respectively, as a model polymer, room temperature ionic liquid, and drug. Large quantities of white colored PCL powder without w-CNT-taxol complexes and gray colored PCL powders containing w-CNT-taxol (1:1 or 1:2 wt/wt) complexes were produced by phase separation between the hydrophilic TOMAC and the hydrophobic PCL. Both microsphere types had a uniform, spherical structure of average diameter 3-5μm. The amount of taxol embedded in PCL microspheres was determined by HPLC and (1)H NMR to be 8-12μg per 1.0mg of PCL (loading capacity (LC): 0.8-1.2%; entrapment efficiency (EE): 16-24%). An in vitro HPLC release assay showed sustain release of taxol without an initial burst over 60days at an average rate of 0.003-0.0073mg per day. The viability patterns of human breast cancer cells (MCF-7) for PCTx-1 and -2 showed dose-dependent inhibitory effects. In the presence of PCTx-1 and -2, the MCF-7 cells showed high viability in the concentration level of, respectably, <70 and <5μg/mL.

  4. Adsorption on Mesoporous Metal-Organic Frameworks in Solution: Aromatic and Heterocyclic Compounds.

    Science.gov (United States)

    Samokhvalov, Alexander

    2015-11-16

    Adsorption and desorption play major roles in separations, purification of water, waste streams, liquid fuels, catalysis, biomedicine and chromatography. Mesoporous metal-organic frameworks (MOFs) with pore sizes 2-50 nm are particularly suitable for adsorption of organic compounds in solution. Tens of thousands of aromatic and heterocyclic compounds are major components of liquid fuels, feedstock for industrial synthesis, solvents, dyestuffs, agricultural chemicals, medicinal drugs, food additives, and so forth. This Review provides a systematization and analysis of studies on adsorption/desorption on mesoporous MOFs in solution and their underlying chemical mechanisms. The (in)stability of mesoporous MOFs in water is critically discussed. Adsorption capacity and selectivity are covered for organic dyes, medicinal drugs, major components of liquid fuels, and miscellaneous industrial chemicals. Ionic interactions, Brønsted acid-base interactions, hydrogen bonding, coordination bonding, π-π interactions, and non-specific interactions are covered amongst adsorption mechanisms. The effects of post-synthetic modifications of mesoporous MOFs on their stability, adsorption capacity, selectivity, and mechanisms of adsorption and desorption are analyzed. To encourage research in this quickly growing field, we identify "niches" for which no application-oriented and/or mechanistic studies were reported. Perspectives and limitations of a wide use of mesoporous MOFs as industrial sorbents are discussed.

  5. Hydrogen adsorption in metal-organic frameworks: the role of nuclear quantum effects

    CERN Document Server

    Wahiduzzaman, Mohammad; Heine, Thomas

    2014-01-01

    The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H2 -host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory (LDFT) and the Grand-Canonical Monte Carlo (GCMC) methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT). The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLD...

  6. Understanding DABCO Nanorotor Dynamics in Isostructural Metal-Organic Frameworks

    NARCIS (Netherlands)

    Burtch, N.C.; Torres-Knoop, A.; Foo, G.S.; Leisen, J.; Sievers, C.; Ensing, B.; Dubbeldam, D.; Walton, K.S.

    2015-01-01

    Flexible framework dynamics present in the subset of metalorganic frameworks known as soft porous crystals give rise to interesting structural properties that are unique to this class of materials. In this work, we use experiments and molecular simulation to understand the highly dynamic nanorotor b

  7. Hydrogen storage in metal-organic frameworks: A review

    CSIR Research Space (South Africa)

    Langmi, Henrietta W

    2014-05-01

    Full Text Available Metal-organic frameworks (MOFs) for hydrogen storage have continued to receive intense interest over the past decade. MOFs are a class of organic-inorganic hybrid crystalline materials consisting of metallic moieties that are linked by strong...

  8. Kinetic Analysis of the Uptake and Release of Fluorescein by Metal-Organic Framework Nanoparticles

    Science.gov (United States)

    Preiß, Tobias; Zimpel, Andreas; Wuttke, Stefan; Rädler, Joachim O.

    2017-01-01

    Metal-organic framework nanoparticles (MOF NPs) are promising guest-host materials with applications in separation, storage, catalysis, and drug delivery. However, on- and off-loading of guest molecules by porous MOF nanostructures are still poorly understood. Here we study uptake and release of fluorescein by two representative MOF NPs, MIL-100(Fe) and MIL-101(Cr). Suspensions of these MOF NPs exhibit well-defined size distributions and crystallinity, as verified by electron microscopy, dynamic light scattering, and X-ray diffraction. Using absorbance spectroscopy the equilibrium dissociation constants and maximum numbers of adsorbed fluorescein molecules per NP were determined. Time-resolved fluorescence studies reveal that rates of release and loading are pH dependent. The kinetics observed are compared to theoretical estimates that account for bulk diffusion into NPs, and retarded internal diffusion and adsorption rates. Our study shows that, rather than being simple volumetric carriers, MOF-NPs are dominated by internal surface properties. The findings will help to optimize payload levels and develop release strategies that exploit varying pH for drug delivery. PMID:28772575

  9. Kinetic Analysis of the Uptake and Release of Fluorescein by Metal-Organic Framework Nanoparticles

    Directory of Open Access Journals (Sweden)

    Tobias Preiß

    2017-02-01

    Full Text Available Metal-organic framework nanoparticles (MOF NPs are promising guest-host materials with applications in separation, storage, catalysis, and drug delivery. However, on- and off-loading of guest molecules by porous MOF nanostructures are still poorly understood. Here we study uptake and release of fluorescein by two representative MOF NPs, MIL-100(Fe and MIL-101(Cr. Suspensions of these MOF NPs exhibit well-defined size distributions and crystallinity, as verified by electron microscopy, dynamic light scattering, and X-ray diffraction. Using absorbance spectroscopy the equilibrium dissociation constants and maximum numbers of adsorbed fluorescein molecules per NP were determined. Time-resolved fluorescence studies reveal that rates of release and loading are pH dependent. The kinetics observed are compared to theoretical estimates that account for bulk diffusion into NPs, and retarded internal diffusion and adsorption rates. Our study shows that, rather than being simple volumetric carriers, MOF-NPs are dominated by internal surface properties. The findings will help to optimize payload levels and develop release strategies that exploit varying pH for drug delivery.

  10. Solvent exchange in a metal-organic framework single crystal monitored by dynamic in situ X-ray diffraction.

    Science.gov (United States)

    Cox, Jordan M; Walton, Ian M; Bateman, Gage; Benson, Cassidy A; Mitchell, Travis; Sylvester, Eric; Chen, Yu Sheng; Benedict, Jason B

    2017-08-01

    Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamic in situ X-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal-organic framework [Co(AIP)(bpy)0.5(H2O)]·2H2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

  11. Symbiosis of zeolite-like metal-organic frameworks (rho-ZMOF) and hydrogels: Composites for controlled drug release

    KAUST Repository

    Ananthoji, Ramakanth

    2011-01-01

    The design and synthesis of new finely tunable porous materials has spurred interest in developing novel uses in a variety of systems. Zeolites, inorganic materials with high thermal and mechanical stability, in particular, have been widely examined for use in applications such as catalysis, ion exchange and separation. A relatively new class of inorganic-organic hybrid materials known as metal-organic frameworks (MOFs) have recently surfaced, and many have exhibited their efficiency in potential applications such as ion exchange and drug delivery. A more recent development is the design and synthesis of a subclass of MOFs based on zeolite topologies (i.e. ZMOFs), which often exhibit traits of both zeolites and MOFs. Bio-compatible hydrogels already play an important role in drug delivery systems, but are often limited by stability issues. Thus, the addition of ZMOFs to hydrogel formulations is expected to enhance the hydrogel mechanical properties, and the ZMOF-hydrogel composites should present improved, symbiotic drug storage and release for delivery applications. Herein we present the novel composites of a hydrogel with a zeolite-like metal-organic framework, rho-ZMOF, using 2-hydroxyethyl methacrylate (HEMA), 2,3-dihydroxypropyl methacrylate (DHPMA), N-vinyl-2-pyrolidinone (VP) and ethylene glycol dimethacrylate (EGDMA), and the corresponding drug release. An ultraviolet (UV) polymerization method is employed to synthesize the hydrogels, VP 0, VP 15, VP 30, VP 45 and the ZMOF-VP 30 composite, by varying the VP content (mol%). The rho-ZMOF, VP 30, and ZMOF-VP 30 composite are all tested for the controlled release of procainamide (protonated, PH), an anti-arrhythmic drug, in phosphate buffer solution (PBS) using UV spectroscopy. © 2011 The Royal Society of Chemistry.

  12. Forceps Delivery

    Science.gov (United States)

    ... in place to control the advance of your baby's head. Forceps deliveries aren't always successful. If your health care ... com. Accessed June 12, 2015. You and your baby: Prenatal care, labor and delivery, and postpartum care. Washington, D.C.: The American ...

  13. Toxic effect of zinc nanoscale metal-organic frameworks on rat pheochromocytoma (PC12) cells in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Fei, E-mail: paper_mail@126.com [Department of Pharmacy, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Yang, Baochun; Cai, Jing [Department of Pharmacy, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Jiang, Yaodong [Department of Urology, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Xu, Jun [Department of Health Economy Administration, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Wang, Shan [Department of Pharmacy, Winthrop University Hospital, Mineola, NY 11501 (United States)

    2014-04-01

    Highlights: • Metal-organic frameworks (MOFs) represent a newborn family of hybrid materials. • MOFs have already shown promise in a number of biological applications. • The biological applications of MOFs raise concerns for potential cytotoxicity. • Substantial information about MOF's neurotoxicity is still quite scarce. • This study reveals for the first time the interaction of MOFs with neural cells. - Abstract: Metal-organic frameworks (MOFs) possess unique properties desirable for delivery of drugs and gaseous therapeutics, but their uncharacterized interactions with cells raise increasing concerns of their safety in such biomedical applications. We evaluated the adverse effects of zinc nanoscale MOFs on the cell morphology, cytoskeleton, cell viability and expression of neurotrophin signaling pathway-associated GAP-43 protein in rat pheochromocytoma PC12 cells. At the concentration of 25 μg/ml, zinc MOFs did not significantly affect morphology, viability and membrane integrity of the cells. But at higher concentrations (over 100 μg/ml), MOFs exhibited a time- and concentration-dependent cytotoxicity, indicating their entry into the cells via endocytosis where they release Zn{sup 2+} into the cytosol to cause increased intracellular concentration of Zn{sup 2+}. We demonstrated that the toxicity of MOFs was associated with a disrupted cellular zinc homeostasis and down-regulation of GAP-43 protein, which might be the underlying mechanism for the improved differentiation in PC12 cells. These findings highlight the importance of cytotoxic evaluation of the MOFs before their biomedical application.

  14. Imaging of intact MOF-5 nanocrystals by advanced TEM at liquid

    OpenAIRE

    Wiktor, Christian; Turner, Stuart; Zacher, Denise; Fischer, Roland A.; Tendeloo, van, G.

    2012-01-01

    Abstract: First results on the imaging of intact metalorganic framework (MOF) pores in MOF-5 nanocrystals by aberration corrected transmission electron microscopy (TEM) under liquid nitrogen conditions are presented. The applied technique is certainly transferable to other MOF systems, permitting detailed studies of MOF interfaces, MOFnanoparticle interaction and MOF thin films.

  15. Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

    Science.gov (United States)

    Wahiduzzaman, Mohammad; Walther, Christian F. J.; Heine, Thomas

    2014-08-01

    The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H2-host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory and the Grand-Canonical Monte Carlo methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the GC-QLDFT. The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H2 in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18, and MOF-177. Finally, we discuss the evolution of the H2 quantum fluid with increasing pressure and lowering temperature.

  16. Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal-organic framework materials

    Science.gov (United States)

    Gould, Jamie A.; Athwal, Harprit Singh; Blake, Alexander J.; Lewis, William; Hubberstey, Peter; Champness, Neil R.; Schröder, Martin

    2017-01-01

    A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H2L1 (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H2L2 (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and H2L3 (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu2(O2CR)4N2] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H2L3, which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L2)] and the isomers of [Cu(L3)], [Cu(L1)] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L1)] were investigated with N2, CO2 and H2, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO2. [Cu(L1)] displays high H2 adsorption, with the density in the pores approaching that of liquid H2. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  17. The metal-organic framework MIL-101(Cr) as efficient adsorbent in a vortex-assisted dispersive solid-phase extraction of imatinib mesylate in rat plasma coupled with ultra-performance liquid chromatography/mass spectrometry: Application to a pharmacokinetic study.

    Science.gov (United States)

    Qi, Chao; Cai, Qianqian; Zhao, Pan; Jia, Xiuna; Lu, Nan; He, Lu; Hou, Xiaohong

    2016-06-03

    Metal-organic framework MIL-101(Cr) was successfully used as an efficient sorbent in a vortex-assisted dispersive solid-phase extraction (VA-DSPE) and applied for the determination and the pharmacokinetic of imatinib mesylate in rat plasma by UPLC-MS/MS. In the enrichment of imatinib from rat plasma, the analyte was efficiently adsorbed on MIL-101(Cr) and simply recovered by using initial mobile phase (0.1% formic acid-methanol (6:4 v/v)) as elution solvent. Meanwhile, the protein in the plasma samples was excluded from the porous structure of MIL-101(Cr), leading to direct extraction of drug molecule from protein-rich biological samples without any other pretreatment procedure. After being removed, the supernatant was filtered and directly injected into the UPLC-MS/MS for the analysis of the target. The experimental parameters, including nature of MOFs, amount of MIL-101(Cr), pH value of aqueous solution, extraction time, type and volume of elution solvent, were systematically optimized. After VA-DSPE, chromatographic separation was performed on an ACQUITY UPLC(®) BEH C18 column (2.1mm×100mm, 1.7μm) with a 3min gradient elution using 0.1% formic acid and methanol as mobile phase at a flow rate of 0.3mL/min. The detection was accomplished on a tandem mass spectrometer via an electrospray ionization (ESI) source by multiple reaction monitoring (MRM) in the positive ionization mode. The lower limit of quantification of 1ng/mL was achieved and the mean recovery of the analyte was higher than 81.2%. Moreover, computational simulation was primarily applied to predict the adsorption behavior and revealed the molecular interactions and free binding energies between MIL-101(Cr) and imatinib with the molecular modeling method, providing certain explanation of the adsorption mechanism. The originally established pretreatment and detection method has some merits, such as less solvent consumption, easy operation, higher sensitivity and lower matrix effect. And the MIL-101

  18. Liquids and liquid mixtures

    CERN Document Server

    Rowlinson, J S; Baldwin, J E; Buckingham, A D; Danishefsky, S

    2013-01-01

    Liquids and Liquid Mixtures, Third Edition explores the equilibrium properties of liquids and liquid mixtures and relates them to the properties of the constituent molecules using the methods of statistical thermodynamics. Topics covered include the critical state, fluid mixtures at high pressures, and the statistical thermodynamics of fluids and mixtures. This book consists of eight chapters and begins with an overview of the liquid state and the thermodynamic properties of liquids and liquid mixtures, including vapor pressure and heat capacities. The discussion then turns to the thermodynami

  19. An Ising model for metal-organic frameworks

    Science.gov (United States)

    Höft, Nicolas; Horbach, Jürgen; Martín-Mayor, Victor; Seoane, Beatriz

    2017-08-01

    We present a three-dimensional Ising model where lines of equal spins are frozen such that they form an ordered framework structure. The frame spins impose an external field on the rest of the spins (active spins). We demonstrate that this "porous Ising model" can be seen as a minimal model for condensation transitions of gas molecules in metal-organic frameworks. Using Monte Carlo simulation techniques, we compare the phase behavior of a porous Ising model with that of a particle-based model for the condensation of methane (CH4) in the isoreticular metal-organic framework IRMOF-16. For both models, we find a line of first-order phase transitions that end in a critical point. We show that the critical behavior in both cases belongs to the 3D Ising universality class, in contrast to other phase transitions in confinement such as capillary condensation.

  20. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    Science.gov (United States)

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy; Schaef, Herbert T.; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-06-01

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  1. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids.

    Science.gov (United States)

    Nandasiri, Manjula I; Liu, Jian; McGrail, B Peter; Jenks, Jeromy; Schaef, Herbert T; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F; Nune, Satish K

    2016-06-15

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  2. Hydrogen Storage in Microporous Metal-Organic Frameworks

    Science.gov (United States)

    Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed; Vodak, David T.; Kim, Jaheon; O'Keeffe, Michael; Yaghi, Omar M.

    2003-05-01

    Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedicarboxylate) with a cubic three-dimensional extended porous structure adsorbed hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. Inelastic neutron scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules indicates the presence of two well-defined binding sites (termed I and II), which we associate with hydrogen binding to zinc and the BDC linker, respectively. Preliminary studies on topologically similar isoreticular metal-organic framework-6 and -8 (IRMOF-6 and -8) having cyclobutylbenzene and naphthalene linkers, respectively, gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.

  3. Hydrogen storage in Li-doped metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Himsl, D.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2010-12-30

    Porous Metal-Organic Frameworks have been considered as potential materials for solid state hydrogen storage in recent times. In this context their properties like high permanent porosity, large surface area and the ease of chemical modification due their modular assembly are highly attractive. Unfortunately these materials suffer from low physisorption interaction energies with hydrogen and consequently the need for low adsorption temperatures (77 K) to achieve sufficient hydrogen loadings. One possible approach to overcome the outlined problem is the introduction of unsaturated metal sites within the interior MOF surface to strengthen the adsorbate-adsorbent interaction. We established the functionalization with lithiumalkoxide groups via a post-synthetic transformation of pendant hydroxyl groups with a suitable lithium base. Our results show a significant increase of the isosteric heat of adsorption for hydrogen within the lithium-containing material, thus showing that our approach is a promising strategy to make hydrogen storage in Metal-Organic Frameworks more efficient. (orig.)

  4. Thermodynamics of Metal-Organic Frameworks

    Science.gov (United States)

    Hughes, James Thomas

    Metal-Organic Frameworks (MOF) are crystalline nanoporous lattices constructed from the combination of cation and multi-dentate organic molecules. MOFs can display both chemical and thermal robustness while having large surface areas and pore volumes. In addition the modular composition of MOFs allows a degree of design and control of MOF structures. These unique physical properties have attracted wide interest and position MOFs to make meaningful contributions towards many applications, such as adsorption, catalysis, separation, and sensing. Despite the extensive investigative work over the last decade on MOF materials, the initial synthesis is still done by trial and error. Of the identified structures some MOFs are robust while others are fragile. It is unclear what role thermodynamics plays in the formation energies of MOFs and guest molecules interactions within the pores. Better understanding of thermochemical properties of MOFs is critical if MOF synthesis is to obtain true predictive design. To address these questions aqueous solution calorimetry was performed on ten different frameworks in both the as-synthesized and activated state. To understand the structural energetics of MOFs, the heat of formation from dense states (metal oxide and protonated organic linkers) to the open MOF framework was measured. Chapter 2 discusses the new aqueous calorimetry methodology developed to measure the enthalpy of solution for hybrid materials. Chapters 3, 4 and 5 detail the enthalpies of formation from their dense states of the frameworks: (MOF-5, ZIF-zni, ZIF-1, ZIF-3, ZIF-4, ZIF-7, ZIF-8, ZIF-9 and Cu-HKUST-1). These chapters also compare the MOF heat of formation energetics to those of zeolites, zeotypes and mesoporous silica materials. Finding that MOFs are metastable with respect to their dense states (metal oxide and protonated organic), following the current destabilization trend of the main group porous materials. The thermochemical effect of solvent on the MOF

  5. A multistimuli-responsive photochromic metal-organic gel.

    Science.gov (United States)

    Wei, Shi-Chao; Pan, Mei; Li, Kang; Wang, Sujuan; Zhang, Jianyong; Su, Cheng-Yong

    2014-04-02

    A photochromic metal-organic gel with thermo-, photo-, and anion-responsive behavior is obtained. Unusually, heating of the Al-ligand solution leads to gel formation and cooling to room temperature reverses the process to reform the solution. The gel is sensitive to weakly coordinating anions. Additionally, reversible photochromic transformations take place both in the solution and gel states, accompanied by reversibly switched luminescence.

  6. Metal-Organic Frameworks for Thin-Layer Chromatographic Applications.

    Science.gov (United States)

    Schenk, Claudia; Kutzscher, Christel; Drache, Franziska; Helten, Stella; Senkovska, Irena; Kaskel, Stefan

    2017-01-25

    Preparation of thin-layer chromatographic (TLC) plates based on metal-organic frameworks (MOFs) as porous stationary phases is described. DUT-67 (DUT = Dresden University of Technology), a zirconium based MOF, was used in combination with a fluorescent indicator as stationary phase for analyzing a small selection of a wide spectrum of relevant analytes. The successful separation of benzaldehyde from trans-cinnamaldehyde and 4-aminophenol from 2-aminotoluene is reported as a model system using optimized eluent mixtures containing acetic acid.

  7. Cadmium and Zinc Thiolate and Selenolate Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Turner, D.; Stone, K; Stephens, P; Vaid, T

    2010-01-01

    Metal-organic frameworks based on metal-sulfur or metal-selenium bonds are relatively rare; herein we describe the synthesis and structural characterization of several examples, including, for example, [Cd(en){sub 3}][Cd(SC{sub 6}H{sub 4}S){sub 2}], which contains the anionic two-dimensional square-grid network [Cd(SC{sub 6}H{sub 4}S){sub 2}]{sub n}{sup 2n-}.

  8. Cadmium and zinc thiolate and selenolate metal-organic frameworks.

    Science.gov (United States)

    Turner, Dayna L; Stone, Kevin H; Stephens, Peter W; Vaid, Thomas P

    2010-06-07

    Metal-organic frameworks based on metal-sulfur or metal-selenium bonds are relatively rare; herein we describe the synthesis and structural characterization of several examples, including, for example, [Cd(en)3][Cd(SC6H4S)2], which contains the anionic two-dimensional square-grid network [Cd(SC6H4S)2]n(2n-).

  9. Nano-architecture of metal-organic frameworks

    Science.gov (United States)

    Milichko, Valentin A.; Zalogina, Anastasiia; Mingabudinova, Leila R.; Vinogradov, Alexander V.; Ubyivovk, Evgeniy; Krasilin, Andrei A.; Mukhin, Ivan; Zuev, Dmitry A.; Makarov, Sergey V.; Pidko, Evgeny A.

    2017-09-01

    Change the shape and size of materials supports new functionalities never found in the sources. This strategy has been recently applied for porous crystalline materials - metal-organic frameworks (MOFs) to create hollow nanoscale structures or mesostructures with improved functional properties. However, such structures are characterized by amorphous state or polycrystallinity which limits their applicability. Here we follow this strategy to create such nano- and mesostructures with perfect crystallinity and new photonics functionalities by laser or focused ion beam fabrication.

  10. Metal-organic framework for the separation of alkane isomers

    Science.gov (United States)

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  11. Metal-organic framework for the separation of alkane isomers

    Energy Technology Data Exchange (ETDEWEB)

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  12. Perspective: Metal-organic frameworks—Opportunities and challenges

    OpenAIRE

    Rosseinsky, M.J.

    2014-01-01

    The interplay of metal-ligand coordination chemistry with the diverse organic chemistry of the molecular linkers in metal-organic frameworks offers exciting new directions not only in the important area of porous materials, but more generally as a route to control of function by the integration of organic and inorganic components. This makes the current APL Materials issue particularly timely. This Perspective summarises some important aspects of the current state of play.

  13. Perspective: Metal-organic frameworks—Opportunities and challenges

    Directory of Open Access Journals (Sweden)

    M. J. Rosseinsky

    2014-12-01

    Full Text Available The interplay of metal-ligand coordination chemistry with the diverse organic chemistry of the molecular linkers in metal-organic frameworks offers exciting new directions not only in the important area of porous materials, but more generally as a route to control of function by the integration of organic and inorganic components. This makes the current APL Materials issue particularly timely. This Perspective summarises some important aspects of the current state of play.

  14. Redox-Active Metal-Organic Composites for Highly Selective Oxygen Separation Applications

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wen [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Banerjee, Debasis [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Liu, Jian [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Schaef, Herbert T. [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Crum, Jarrod V. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Fernandez, Carlos A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Kukkadapu, Ravi K. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Nie, Zimin [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Nune, Satish K. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Motkuri, Radha K. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Chapman, Karena W. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Hayes, James C. [National Security Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Silvers, Kurt L. [National Security Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Krishna, Rajamani [Van' t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904 1098 XH Amsterdam The Netherlands; McGrail, B. Peter [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Liu, Jun [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Thallapally, Praveen K. [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA

    2016-03-08

    A redox-active metal-organic composite material shows improved and selective O-2 adsorption over N-2 with respect to individual components (MIL-101 and ferrocene). The O-2 sensitivity of the composite material arises due to the formation of maghemite nanoparticles with the pore of the metal-organic framework material.

  15. Nanoporous metal oxides with tunable and nanocrystalline frameworks via conversion of metal-organic frameworks.

    Science.gov (United States)

    Kim, Tae Kyung; Lee, Kyung Joo; Cheon, Jae Yeong; Lee, Jae Hwa; Joo, Sang Hoon; Moon, Hoi Ri

    2013-06-19

    Nanoporous metal oxide materials are ubiquitous in the material sciences because of their numerous potential applications in various areas, including adsorption, catalysis, energy conversion and storage, optoelectronics, and drug delivery. While synthetic strategies for the preparation of siliceous nanoporous materials are well-established, nonsiliceous metal oxide-based nanoporous materials still present challenges. Herein, we report a novel synthetic strategy that exploits a metal-organic framework (MOF)-driven, self-templated route toward nanoporous metal oxides via thermolysis under inert atmosphere. In this approach, an aliphatic ligand-based MOF is thermally converted to nanoporous metal oxides with highly nanocrystalline frameworks, in which aliphatic ligands act as the self-templates that are afterward evaporated to generate nanopores. We demonstrate this concept with hierarchically nanoporous magnesia (MgO) and ceria (CeO2), which have potential applicability for adsorption, catalysis, and energy storage. The pore size of these nanoporous metal oxides can be readily tuned by simple control of experimental parameters. Significantly, nanoporous MgO exhibits exceptional CO2 adsorption capacity (9.2 wt %) under conditions mimicking flue gas. This MOF-driven strategy can be expanded to other nanoporous monometallic and multimetallic oxides with a multitude of potential applications.

  16. Zr-based metal-organic frameworks: design, synthesis, structure, and applications.

    Science.gov (United States)

    Bai, Yan; Dou, Yibo; Xie, Lin-Hua; Rutledge, William; Li, Jian-Rong; Zhou, Hong-Cai

    2016-04-21

    Among the large family of metal-organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.

  17. Recent advances in metal-organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis.

    Science.gov (United States)

    Wang, Xuan; Ye, Nengsheng

    2017-09-04

    In the field of analytical chemistry, sample preparation and chromatographic separation are two core procedures. The means by which to improve the sensitivity, selectivity and detection limit of a method have become a topic of great interest. Recently, porous organic frameworks, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely used in this research area because of their special features, and different methods have been developed. This review summarizes the applications of MOFs and COFs in sample preparation and chromatographic stationary phases. The MOF- or COF-based solid-phase extraction (SPE), solid-phase microextraction (SPME), gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) methods are described. The excellent properties of MOFs and COFs have resulted in intense interest in exploring their performance and mechanisms for sample preparation and chromatographic separation. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  18. Highly sensitive and selective fluoride detection in water through fluorophore release from a metal-organic framework.

    Science.gov (United States)

    Hinterholzinger, Florian M; Rühle, Bastian; Wuttke, Stefan; Karaghiosoff, Konstantin; Bein, Thomas

    2013-01-01

    The detection, differentiation and visualization of compounds such as gases, liquids or ions are key challenges for the design of selective optical chemosensors. Optical chemical sensors employ a transduction mechanism that converts a specific analyte recognition event into an optical signal. Here we report a novel concept for fluoride ion sensing where a porous crystalline framework serves as a host for a fluorescent reporter molecule. The detection is based on the decomposition of the host scaffold which induces the release of the fluorescent dye molecule. Specifically, the hybrid composite of the metal-organic framework NH2-MIL-101(Al) and fluorescein acting as reporter shows an exceptional turn-on fluorescence in aqueous fluoride-containing solutions. Using this novel strategy, the optical detection of fluoride is extremely sensitive and highly selective in the presence of many other anions.

  19. Dispersive micro-solid-phase extraction of herbicides in vegetable oil with metal-organic framework MIL-101.

    Science.gov (United States)

    Li, Na; Zhang, Liyuan; Nian, Li; Cao, Bocheng; Wang, Zhibing; Lei, Lei; Yang, Xiao; Sui, Jiaqi; Zhang, Hanqi; Yu, Aimin

    2015-03-04

    Dispersive microsolid-phase extraction based on metal-organic framework has been developed and applied to the extraction of triazine and phenylurea herbicides in vegetable oils in this work. The herbicides were directly extracted with MIL-101 from diluted vegetables oils without any further cleanup. The separation and determination of herbicides were carried out on high performance liquid chromatography. The effects of experimental parameters, including volume ratio of n-hexane to oil sample, mass of MIL-101, extraction time, centrifugation time, eluting solvent, and elution time were investigated. The Student's t test was applied to evaluate the selected experimental conditions. The limits of detection for the herbicides ranged from 0.585 to 1.04 μg/L. The recoveries of the herbicides ranged from 87.3 to 107%. Our results showed that the present method is rapid, simple, and effective for extracting herbicides in vegetable oils.

  20. A REVIEW ON OSMOTIC DRUG DELIVERY SYSTEM

    Directory of Open Access Journals (Sweden)

    Harnish Patel

    2012-04-01

    Full Text Available Conventional oral drug delivery systems supply an instantaneous release of drug, which cannot control the release of the drug and effective concentration at the target site. This kind of dosing pattern may result in constantly changing, unpredictable plasma concentrations. Drugs can be delivered in a controlled pattern over a long period of time by the process of osmosis. Osmotic devices are the most promising strategy based systems for controlled drug delivery. They are the most reliable controlled drug delivery systems and could be employed as oral drug delivery systems. Various patents available for osmotic drug delivery system like Rose-Nelson pump, Higuchi leeper pump, Higuchi Theeuwes pump, Elementary Osmotic pump etc. ODDS are useful for poorly soluble drug, for pulsatile drug release, zero order release. Various techniques available for preparation of ODDS include push pull osmotic Pump, osmotic Brusting osmotic pump, liquid oral osmotic system, sandwiched osmotic tablets , delayed delivery osmotic device, monolithic osmotic System and controlled porosity osmotic Pump. Osmotically controlled oral drug delivery systems utilize osmotic pressure for controlled delivery of active agents. These systems can be utilized for systemic as well as targeted delivery of drugs. The release of drugs from osmotic systems is governed by various formulation factors such as solubility and osmotic pressure of the core components, size of the delivery orifice, and nature of the rate-controlling membrane. In this Paper mainly focused on the Osmotic System with example, the basic component of osmotic system and evaluation parameter of the osmotic drug delivery system.

  1. Homochiral metal-organic frameworks based on amino acid ligands for HPLC separation of enantiomers.

    Science.gov (United States)

    Zhang, Jun-Hui; Nong, Rui-Yu; Xie, Sheng-Ming; Wang, Bang-Jin; Ai, Ping; Yuan, Li-Ming

    2017-07-05

    Natural amino acids are well known to form coordination polymers with transition metal ions. In this study, six homochiral metal-organic frameworks constructed from Zn(2+) or Co(2+) ions and various enantiopure amino acid (L-tyrosine, L-histidine, L-tryptophan and L-glutamic acid), namely [Zn(L-tyr)]n (L-tyrZn), [Zn4 (btc)2 (Hbtc)(L-His)2 (H2 O)4 ]·1.5H2 O, {[Zn2 (L-trp)2 (bpe)2 (H2 O)2 ]·2H2 O·2NO3 }n , [Co2 (L-Trp)(INT)2 (H2 O)2 (ClO4 )], [Co2 (sdba)((L-Trp)2 ] and [Co(L-Glu)(H2 O)·H2 O]∞ , were synthesized according to the methods previously reported in the literature. The six homochiral MOFs were explored as the chiral stationary phases for high-performance liquid chromatographic separation of enantiomers using hexane/isopropanol or hexane/dichloromethane as mobile phase. Various types of enantiomers such as alcohols, amines, ketones, ethers, organic acids, etc. can be resolved on these homochiral MOF columns. The results revealed that the enantioseletivities of homochiral MOFs based on amino acids as chiral bridging ligands used as stationary phases are practical in HPLC. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Impedance spectroscopy of manganite films prepared by metalorganic chemical vapor deposition.

    Science.gov (United States)

    Nakamura, Toshihiro; Homma, Kohei; Tachibana, Kunihide

    2011-09-01

    Polycrystalline Pr(1-x)CaxMnO3 (PCMO) films were prepared by liquid source metalorganic chemical vapor deposition using in situ infrared spectroscopic monitoring. The electric properties of the PCMO-based devices with Ni and Al electrodes (Ni-PCMO-Ni and Al-PCMO-Al devices) were studied by dc current-voltage (I-V) measurements and ac impedance spectroscopy. The current varied linearly with the applied voltage in Ni-PCMO-Ni devices, while nonlinear behavior was observed in I-V curves for Al-PCMO-Al devices. Impedance spectra were also different between Ni-PCMO-Ni and Al-PCMO-Al devices. The Cole-Cole plots for the Ni-PCMO-Ni devices showed only a single semicircular arc, which was assigned to the PCMO bulk impedance. Impedance spectra for the Al-PCMO-Al devices had two distinct components, which could be attributed to the PCMO bulk and to the interface between the PCMO film and the Al electrode, respectively. The bias dependence of the impedance spectra suggested that the resistance switching in the Al-PCMO-Al devices was mainly due to the resistance change in the interface between the film and the electrode. The metal electrode plays an important role in the resistance switching in the PCMO-based devices. The choice of the optimum metal electrodes is essential to the ReRAM application of the manganite-based devices.

  3. Adsorptive removal and separation of chemicals with metal-organic frameworks: Contribution of π-complexation.

    Science.gov (United States)

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2017-03-05

    Efficient removal and separation of chemicals from the environment has become a vital issue from a biological and environmental point of view. Currently, adsorptive removal/separation is one of the most promising approaches for cleaning purposes. Selective adsorption/removal of various sulfur- and nitrogen-containing compounds, olefins, and π-electron-rich gases via π-complex formation between an adsorbent and adsorbate molecules is very competitive. Porous metal-organic framework (MOF) materials are very promising in the adsorption/separation of various liquids and gases owing to their distinct characteristics. This review summarizes the literature on the adsorptive removal/separation of various π-electron-rich compounds mainly from fuel and gases using MOF materials containing metal ions that are active for π-complexation. Details of the π-complexation, including mechanism, pros/cons, applications, and efficient ways to form the complex, are discussed systematically. For in-depth understanding, molecular orbital calculations regarding charge transfer between the π-complexing species are also explained in a separate section. From this review, readers will gain an understanding of π-complexation for adsorption and separation, especially with MOFs, to develop new insight for future research.

  4. Valuing Metal-Organic Frameworks for Postcombustion Carbon Capture: A Benchmark Study for Evaluating Physical Adsorbents

    KAUST Repository

    Adil, Karim

    2017-08-22

    The development of practical solutions for the energy-efficient capture of carbon dioxide is of prime importance and continues to attract intensive research interest. Conceivably, the implementation of adsorption-based processes using different cycling modes, e.g., pressure-swing adsorption or temperature-swing adsorption, offers great prospects to address this challenge. Practically, the successful deployment of practical adsorption-based technologies depends on the development of made-to-order adsorbents expressing mutually two compulsory requisites: i) high selectivity/affinity for CO2 and ii) excellent chemical stability in the presence of impurities. This study presents a new comprehensive experimental protocol apposite for assessing the prospects of a given physical adsorbent for carbon capture under flue gas stream conditions. The protocol permits: i) the baseline performance of commercial adsorbents such as zeolite 13X, activated carbon versus liquid amine scrubbing to be ascertained, and ii) a standardized evaluation of the best reported metal-organic framework (MOF) materials for carbon dioxide capture from flue gas to be undertaken. This extensive study corroborates the exceptional CO2 capture performance of the recently isolated second-generation fluorinated MOF material, NbOFFIVE-1-Ni, concomitant with an impressive chemical stability and a low energy for regeneration. Essentially, the NbOFFIVE-1-Ni adsorbent presents the best compromise by satisfying all the required metrics for efficient CO2 scrubbing.

  5. Valuing Metal-Organic Frameworks for Postcombustion Carbon Capture: A Benchmark Study for Evaluating Physical Adsorbents.

    Science.gov (United States)

    Adil, Karim; Bhatt, Prashant M; Belmabkhout, Youssef; Abtab, Sk Md Towsif; Jiang, Hao; Assen, Ayalew H; Mallick, Arijit; Cadiau, Amandine; Aqil, Jamal; Eddaoudi, Mohamed

    2017-08-22

    The development of practical solutions for the energy-efficient capture of carbon dioxide is of prime importance and continues to attract intensive research interest. Conceivably, the implementation of adsorption-based processes using different cycling modes, e.g., pressure-swing adsorption or temperature-swing adsorption, offers great prospects to address this challenge. Practically, the successful deployment of practical adsorption-based technologies depends on the development of made-to-order adsorbents expressing mutually two compulsory requisites: i) high selectivity/affinity for CO2 and ii) excellent chemical stability in the presence of impurities. This study presents a new comprehensive experimental protocol apposite for assessing the prospects of a given physical adsorbent for carbon capture under flue gas stream conditions. The protocol permits: i) the baseline performance of commercial adsorbents such as zeolite 13X, activated carbon versus liquid amine scrubbing to be ascertained, and ii) a standardized evaluation of the best reported metal-organic framework (MOF) materials for carbon dioxide capture from flue gas to be undertaken. This extensive study corroborates the exceptional CO2 capture performance of the recently isolated second-generation fluorinated MOF material, NbOFFIVE-1-Ni, concomitant with an impressive chemical stability and a low energy for regeneration. Essentially, the NbOFFIVE-1-Ni adsorbent presents the best compromise by satisfying all the required metrics for efficient CO2 scrubbing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. On the mechanism of hydrogen storage in a metal-organic framework material.

    Science.gov (United States)

    Belof, Jonathan L; Stern, Abraham C; Eddaoudi, Mohamed; Space, Brian

    2007-12-12

    Monte Carlo simulations were performed modeling hydrogen sorption in a recently synthesized metal-organic framework material (MOF) that exhibits large molecular hydrogen uptake capacity. The MOF is remarkable because at 78 K and 1.0 atm it sorbs hydrogen at a density near that of liquid hydrogen (at 20 K and 1.0 atm) when considering H2 density in the pores. Unlike most other MOFs that have been investigated for hydrogen storage, it has a highly ionic framework and many relatively small channels. The simulations demonstrate that it is both of these physical characteristics that lead to relatively strong hydrogen interactions in the MOF and ultimately large hydrogen uptake. Microscopically, hydrogen interacts with the MOF via three principle attractive potential energy contributions: Van der Waals, charge-quadrupole, and induction. Previous simulations of hydrogen storage in MOFs and other materials have not focused on the role of polarization effects, but they are demonstrated here to be the dominant contribution to hydrogen physisorption. Indeed, polarization interactions in the MOF lead to two distinct populations of dipolar hydrogen that are identified from the simulations that should be experimentally discernible using, for example, Raman spectroscopy. Since polarization interactions are significantly enhanced by the presence of a charged framework with narrow pores, MOFs are excellent hydrogen storage candidates.

  7. Solution growth of metal-organic complex CuTCNQ in small dimension interconnect structures

    Science.gov (United States)

    Demolliens, A.; Muller, Ch.; Müller, R.; Turquat, Ch.; Goux, L.; Deleruyelle, D.; Wouters, D. J.

    2010-11-01

    In this paper, we report two different elaboration routes to grow metal-organic complex CuTCNQ in liquid phase within small interconnect structures (i.e. via holes opened in SiO 2/SiC stack). The basic common idea relies on the formation of CuTCNQ material from the partial corrosion of a Cu bottom electrode by a TCNQ-based solution. The two solution growth methods are compared in terms of (i) via holes filling; (ii) local microstructure of CuTCNQ complex and (iii) quality of interface between CuTCNQ and copper metallic electrode. In the first route, in the reaction of the substrate with a TCNQ/copper salt solution in acetonitrile/toluene, a rapid formation of porous CuTCNQ complex is observed with an over-growth outside interconnect structures and many voids within via holes and at the interface with Cu layer. In contrast to this "mushroom-like" growth, the reaction of the substrate with a TCNQ solution in acetonitrile/2-butanone results in a "crystal-like" dense CuTCNQ complex within via holes and a CuTCNQ/Cu interface free of voids. In the latter case, satisfactory electrical performances are expected for future resistive switching memory devices.

  8. Homochiral metal-organic frameworks and their application in chromatography enantioseparations.

    Science.gov (United States)

    Peluso, Paola; Mamane, Victor; Cossu, Sergio

    2014-10-10

    The last frontier in the chiral stationary phases (CSPs) field for chromatography enantioseparations is represented by homochiral metal-organic frameworks (MOFs), a class of organic-inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. The modular nature of these materials allows to design focused structures by combining properly metal, organic ligands and rigid polytopic spacers. Intriguingly, chiral ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins, polysaccharides) which are characterized by a definite helical sense associated with the chirality of their building blocks (amino acids or sugars). Nowadays, robust and flexible materials characterized by high porosity and surface area became available by using preparative procedures typical of the so-called reticular synthesis. This review focuses on recent developments in the synthesis and applications of homochiral MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy, interesting results have been produced and a critical overview of the 12 reported applications for gas chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this field is provided.

  9. Structural Effects in Visible-Light-Responsive Metal-Organic Frameworks Incorporating ortho-Fluoroazobenzenes.

    Science.gov (United States)

    Castellanos, Sonia; Goulet-Hanssens, Alexis; Zhao, Fangli; Dikhtiarenko, Alla; Pustovarenko, Alexey; Hecht, Stefan; Gascon, Jorge; Kapteijn, Freek; Bléger, David

    2016-01-11

    The ability to control the interplay of materials with low-energy photons is important as visible light offers several appealing features compared to ultraviolet radiation (less damaging, more selective, predominant in the solar spectrum, possibility to increase the penetration depth). Two different metal-organic frameworks (MOFs) were synthesized from the same linker bearing all-visible ortho-fluoroazobenzene photoswitches as pendant groups. The MOFs exhibit different architectures that strongly influence the ability of the azobenzenes to isomerize inside the voids. The framework built with Al-based nodes has congested 1D channels that preclude efficient isomerization. As a result, local light-heat conversion can be used to alter the CO2 adsorption capacity of the material on exposure to green light. The second framework, built with Zr nodes, provides enough room for the photoswitches to isomerize, which leads to a unique bistable photochromic MOF that readily responds to blue and green light. The superiority of green over UV irradiation was additionally demonstrated by reflectance spectroscopy and analysis of digested samples. This material offers promising perspectives for liquid-phase applications such as light-controlled catalysis and adsorptive separation.

  10. Electron-Vibron Coupling at Metal-Organic Interfaces

    CERN Document Server

    Rosenow, Phil; Tonner, Ralf

    2015-01-01

    We study the significance and characteristics of interfacial dynamical charge transfer at metal-organic interfaces for the model system of organic semiconductor NTCDA on Ag(111). We combine infrared absorption spectroscopy and dispersion-corrected density functional theory calculations to analyze dynamic dipole moments and electron-vibron coupling at the interface. We demonstrate that interfacial dynamical charge transfer is the dominant cause of infrared activity in these systems and that it correlates with results from partial charge and density of states analysis. Nuclear motion generates an additional dynamic dipole moment but represents a minor effect except for modes with significant out-of-plane amplitudes.

  11. Metal-Organic Frameworks for Highly Selective Separations

    Energy Technology Data Exchange (ETDEWEB)

    Omar M. Yaghi

    2009-09-28

    This grant was focused on the study of metal-organic frameworks with these specific objectives. (1) To examine the use of MOFs with well-defined open metal sites for binding of gases and small organics. (2) To develop a strategy for producing MOFs that combine large pore size with high surface area for their use in gas adsorption and separation of polycyclic organic compounds. (3) To functionalize MOFs for the storage of inert gases such as methane. A brief outline of our progress towards these objectives is presented here as it forms part of the basis for the ideas to be developed under the present proposal.

  12. Boron Trifluoride Gas Adsorption in Metal-Organic Frameworks.

    Science.gov (United States)

    Siu, Paul W; Siegfried, John P; Weston, Mitchell H; Fuller, Patrick E; Morris, William; Murdock, Christopher R; Hoover, William J; Richardson, Rachelle K; Rodriguez, Stephanie; Farha, Omar K

    2016-12-05

    Coordinatively unsaturated metal-organic frameworks (MOFs) were studied for boron trifluoride (BF3) sorption. MOF-74-Mg, MOF-74-Mn, and MOF-74-Co show high initial uptake (below 6.7 × 10(-3) bar) with negligible deliverable capacity. The BF3 isotherm of MOF-74-Cu exhibits gradual uptake up to 0.9 bar and has a deliverable gravimetric capacity that is more than 100% higher than activated carbon. Two other Cu(2+) MOFs, MOF-505 and HKUST-1, have slightly lower deliverable capacities compared to MOF-74-Cu.

  13. Nanostructure and hydrogen spillover of bridged metal-organic frameworks.

    Science.gov (United States)

    Tsao, Cheng-Si; Yu, Ming-Sheng; Wang, Cheng-Yu; Liao, Pin-Yen; Chen, Hsin-Lung; Jeng, U-Ser; Tzeng, Yi-Ren; Chung, Tsui-Yun; Wu, Hsiu-Chu

    2009-02-04

    The metal-organic frameworks (MOF) with low and medium specific surface areas (SSA) were shown to be able to adsorb hydrogen via bridged spillover at room temperature (RT) up to an amount of full coverage of hydrogen in the MOF. Anomalous small-angle X-ray scattering was employed to investigate the key relationship between the structures and storage properties of the involved materials. It was found that the tunable imperfect lattice defects and the 3D pore network in the MOF crystal are the most critical structures for RT hydrogen uptake rather than the known micropores in the crystal, SSA, and Pt catalyst structure.

  14. OH-functionalization strategy in Metal-Organic Frameworks for drug delivery

    Science.gov (United States)

    Kotzabasaki, Marianna; Tylianakis, Emmanuel; Klontzas, Emmanuel; Froudakis, George E.

    2017-10-01

    With the goal in mind of developing new and much-improved drug anchoring regimes, we strategically modified the organic linker of IRMOF-16 by introducing hydroxyl groups. In this way, we improved the interaction energy of the anticancer drug gemcitabine with the nano-carrier by 40% compared to the unmodified one. Moreover, our simulations revealed high drug loading capacity in the OH-functionalized-IRMOF-16 (4343 mg/g), outperforming other drug storage materials. Drug release profiles, obtained via Grand Canonical Monte Carlo simulations, confirmed slower drug release in the case of the OH-functionalized IRMOF.

  15. Liquid hydrogen in Japan

    Energy Technology Data Exchange (ETDEWEB)

    Yasumi, S. [Iwatani Corp., Osaka (Japan). Dept. of Overseas Business Development

    2009-07-01

    Japan's Iwatani Corporation has focused its attention on hydrogen as the ultimate energy source in future. Unlike the United States, hydrogen use and delivery in liquid form is extremely limited in the European Union and in Japan. Iwatani Corporation broke through industry stereotypes by creating and building Hydro Edge Co. Ltd., Japan's largest liquid hydrogen plant. It was established in 2006 as a joint venture between Iwatani and Kansai Electric Power Group in Osaka. Hydro Edge is Japan's first combined liquid hydrogen and ASU plant, and is fully operational. Liquid oxygen, liquid nitrogen and liquid argon are separated from air using the cryogenic energy of liquefied natural gas fuel that is used for power generation. Liquid hydrogen is produced efficiently and simultaneously using liquid nitrogen. Approximately 12 times as much hydrogen in liquid form can be transported and supplied as pressurized hydrogen gas. This technology is a significant step forward in the dissemination and expansion of hydrogen in a hydrogen-based economy.

  16. Separation of Industrially-Relevant Gas Mixtures With Metal-Organic Frameworks

    Science.gov (United States)

    Herm, Zoey Rose

    The work herein describes the investigation of metal-organic frameworks for industrial applications, specifically gas phase separations of mixtures. Metal-organic frameworks are crystalline molecular scaffolds built from cationic metal vertices and organic bridging ligands. They are porous on a molecular scale and can separate gas mixtures when one component interacts more strongly with the pore walls than others. The near-infinite combination of metals and ligands allows for optimization of metal-organic framework structures for specific separations. (Abstract shortened by UMI.)

  17. Nanosuspension Technology for Drug Delivery

    Directory of Open Access Journals (Sweden)

    Jiraporn CHINGUNPITUK

    2007-06-01

    Full Text Available The poor water solubility of drugs is major problem for drug formulation. To date, nanoscale systems for drug delivery have gained much interest as a way to improve the solubility problems. The reduction of drug particles into the sub-micron range leads to a significant increase in the dissolution rate and therefore enhances bioavailability. Nanosuspensions are promising candidates that can be used for enhancing the dissolution of poorly water soluble drugs. Nanosuspensions contain submicron colloidal dispersion of pharmaceutical active ingredient particles in a liquid phase stabilized by surfactants. Production of drugs as nanosuspensions has been developed for drug delivery systems as an oral formulation and non-oral administration. This review describes the methods of pharmaceutical nanosuspension production, formulations and pharmaceutical applications in drug delivery as well as the marketed products.

  18. Premature delivery

    Directory of Open Access Journals (Sweden)

    Bernardita Donoso Bernales

    2012-09-01

    Full Text Available Preterm delivery is the single most important cause of perinatal morbidity and mortality. In Chile, preterm births have increased in the past decade, although neonatal morbidity and mortality attributable to it shows a downward trend, thanks to improvements in neonatal care of premature babies, rather than the success of obstetric preventive and therapeutic strategies. This article describes clinical entities, disease processes and conditions that constitute predisposing factors of preterm birth, as well as an outline for the prevention and clinical management of women at risk of preterm birth.

  19. Solidified self-nanoemulsifying formulation for oral delivery of combinatorial therapeutic regimen

    DEFF Research Database (Denmark)

    Jain, Amit K; Thanki, Kaushik; Jain, Sanyog

    2014-01-01

    PURPOSE: The present work reports rationalized development and characterization of solidified self-nanoemulsifying drug delivery system for oral delivery of combinatorial (tamoxifen and quercetin) therapeutic regimen. METHODS: Suitable oil for the preparation of liquid SNEDDS was selected based o...

  20. Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions.

    Science.gov (United States)

    Hasan, Zubair; Jhung, Sung Hwa

    2015-01-01

    Provision of clean water is one of the most important issues worldwide because of continuing economic development and the steady increase in the global population. However, clean water resources are decreasing everyday, because of contamination with various pollutants including organic chemicals. Pharmaceutical and personal care products, herbicides/pesticides, dyes, phenolics, and aromatics (from sources such as spilled oil) are typical organics that should be removed from water. Because of their huge porosities, designable pore structures, and facile modification, metal-organic frameworks (MOFs) are used in various adsorption, separation, storage, and delivery applications. In this review, the adsorptive purifications of contaminated water with MOFs are discussed, in order to understand possible applications of MOFs in clean water provision. More importantly, plausible adsorption or interaction mechanisms and selective adsorptions are summarized. The mechanisms of interactions such as electrostatic interaction, acid-base interaction, hydrogen bonding, π-π stacking/interaction, and hydrophobic interaction are discussed for the selective adsorption of organics over MOFs. The adsorption mechanisms will be very helpful not only for understanding adsorptions but also for applications of adsorptions in selective removal, storage, delivery and so on.

  1. Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material, iron terephthalate (MOF-235).

    Science.gov (United States)

    Haque, Enamul; Jun, Jong Won; Jhung, Sung Hwa

    2011-01-15

    An iron terephthalate (MOF-235), one of the metal-organic frameworks (MOFs), has been used for the removal of harmful dyes (anionic dye methyl orange (MO) and cationic dye methylene blue (MB)) from contaminated water via adsorption. The adsorption capacities of MOF-235 are much higher than those of an activated carbon. The performance of MOF-235 having high adsorption capacity is remarkable because the MOF-235 does not adsorb nitrogen at liquid nitrogen temperature. Based on this study, MOFs, even if they do not adsorb gases, can be suggested as potential adsorbents to remove harmful materials in the liquid phase. Adsorption of MO and MB at various temperatures shows that the adsorption is a spontaneous and endothermic process and that the entropy increases (the driving force of the adsorption) with adsorption of MO and MB. Copyright © 2010 Elsevier B.V. All rights reserved.

  2. Previously unknown class of metalorganic compounds revealed in meteorites

    Science.gov (United States)

    Ruf, Alexander; Kanawati, Basem; Hertkorn, Norbert; Yin, Qing-Zhu; Moritz, Franco; Harir, Mourad; Lucio, Marianna; Michalke, Bernhard; Wimpenny, Joshua; Shilobreeva, Svetlana; Bronsky, Basil; Saraykin, Vladimir; Gabelica, Zelimir; Gougeon, Régis D.; Quirico, Eric; Ralew, Stefan; Jakubowski, Tomasz; Haack, Henning; Gonsior, Michael; Jenniskens, Peter; Hinman, Nancy W.; Schmitt-Kopplin, Philippe

    2017-01-01

    The rich diversity and complexity of organic matter found in meteorites is rapidly expanding our knowledge and understanding of extreme environments from which the early solar system emerged and evolved. Here, we report the discovery of a hitherto unknown chemical class, dihydroxymagnesium carboxylates [(OH)2MgO2CR]−, in meteoritic soluble organic matter. High collision energies, which are required for fragmentation, suggest substantial thermal stability of these Mg-metalorganics (CHOMg compounds). This was corroborated by their higher abundance in thermally processed meteorites. CHOMg compounds were found to be present in a set of 61 meteorites of diverse petrological classes. The appearance of this CHOMg chemical class extends the previously investigated, diverse set of CHNOS molecules. A connection between the evolution of organic compounds and minerals is made, as Mg released from minerals gets trapped into organic compounds. These CHOMg metalorganic compounds and their relation to thermal processing in meteorites might shed new light on our understanding of carbon speciation at a molecular level in meteorite parent bodies. PMID:28242686

  3. Previously unknown class of metalorganic compounds revealed in meteorites.

    Science.gov (United States)

    Ruf, Alexander; Kanawati, Basem; Hertkorn, Norbert; Yin, Qing-Zhu; Moritz, Franco; Harir, Mourad; Lucio, Marianna; Michalke, Bernhard; Wimpenny, Joshua; Shilobreeva, Svetlana; Bronsky, Basil; Saraykin, Vladimir; Gabelica, Zelimir; Gougeon, Régis D; Quirico, Eric; Ralew, Stefan; Jakubowski, Tomasz; Haack, Henning; Gonsior, Michael; Jenniskens, Peter; Hinman, Nancy W; Schmitt-Kopplin, Philippe

    2017-03-14

    The rich diversity and complexity of organic matter found in meteorites is rapidly expanding our knowledge and understanding of extreme environments from which the early solar system emerged and evolved. Here, we report the discovery of a hitherto unknown chemical class, dihydroxymagnesium carboxylates [(OH)2MgO2CR](-), in meteoritic soluble organic matter. High collision energies, which are required for fragmentation, suggest substantial thermal stability of these Mg-metalorganics (CHOMg compounds). This was corroborated by their higher abundance in thermally processed meteorites. CHOMg compounds were found to be present in a set of 61 meteorites of diverse petrological classes. The appearance of this CHOMg chemical class extends the previously investigated, diverse set of CHNOS molecules. A connection between the evolution of organic compounds and minerals is made, as Mg released from minerals gets trapped into organic compounds. These CHOMg metalorganic compounds and their relation to thermal processing in meteorites might shed new light on our understanding of carbon speciation at a molecular level in meteorite parent bodies.

  4. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks

    National Research Council Canada - National Science Library

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-01-01

    .... Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core...

  5. Metal-organic Materials (moms) For Co2 Adsorption And Methods Of Using Moms

    KAUST Repository

    Eddaoudi, Mohamed

    2015-06-11

    Embodiments of the present disclosure provide for metal-organic materials (MOMs), systems that exhibit permanent porosity and using hydrophobic MOMs to separate components in a gas, methods of separating CO.sub.2 from a gas, and the like.

  6. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks

    Science.gov (United States)

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M.; Arvapally, Ravi K.; Martin, Richard L.; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A.; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-01

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  7. Automated growth of metal-organic framework coatings on flow-through functional supports.

    Science.gov (United States)

    Maya, F; Palomino Cabello, C; Clavijo, S; Estela, J M; Cerdà, V; Turnes Palomino, G

    2015-05-11

    A fully automated method for the controlled growth of metal-organic framework coatings on flow-through functional supports is reported. The obtained hybrid flow-through supports show high performance for the automated extraction of water pollutants.

  8. A highly stable dynamic fluorescent metal-organic framework for selective sensing of nitroaromatic explosives.

    Science.gov (United States)

    Gong, Yun-Nan; Jiang, Long; Lu, Tong-Bu

    2013-12-07

    A dynamic fluorescent metal-organic framework has been constructed using triphenylene-2,6,10-tricarboxylate and Tb(3+) as building blocks, which exhibits guest-responsive structural dynamism and selective sensing of nitroaromatic explosives.

  9. Synthesis of Metal-Organic Zeolites with Homochirality and High Porosity for Enantioselective Separation.

    Science.gov (United States)

    Xu, Zhong-Xuan; Liu, Liyang; Zhang, Jian

    2016-07-01

    Using lactic acid derivatives as chiral ligands, a pair of unprecedented homochiral metal-organic zeolites have been synthesized that feature zeotype CAN topology and have high porosity for enantioselective separation of racemates.

  10. Metal-organic materials (MOMs) for adsorption of polarizable gases and methods of using MOMs

    Energy Technology Data Exchange (ETDEWEB)

    Zaworotko, Michael; Mohamed, Mona H.; Elsaidi, Sameh

    2017-06-14

    Embodiments of the present disclosure provide for multi-component metal-organic materials (MOMs), systems including the MOM, systems for separating components in a gas, methods of separating polarizable gases from a gas mixture, and the like.

  11. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks.

    Science.gov (United States)

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-04

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  12. Metal-Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal-Organic Framework.

    Science.gov (United States)

    Cliffe, Matthew J; Castillo-Martínez, Elizabeth; Wu, Yue; Lee, Jeongjae; Forse, Alexander C; Firth, Francesca C N; Moghadam, Peyman Z; Fairen-Jimenez, David; Gaultois, Michael W; Hill, Joshua A; Magdysyuk, Oxana V; Slater, Ben; Goodwin, Andrew L; Grey, Clare P

    2017-04-19

    We report a hafnium-containing MOF, hcp UiO-67(Hf), which is a ligand-deficient layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its lower ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed "double cluster" (Hf12O8(OH)14), analogous to the condensation of coordination polyhedra in oxide frameworks. In oxide frameworks, variable stoichiometry can lead to more complex defect structures, e.g., crystallographic shear planes or modules with differing compositions, which can be the source of further chemical reactivity; likewise, the layered hcp UiO-67 can react further to reversibly form a two-dimensional metal-organic framework, hxl UiO-67. Both three-dimensional hcp UiO-67 and two-dimensional hxl UiO-67 can be delaminated to form metal-organic nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions, suggesting that defect-ordered MOFs could be a productive route to porous two-dimensional materials.

  13. Stimuli-Responsive DNA-Functionalized Metal-Organic Frameworks (MOFs).

    Science.gov (United States)

    Kahn, Jason S; Freage, Lina; Enkin, Natalie; Garcia, Miguel Angel Aleman; Willner, Itamar

    2017-02-01

    The synthesis of nucleic acid-functionalized metal-organic frameworks (MOFs) is described. The metal-organic frameworks are loaded with a dye being locked in the structures by means of stimuli-responsive nucleic acid caps. The pH and K(+) -ion-triggered release, and switchable release, are demonstrated. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Pulsed supersonic molecular beam for characterization of chemically active metal-organic complexes at surfaces

    Science.gov (United States)

    Lear, Amanda M.

    Metal-organic coordination networks (MOCNs) at surfaces consist of a complex of organic ligands bound to an atomic metal center. The MOCNs, when chosen appropriately, can form highly-ordered arrays at surfaces. Ultra-high vacuum surface studies allow control of surface composition and provide 2D growth restrictions, which lead to under-coordinated metal centers. These systems provide an opportunity to tailor the chemical function of the metal centers due to the steric restrictions imposed by the surface. Tuning the adsorption/desorption energy at a metal center and developing a cooperative environment for catalysis are the key scientific questions that motivate the construction of a molecular beam surface analysis system. Characterization of the created systems can be performed utilizing a pulsed supersonic molecular beam (PSMB) in unison with a quadrupole mass spectrometer. A PSMB allows for the highly controlled delivery of reactants with well-defined energy to a given platform making it possible to elucidate detailed chemical tuning information. In this thesis, a summary of prior theoretical molecular beam derivations is provided. Design considerations and an overview of the construction procedure for the current molecular beam apparatus, including initial characterization experiments, are presented. By impinging an Ar beam on a Ag(111) surface, the location of the specular angle (˜65°) and rough sample perimeter coordinates were determined. Additionally, surface analysis experiments, mainly Auger Electron Spectroscopy (AES), were performed to investigate the oxidation of epitaxial graphene on the SiC(0001) surface utilizing an oxygen cracking method. The AES experiments are described in detail and highlight the challenges that were faced when several different graphene samples were used for the oxygen adsorption/desorption experiments.

  15. Water adsorption in porous metal-organic frameworks and related materials.

    Science.gov (United States)

    Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao; Jiang, Juncong; Queen, Wendy L; Hudson, Matthew R; Yaghi, Omar M

    2014-03-19

    Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal-organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset of these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)4(-CO2)n secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.

  16. Optimized synthesis and crystalline stability of γ-cyclodextrin metal-organic frameworks for drug adsorption.

    Science.gov (United States)

    Liu, Botao; Li, Haiyan; Xu, Xiaonan; Li, Xue; Lv, Nana; Singh, Vikramjeet; Stoddart, J Fraser; York, Peter; Xu, Xu; Gref, Ruxandra; Zhang, Jiwen

    2016-11-30

    The biocompatible and renewable cyclodextrin metal-organic frameworks (CD-MOFs) have addressed a range of opportunities in molecular storage and separation sciences. The reported protocols for their synthesis, however, were carried out at room temperature over long time periods of time (24h), producing crystals of relatively poor uniformity. In this investigation, micron sized γ-CD-MOFs were synthesized by an optimized vapor diffusion method at elevated temperature (50°C) within 6h, after which the size control, crystalline stability and drug adsorption behavior were investigated in detail. In this manner, uniform cubic γ-CD-MOF crystals were obtained when the reaction temperature was raised to 50°C with pre-addition of the reaction solvent. The size of γ-CD-MOFs was adjusted efficiently by changing the reactant concentrations, temperatures, time, γ-CD ratios to KOH and surfactant concentrations, without influencing the porosity and crystallinity of the material markedly. Varing degrees of reduction in crystallinity and change in morphology were observed when the γ-CD-MOF crystals are treated under conditions of high temperature (100°C), high humidity (92.5%) and polar solvents (e.g., MeOH and DMF). In relation to drug adsorption by γ-CD-MOFs, most of the drug molecules containing carboxyl groups showed relatively high adsorption (>5%), while low adsorption (synthesis and size control of γ-CD-MOFs, the crystalline stability and drug adsorption characteristics of γ-CD-MOF crystals have been evaluated as a fundamental requirement of a potential vehicle for drug delivery.

  17. Synthesis and gas adsorption study of porous metal-organic framework materials

    Science.gov (United States)

    Mu, Bin

    Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) have become the focus of intense study over the past decade due to their potential for advancing a variety of applications including air purification, gas storage, adsorption separations, catalysis, gas sensing, drug delivery, and so on. These materials have some distinct advantages over traditional porous materials such as the well-defined structures, uniform pore sizes, chemically functionalized sorption sites, and potential for postsynthetic modification, etc. Thus, synthesis and adsorption studies of porous MOFs have increased substantially in recent years. Among various prospective applications, air purification is one of the most immediate concerns, which has urgent requirements to improve current nuclear, biological, and chemical (NBC) filters involving commercial and military purposes. Thus, the major goal of this funded project is to search, synthesize, and test these novel hybrid porous materials for adsorptive removal of toxic industrial chemicals (TICs) and chemical warfare agents (CWAs), and to install the benchmark for new-generation NBC filters. The objective of this study is three-fold: (i) Advance our understanding of coordination chemistry by synthesizing novel MOFs and characterizing these porous coordination polymers; (ii) Evaluate porous MOF materials for gasadsorption applications including CO2 capture, CH4 storage, other light gas adsorption and separations, and examine the chemical and physical properties of these solid adsorbents including thermal stability and heat capacity of MOFs; (iii) Evaluate porous MOF materials for next-generation NBC filter media by adsorption breakthrough measurements of TICs on MOFs, and advance our understanding about structureproperty relationships of these novel adsorbents.

  18. From ionic-liquid@metal-organic framework composites to heteroatom-decorated large-surface area carbons: superior CO2 and H2 uptake.

    Science.gov (United States)

    Aijaz, Arshad; Akita, Tomoki; Yang, Hui; Xu, Qiang

    2014-06-21

    For the first time, high surface area uniformly nitrogen (N)- and boron-nitrogen (BN)-decorated nanoporous carbons have been successfully fabricated by impregnation of ionic liquids (ILs) within a metal-organic framework (MOF), MIL-100(Al), followed by carbonization, which exhibit remarkable CO2 and H2 adsorption capacities.

  19. Semiconductor Metal-Organic Frameworks: Future Low-Bandgap Materials.

    Science.gov (United States)

    Usman, Muhammad; Mendiratta, Shruti; Lu, Kuang-Lieh

    2017-02-01

    Metal-organic frameworks (MOFs) with low density, high porosity, and easy tunability of functionality and structural properties, represent potential candidates for use as semiconductor materials. The rapid development of the semiconductor industry and the continuous miniaturization of feature sizes of integrated circuits toward the nanometer (nm) scale require novel semiconductor materials instead of traditional materials like silicon, germanium, and gallium arsenide etc. MOFs with advantageous properties of both the inorganic and the organic components promise to serve as the next generation of semiconductor materials for the microelectronics industry with the potential to be extremely stable, cheap, and mechanically flexible. Here, a perspective of recent research is provided, regarding the semiconducting properties of MOFs, bandgap studies, and their potential in microelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Metal-Organic Frameworks for CO2 Chemical Transformations.

    Science.gov (United States)

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Multi-Photon Absorption in Metal-Organic Frameworks.

    Science.gov (United States)

    Medishetty, Raghavender; Nemec, Lydia; Nalla, Venkatram; Henke, Sebastian; Samoc, Marek; Reuter, Karsten; Fischer, Roland A

    2017-09-12

    Multi-photon absorption (MPA) is among the most prominent nonlinear optical (NLO) effects and has applications, for example in telecommunications, defense, photonics and bio-medicines. Established MPA materials include dyes, quantum dots, organometallics and conjugated polymers, most often dispersed in solution. We demonstrate how metal-organic frameworks (MOFs), a novel NLO solid-state materials class, can be designed for exceptionally strong MPA behavior. MOFs consisting of zirconium- and hafnium-oxo-clusters and featuring a chromophore linker based on the tetraphenylethene (TPE) molecule exhibit record high two-photon absorption (2PA) cross section values, up to 3600 GM. The unique modular building-block principle of MOFs allows enhancing and optimizing their MPA properties in a theory guided approach by combining tailored charge polarization, conformational strain, three-dimensional arrangement and alignment of the chromophore linkers in the crystal. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Melt-Quenched Hybrid Glasses from Metal-Organic Frameworks.

    Science.gov (United States)

    Tao, Haizheng; Bennett, Thomas D; Yue, Yuanzheng

    2017-05-01

    While glasses formed by quenching the molten states of inorganic non-metallic, organic, and metallic species are known, those containing both inorganic and organic moieties are far less prevalent. Network materials consisting of inorganic nodes linked by organic ligands do however exist in the crystalline or amorphous domain. This large family of open framework compounds, called metal-organic frameworks (MOFs) or coordination polymers, has been investigated intensively in the past two decades for a variety of applications, almost all of which stem from their high internal surface areas and chemical versatility. Recently, a selection of MOFs has been demonstrated to undergo melting and vitrification upon cooling. Here, these recent discoveries and the connections between the fields of MOF chemistry and glass science are summarized. Possible advantages and applications for MOF glasses produced by utilizing the tunable chemistry of the crystalline state are also highlighted. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Structure and Properties of an Amorphous Metal-Organic Framework

    Science.gov (United States)

    Bennett, Thomas D.; Goodwin, Andrew L.; Dove, Martin T.; Keen, David A.; Tucker, Matthew G.; Barney, Emma R.; Soper, Alan K.; Bithell, Erica G.; Tan, Jin-Chong; Cheetham, Anthony K.

    2010-03-01

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300°C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400°C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  4. Transformation of metal-organic frameworks for molecular sieving membranes

    Science.gov (United States)

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-04-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively.

  5. Seed-Mediated Synthesis of Metal-Organic Frameworks.

    Science.gov (United States)

    Xu, Hai-Qun; Wang, Kecheng; Ding, Meili; Feng, Dawei; Jiang, Hai-Long; Zhou, Hong-Cai

    2016-04-27

    The synthesis of phase-pure metal-organic frameworks (MOFs) is of prime importance but remains a significant challenge because of the flexible and diversified coordination modes between metal ions and organic linkers. In this work, we report the synthesis of phase-pure MOFs via a facile seed-mediated approach. For several "accompanying" pairs of Zr-porphyrinic MOFs that are prone to yield mixtures, by fixing all reaction parameters except introducing seed crystals, MOFs in phase-pure forms have been obtained because the stage of MOF nucleation, which generates mixed nuclei, is bypassed. In addition, phase-pure MOF isomers with distinct pore structures have also been prepared through such an approach, revealing its versatility. To the best of our knowledge, this is an initial report on seed-assisted synthesis of phase-pure MOFs.

  6. Metal-organic frameworks for Xe/Kr separation

    Science.gov (United States)

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2014-07-22

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  7. Correlated defect nanoregions in a metal-organic framework

    Science.gov (United States)

    Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong; Chater, Philip A.; Kleppe, Annette K.; Tucker, Matthew G.; Wilhelm, Heribert; Funnell, Nicholas P.; Coudert, François-Xavier; Goodwin, Andrew L.

    2014-06-01

    Throughout much of condensed matter science, correlated disorder is a key to material function. While structural and compositional defects are known to exist within a variety of metal-organic frameworks (MOFs), the prevailing understanding is that these defects are only ever included in a random manner. Here we show—using a combination of diffuse scattering, electron microscopy, anomalous X-ray scattering and pair distribution function measurements—that correlations between defects can in fact be introduced and controlled within a hafnium terephthalate MOF. The nanoscale defect structures that emerge are an analogue of correlated Schottky vacancies in rocksalt-structured transition metal monoxides and have implications for storage, transport, optical and mechanical responses. Our results suggest how the diffraction behaviour of some MOFs might be reinterpreted, and establish a strategy of exploiting correlated nanoscale disorder as a targetable and desirable motif in MOF design.

  8. High methane storage capacity in aluminum metal-organic frameworks.

    Science.gov (United States)

    Gándara, Felipe; Furukawa, Hiroyasu; Lee, Seungkyu; Yaghi, Omar M

    2014-04-09

    The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal-organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm(3) cm(-3) at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm(3) cm(-3) under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm(3) cm(-3), and between 5 and 80 bar, 230 cm(3) cm(-3).

  9. Chemical, thermal and mechanical stabilities of metal-organic frameworks

    Science.gov (United States)

    Howarth, Ashlee J.; Liu, Yangyang; Li, Peng; Li, Zhanyong; Wang, Timothy C.; Hupp, Joseph T.; Farha, Omar K.

    2016-03-01

    The construction of thousands of well-defined, porous, metal-organic framework (MOF) structures, spanning a broad range of topologies and an even broader range of pore sizes and chemical functionalities, has fuelled the exploration of many applications. Accompanying this applied focus has been a recognition of the need to engender MOFs with mechanical, thermal and/or chemical stability. Chemical stability in acidic, basic and neutral aqueous solutions is important. Advances over recent years have made it possible to design MOFs that possess different combinations of mechanical, thermal and chemical stability. Here, we review these advances and the associated design principles and synthesis strategies. We focus on how these advances may render MOFs effective as heterogeneous catalysts, both in chemically harsh condensed phases and in thermally challenging conditions relevant to gas-phase reactions. Finally, we briefly discuss future directions of study for the production of highly stable MOFs.

  10. Metal-organic frameworks for artificial photosynthesis and photocatalysis.

    Science.gov (United States)

    Zhang, Teng; Lin, Wenbin

    2014-08-21

    Solar energy is an alternative, sustainable energy source for mankind. Finding a convenient way to convert sunlight energy into chemical energy is a key step towards realizing large-scale solar energy utilization. Owing to their structural regularity and synthetic tunability, metal-organic frameworks (MOFs) provide an interesting platform to hierarchically organize light-harvesting antennae and catalytic centers to achieve solar energy conversion. Such photo-driven catalytic processes not only play a critical role in the solar to chemical energy conversion scheme, but also provide a novel methodology for the synthesis of fine chemicals. In this review, we summarize the fundamental principles of energy transfer and photocatalysis and provide an overview of the latest progress in energy transfer, light-harvesting, photocatalytic proton and CO2 reduction, and water oxidation using MOFs. The applications of MOFs in organic photocatalysis and degradation of model organic pollutants are also discussed.

  11. Plasmonic nanoantenna array with single-chip integrated metal-organic framework for infrared absorption gas sensing (Conference Presentation)

    Science.gov (United States)

    Chong, Xinyuan; Kim, Ki-Joong; Li, Erwen; Zhang, Yujing; Ohodnicki, Paul R.; Chang, Chih-Hung; Wang, Alan X.

    2017-03-01

    Surface-enhanced infrared absorption (SEIRA) is a spectroscopic technique used to identify molecular fingerprints by resonant detection of infrared vibrational modes through coupling with the plasmonic modes of metallic nanostructures. Many reported works have demonstrated its capability to enhance the infrared absorption of solid or liquid samples. However, this technique has not been successfully applied to gas sensing yet due to the short light-matter interaction length and intrinsically weak absorption of gas compared to solid or liquid materials. Usually, IR gas sensing is conducted in a gas cell with a long absorption path. In the paper, we propose an integrated photonic device to expand the application of SEIRA to gas sensing by combining metal-organic framework (MOF) ZIF-8 (zeolitic imidazole framework) with plasmonic nanoantenna array. The device consists of an Au nanopatch array on sapphire substrate and is covered by a thin layer of MOF material. The MOF thin film, which is a new class of highly nanoporous material, serves as a gas absorber to selectively adsorb and concentrate CO2 from ambient environment into the thin layer, which has a high spatial overlap with the high intensity optical field of the plasmonic nanopatch antenna array. Namely, we can effectively increase the gas molecule concentration at the hot-spots for the SEIRA device. The experimentally demonstrated peak IR enhancement factor of the device for carbon dioxide sensing is over 1,100 times.

  12. Metal-organic frameworks: A new hydrogen storage system

    Science.gov (United States)

    Yaghi, Omar

    2004-03-01

    Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedi-carboxylate) with a cubic 3-D extended porous structure was found to be capable of adsorbing hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 K. At room temperature and pressures up to 20 bar this material has a hydrogen storage capacity which increases linearly as a function of the applied pressure up to 1.0 percent by weight at 20 bar. Inelastic Neutron Scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules was performed on hydrogen loaded MOF-5 using doses equivalent to four, eight and twenty-four hydrogen molecules per formula unit at 10 K. The spectra show peaks at 10.3 and 12.3 meV that are sharper than those observed for hydrogen in other porous materials, indicating the presence of two well-defined binding sites (termed I and II), which we associate with hydrogen binding to zinc and the BDC linker, respectively. At the highest dose (twenty-four hydrogen molecules), the peak corresponding to site II splits into four peaks, suggesting that higher capacity for hydrogen may be achieved by the use of larger linkers. Indeed, preliminary studies on isoreticular (of the same topology) metal-organic framework-6 and 8 having cyclobutyl and benzene moieties respectively fused to the benzene of MOF-5 gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.

  13. Controlling the magnetism of adsorbed metal-organic molecules

    Science.gov (United States)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  14. Superior performance of metal-organic frameworks over zeolites as solid acid catalysts in the Prins reaction: green synthesis of nopol.

    Science.gov (United States)

    Opanasenko, Maksym; Dhakshinamoorthy, Amarajothi; Hwang, Young Kyu; Chang, Jong-San; Garcia, Hermenegildo; Čejka, Jiří

    2013-05-01

    The catalytic performance of a set of metal-organic frameworks [CuBTC, FeBTC, MIL-100(Fe), MIL-100(Cr), ZIF-8, MIL-53(Al)] was investigated in the Prins condensation of β-pinene with formaldehyde and compared with the catalytic behavior of conventional aluminosilicate zeolites BEA and FAU and titanosilicate zeolite MFI (TS-1). The activity of the investigated metal-organic frameworks (MOFs) increased with the increasing concentration of accessible Lewis acid sites in the order ZIF-8zeolites BEA and FAU, which showed significantly lower selectivity to the target nopol than the MOFs. Its high activity, the preservation of its structure and active sites, and the possibility to use it in at least three catalytic cycles without loss of activity make MIL-100 (Fe) the best performing catalyst of the series for the Prins condensation of β-pinene and paraformaldehyde. Our report exemplifies the advantages of MOFs over zeolites as solid catalysts in liquid-phase reactions for the production of fine chemicals.

  15. Cubosomes and hexosomes as versatile platforms for drug delivery

    DEFF Research Database (Denmark)

    Mat Azmi, Intan Diana Binti; Moghimi, Seyed M; Yaghmur, Anan

    2015-01-01

    Nonlamellar liquid crystalline phases are attractive platforms for drug solubilization and targeted delivery. The attractiveness of this formulation principle is linked to the nanostructural versatility, compatiblity, digestiblity and bioadhesive properties of their lipid constituents......, and the capability of solubilizing and sustaining the release of amphiphilic, hydrophobic and hydrophilic drugs. Nonlamellar liquid crystalline phases offer two distinct promising strategies in the development of drug delivery systems. These comprise formation of ISAsomes (internally self-assembled 'somes...

  16. Insight into the construction of metal-organic polyhedra: Metal-organic cubes as a case study

    KAUST Repository

    Al Kordi, Mohamed

    2011-01-01

    Systematic studies were conducted to gain a better understanding of the metal-organic cubes (MOCs) directed assembly and their crystallization under predetermined reaction conditions, i.e. charge and size of metal ions, solvent type, counter anions, pH, and temperature. Four novel metal-organic materials are constructed via solvothermal reactions of different metal ions and 2,2′-(1H-imidazole-4,5-diyl)di-1,4,5,6-tetrahydropyrimidine, namely [Co8(C11N6H15)12]Cl 12·4H2O (1), [Ni4(C11N 6H15)4](NO3)4· 4DMF (2), {Cd(C11N6H15)(NO3) ·DMF}n (3), and [In8(C11N 6H15)12](NO3)12· 4H2O (4). In addition, syntheses and crystal structures for compounds 1(a-f), constructed under deliberately modified reaction conditions of 1, are reported. In compounds 1(a-f), the CoIII-based cationic MOCs crystallize in various packing arrangements in the presence of different counter-ions. Discrete MOCs retain their structural integrity, when crystalline solid was dissolved in water, under various pH (2.03-8.07) and temperatures (298-333 K), as confirmed by solution NMR studies. The assembly of the discrete MOC, from its basic molecular building blocks under mild reaction conditions, is demonstrated and monitored through solution NMR and UV-vis studies. © The Royal Society of Chemistry 2011.

  17. Transdermal drug delivery

    OpenAIRE

    Prausnitz, Mark R.; Langer, Robert

    2008-01-01

    Transdermal drug delivery has made an important contribution to medical practice, but has yet to fully achieve its potential as an alternative to oral delivery and hypodermic injections. First-generation transdermal delivery systems have continued their steady increase in clinical use for delivery of small, lipophilic, low-dose drugs. Second-generation delivery systems using chemical enhancers, non-cavitational ultrasound and iontophoresis have also resulted in clinical products; the ability ...

  18. A spray-drying strategy for synthesis of nanoscale metal-organic frameworks and their assembly into hollow superstructures

    Science.gov (United States)

    Carné-Sánchez, Arnau; Imaz, Inhar; Cano-Sarabia, Mary; Maspoch, Daniel

    2013-03-01

    Metal-organic frameworks (MOFs) are among the most attractive porous materials known today. Their miniaturization to the nanoscale—into nanoMOFs—is expected to serve myriad applications from drug delivery to membranes, to open up novel avenues to more traditional storage and catalysis applications, and to enable the creation of sophisticated superstructures. Here, we report the use of spray-drying as a versatile methodology to assemble nanoMOFs, yielding spherical hollow superstructures with diameters smaller than 5 µm. This strategy conceptually mimics the emulsions used by chemists to confine the synthesis of materials, but does not require secondary immiscible solvents or surfactants. We demonstrate that the resulting spherical, hollow superstructures can be processed into stable colloids, whose disassembly by sonication affords discrete, homogeneous nanoMOFs. This spray-drying strategy enables the construction of multicomponent MOF superstructures, and the encapsulation of guest species within these superstructures. We anticipate that this will provide new routes to capsules, reactors and composite materials.

  19. Toxic effect of zinc nanoscale metal-organic frameworks on rat pheochromocytoma (PC12) cells in vitro.

    Science.gov (United States)

    Ren, Fei; Yang, Baochun; Cai, Jing; Jiang, Yaodong; Xu, Jun; Wang, Shan

    2014-04-30

    Metal-organic frameworks (MOFs) possess unique properties desirable for delivery of drugs and gaseous therapeutics, but their uncharacterized interactions with cells raise increasing concerns of their safety in such biomedical applications. We evaluated the adverse effects of zinc nanoscale MOFs on the cell morphology, cytoskeleton, cell viability and expression of neurotrophin signaling pathway-associated GAP-43 protein in rat pheochromocytoma PC12 cells. At the concentration of 25 μg/ml, zinc MOFs did not significantly affect morphology, viability and membrane integrity of the cells. But at higher concentrations (over 100 μg/ml), MOFs exhibited a time- and concentration-dependent cytotoxicity, indicating their entry into the cells via endocytosis where they release Zn(2+) into the cytosol to cause increased intracellular concentration of Zn(2+). We demonstrated that the toxicity of MOFs was associated with a disrupted cellular zinc homeostasis and down-regulation of GAP-43 protein, which might be the underlying mechanism for the improved differentiation in PC12 cells. These findings highlight the importance of cytotoxic evaluation of the MOFs before their biomedical application.

  20. A spray-drying strategy for synthesis of nanoscale metal-organic frameworks and their assembly into hollow superstructures.

    Science.gov (United States)

    Carné-Sánchez, Arnau; Imaz, Inhar; Cano-Sarabia, Mary; Maspoch, Daniel

    2013-03-01

    Metal-organic frameworks (MOFs) are among the most attractive porous materials known today. Their miniaturization to the nanoscale--into nanoMOFs--is expected to serve myriad applications from drug delivery to membranes, to open up novel avenues to more traditional storage and catalysis applications, and to enable the creation of sophisticated superstructures. Here, we report the use of spray-drying as a versatile methodology to assemble nanoMOFs, yielding spherical hollow superstructures with diameters smaller than 5 µm. This strategy conceptually mimics the emulsions used by chemists to confine the synthesis of materials, but does not require secondary immiscible solvents or surfactants. We demonstrate that the resulting spherical, hollow superstructures can be processed into stable colloids, whose disassembly by sonication affords discrete, homogeneous nanoMOFs. This spray-drying strategy enables the construction of multicomponent MOF superstructures, and the encapsulation of guest species within these superstructures. We anticipate that this will provide new routes to capsules, reactors and composite materials.

  1. Lithium-functionalized metal-organic frameworks that show >10 wt% H2 uptake at ambient temperature.

    Science.gov (United States)

    Han, Sang Soo; Jung, Dong Hyun; Choi, Seung-Hoon; Heo, Jiyoung

    2013-08-26

    We have used grand canonical Monte Carlo simulations with a first-principles-based force field to show that metal-organic frameworks (MOFs) with Li functional groups (i.e. C-Li bonds) allow for exceptional H2 uptake at ambient temperature. For example, at 298 K and 100 bar, IRMOF-1-4Li shows a total H2 uptake of 5.54 wt% and MOF-200-27Li exhibits a total H2 uptake of 10.30 wt%, which are much higher than the corresponding values with pristine MOFs. Li-functionalized MOF-200 (MOF-200-27Li) shows 11.84 wt% H2 binding at 243 K and 100 bar. These hydrogen-storage capacities exceed the 2015 DOE target of 5.5 wt% H2. Moreover, the incorporation of Li functional groups into MOFs provides more benefits, such as higher delivery amount, for H2 uptake than previously reported Li-doped MOFs.

  2. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage.

    Science.gov (United States)

    Gu, Xiaojun; Lu, Zhang-Hui; Jiang, Hai-Long; Akita, Tomoki; Xu, Qiang

    2011-08-10

    Bimetallic Au-Pd nanoparticles (NPs) were successfully immobilized in the metal-organic frameworks (MOFs) MIL-101 and ethylenediamine (ED)-grafted MIL-101 (ED-MIL-101) using a simple liquid impregnation method. The resulting composites, Au-Pd/MIL-101 and Au-Pd/ED-MIL-101, represent the first highly active MOF-immobilized metal catalysts for the complete conversion of formic acid to high-quality hydrogen at a convenient temperature for chemical hydrogen storage. Au-Pd NPs with strong bimetallic synergistic effects have a much higher catalytic activity and a higher tolerance with respect to CO poisoning than monometallic Au and Pd counterparts. © 2011 American Chemical Society

  3. Effect of central metal ions of analogous metal-organic frameworks on the adsorptive removal of benzothiophene from a model fuel.

    Science.gov (United States)

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2013-09-15

    Liquid phase adsorption of benzothiophene (BT) has been studied over CuCl₂-loaded analogous metal-organic frameworks (MOFs), metal-benzenedicarboxylates (Me-BDCs, Me: Al, Cr and V), to understand the effect of central metal ions on the adsorptive removal of BT from a model fuel. Among the central metal ions (Al(3+), Cr(3+) and V(3+)) of the Me-BDCs only V(3+) was oxidized by the loaded CuCl₂ (or Cu(2+)) at ambient condition resulting in V(4+) and Cu(+) species. Different from the CuCl₂-loaded Al- and Cr-BDCs, the CuCl₂/V-BDC adsorbed BT remarkably well compared to the virgin V-BDCs which suggests a specific favorable interaction (π-complexation) between the obtained Cu(+) in the CuCl₂/V-BDC and BT.

  4. Synthesis of Supported Ultrafine Non-noble Subnanometer-Scale Metal Particles Derived from Metal-Organic Frameworks as Highly Efficient Heterogeneous Catalysts.

    Science.gov (United States)

    Kang, Xinchen; Liu, Huizhen; Hou, Minqiang; Sun, Xiaofu; Han, Hongling; Jiang, Tao; Zhang, Zhaofu; Han, Buxing

    2016-01-18

    The properties of supported non-noble metal particles with a size of less than 1 nm are unknown because their synthesis is a challenge. A strategy has now been created to immobilize ultrafine non-noble metal particles on supports using metal-organic frameworks (MOFs) as metal precursors. Ni/SiO2 and Co/SiO2 catalysts were synthesized with an average metal particle size of 0.9 nm. The metal nanoparticles were immobilized uniformly on the support with a metal loading of about 20 wt%. Interestingly, the ultrafine non-noble metal particles exhibited very high activity for liquid-phase hydrogenation of benzene to cyclohexane even at 80 °C, while Ni/SiO2 with larger Ni particles fabricated by a conventional method was not active under the same conditions.

  5. Porous metal-organic frameworks for heterogeneous biomimetic catalysis.

    Science.gov (United States)

    Zhao, Min; Ou, Sha; Wu, Chuan-De

    2014-04-15

    Metalloporphyrins are the active sites in monooxygenases that oxidize a variety of substrates efficiently and under mild conditions. Researchers have developed artificial metalloporphyrins, but these structures have had limited catalytic applications. Homogeneous artificial metalloporphyrins can undergo catalytic deactivation via suicidal self-oxidation, which lowers their catalytic activity and sustainability relative to their counterparts in Nature. Heme molecules in protein scaffolds can maintain high efficiency over numerous catalytic cycles. Therefore, we wondered if immobilizing metalloporphyrin moieties within porous metal-organic frameworks (MOFs) could stabilize these structures and facilitate the molecular recognition of substrates and produce highly efficient biomimetic catalysis. In this Account, we describe our research to develop multifunctional porphyrinic frameworks as highly efficient heterogeneous biomimetic catalysts. Our studies indicate that porous porphyrinic frameworks provide an excellent platform for mimicking the activity of biocatalysts and developing new heterogeneous catalysts that effect new chemical transformations under mild conditions. The porous structures and framework topologies of the porphyrinic frameworks depend on the configurations, coordination donors, and porphyrin metal ions of the metalloporphyrin moieties. To improve the activity of porous porphyrinic frameworks, we have developed a two-step synthesis that introduces the functional polyoxometalates (POMs) into POM-porphyrin hybrid materials. To tune the pore structures and the catalytic properties of porphyrinic frameworks, we have designed metalloporphyrin M-H8OCPP ligands with four m-benzenedicarboxylate moieties, and introduced the secondary auxiliary ligands. The porphyrin metal ions and the secondary functional moieties that are incorporated into porous metal-organic frameworks greatly influence the catalytic properties and activities of porphyrinic frameworks in

  6. In Vivo Targeting and Positron Emission Tomography Imaging of Tumor with Intrinsically Radioactive Metal-Organic Frameworks Nanomaterials.

    Science.gov (United States)

    Chen, Daiqin; Yang, Dongzhi; Dougherty, Casey A; Lu, Weifei; Wu, Hongwei; He, Xianran; Cai, Ting; Van Dort, Marcian E; Ross, Brian D; Hong, Hao

    2017-04-25

    Nanoscale metal-organic frameworks (nMOF) materials represent an attractive tool for various biomedical applications. Due to the chemical versatility, enormous porosity, and tunable degradability of nMOFs, they have been adopted as carriers for delivery of imaging and/or therapeutic cargos. However, the relatively low stability of most nMOFs has limited practical in vivo applications. Here we report the production and characterization of an intrinsically radioactive UiO-66 nMOF ((89)Zr-UiO-66) with incorporation of positron-emitting isotope zirconium-89 ((89)Zr). (89)Zr-UiO-66 was further functionalized with pyrene-derived polyethylene glycol (Py-PGA-PEG) and conjugated with a peptide ligand (F3) to nucleolin for targeting of triple-negative breast tumors. Doxorubicin (DOX) was loaded onto UiO-66 with a relatively high loading capacity (1 mg DOX/mg UiO-66) and served as both a therapeutic cargo and a fluorescence visualizer in this study. Functionalized (89)Zr-UiO-66 demonstrated strong radiochemical and material stability in different biological media. Based on the findings from cellular targeting and in vivo positron emission tomography (PET) imaging, we can conclude that (89)Zr-UiO-66/Py-PGA-PEG-F3 can serve as an image-guidable, tumor-selective cargo delivery nanoplatform. In addition, toxicity evaluation confirmed that properly PEGylated UiO-66 did not impose acute or chronic toxicity to the test subjects. With selective targeting of nucleolin on both tumor vasculature and tumor cells, this intrinsically radioactive nMOF can find broad application in cancer theranostics.

  7. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries

    Science.gov (United States)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-01

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  8. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries.

    Science.gov (United States)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-06

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  9. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium–sulfur batteries

    Science.gov (United States)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-01-01

    Lithium–sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium–sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density. PMID:28262801

  10. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules

    Science.gov (United States)

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo

    2015-06-01

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

  11. Effect of organic substituents on the adsorption of carbon dioxide on a metal-organic framework

    Science.gov (United States)

    Thu Ha, Nguyen Thi; Lefedova, O. V.; Ha, Nguyen Ngoc

    2017-01-01

    The adsorption of carbon dioxide on the MOF-5 metal-organic framework and modifications of it obtained by replacing the hydrogen atoms in the organic ligands with electron donor (-CH3,-OCH3) or electron acceptor groups (-CN,-NO2) is investigated using the grand canonical Monte Carlo (GCMC) method and density functional theory (DFT). It is shown that the adsorption of carbon dioxide molecules on the structures of metal-organic frameworks is most likely on Zn4O clusters, and that the adsorption of carbon dioxide is of a physical nature. The presence of substituents-CH3,-OCH3,-CN in metal-organic frameworks increases their capacity to adsorb carbon dioxide, while that of nitro groups (-NO2) has the opposite effect.

  12. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules.

    Science.gov (United States)

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M; Styles, Mark J; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J; Doonan, Christian J; Falcaro, Paolo

    2015-06-04

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

  13. Hydrogen storage and delivery system development

    Energy Technology Data Exchange (ETDEWEB)

    Handrock, J.L.; Wally, K.; Raber, T.N. [Sandia National Labs., Livermore, CA (United States)

    1995-09-01

    Hydrogen storage and delivery is an important element in effective hydrogen utilization for energy applications and is an important part of the FY1994-1998 Hydrogen Program Implementation Plan. The purpose of this project is to develop a platform for the engineering evaluation of hydrogen storage and delivery systems with an added focus on lightweight hydride utilization. Hybrid vehicles represent the primary application area of interest, with secondary interests including such items as existing vehicles and stationary uses. The near term goal is the demonstration of an internal combustion engine/storage/delivery subsystem. The long term goal is optimization of storage technologies for both vehicular and industrial stationary uses. In this project an integrated approach is being used to couple system operating characteristics to hardware development. A model has been developed which integrates engine and storage material characteristics into the design of hydride storage and delivery systems. By specifying engine operating parameters, as well as a variety of storage/delivery design features, hydride bed sizing calculations are completed. The model allows engineering trade-off studies to be completed on various hydride material/delivery system configurations. A more generalized model is also being developed to allow the performance characteristics of various hydrogen storage and delivery systems to be compared (liquid, activated carbon, etc.). Many of the features of the hydride storage model are applicable to the development of this more generalized model.

  14. Controlling Thermal Expansion: A Metal-Organic Frameworks Route.

    Science.gov (United States)

    Balestra, Salvador R G; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2016-11-22

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal-organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host-guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

  15. Recent Advances in Carbon Capture with Metal-Organic Frameworks.

    Science.gov (United States)

    Stylianou, Kyriakos C; Queen, Wendy L

    2015-01-01

    The escalating level of CO(2) in the atmosphere is one of the most critical environmental issues of our age. The carbon capture and storage from pilot test plants represents an option for reducing CO(2) emissions, however, the energy cost associated with post-combustion carbon capture process alone is ∼30% of the total energy generated by the power plant. Thus, the generation of carbon capture adsorbents with high uptake capacities, great separation performance and low cost is of paramount importance. Metal-organic frameworks are infinite networks of metal-containing nodes bridged by organic ligands through coordination bonds into porous extended structures and several reports have revealed that they are ideal candidates for the selective capture of CO(2). In this review we summarize recent advances related to the synthesis of porous MOFs and the latest strategies to enhance the CO(2) adsorption enthalpies and capacities at low-pressures, increase hydrolytic and mechanical stabilities, and improve the ease of regeneration. Although they show great promise for post-combustion carbon capture, there are still major challenges that must be overcome before they can be used for such a large-scale application.

  16. Multi-shelled Hollow Metal-Organic Frameworks.

    Science.gov (United States)

    Liu, Wenxian; Huang, Jijiang; Yang, Qiu; Wang, Shiji; Sun, Xiaoming; Zhang, Weina; Liu, Junfeng; Huo, Fengwei

    2017-05-08

    Hollow metal-organic frameworks (MOFs) are promising materials with sophisticated structures, such as multiple shells, that cannot only enhance the properties of MOFs but also endow them with new functions. Herein, we show a rational strategy to fabricate multi-shelled hollow chromium (III) terephthalate MOFs (MIL-101) with single-crystalline shells through step-by-step crystal growth and subsequent etching processes. This strategy relies on the creation of inhomogeneous MOF crystals in which the outer layer is chemically more robust than the inner layer and can be selectively etched by acetic acid. The regulation of MOF nucleation and crystallization allows the tailoring of the cavity size and shell thickness of each layer. The resultant multi-shelled hollow MIL-101 crystals show significantly enhanced catalytic activity during styrene oxidation. The insight gained from this systematic study will aid in the rational design and synthesis of other multi-shelled hollow structures and the further expansion of their applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Xenon Recovery at Room Temperature using Metal-Organic Frameworks.

    Science.gov (United States)

    Elsaidi, Sameh K; Ongari, Daniele; Xu, Wenqian; Mohamed, Mona H; Haranczyk, Maciej; Thallapally, Praveen K

    2017-08-10

    Xenon is known to be a very efficient anesthetic gas, but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycling from anesthetic gas mixtures can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low-temperature distillation to recover Xe; this method is expensive to use in medical facilities. Herein, we propose a much simpler and more efficient system to recover and recycle Xe from exhaled anesthetic gas mixtures at room temperature using metal-organic frameworks (MOFs). Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity and Xe/O2 , Xe/N2 and Xe/CO2 selectivity at room temperature. The in situ synchrotron measurements suggest that Xe is occupies the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Controlled Growth of Metal-Organic Frameworks on Polymer Brushes.

    Science.gov (United States)

    Hou, Liman; Zhou, Mingdong; Dong, Xiaozhe; Wang, Lei; Xie, Zhigang; Dong, Dewen; Zhang, Ning

    2017-08-17

    Polymer brushes are for the first time used to induce the synthesis of metal-organic frameworks (MOFs). The semi-fixed polymer chains provide a confined environment, which allows a mild growth of MOFs in between polymer chains to give surface-attached spherical MOF nanoparticles, in contrast to the larger MOF cubes/plates formed simultaneously in solution. Polymer brushes bearing carboxylate acid functionalities are indispensable for the formation of surface bound MOFs, while no MOF nanoparticles are observed on neutral polymer brushes. Characterization of the resultant MOF/polymer brushes hybrid film indicates the formation of crystalline MOF structure. The dimension of surface-attached MOFs can be fine-tuned from 20 nm to 1.4 μm simply by varying the structural parameter of polymer brushes and the nucleation duration. The method is not only applicable to the synthesis of MOF-5 and MIL-125, but shows great potential for the preparation of other surface-attached MOFs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Increasing the Stability of Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Mathieu Bosch

    2014-01-01

    Full Text Available Metal-organic frameworks (MOFs are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

  20. Functionalization of silicon nanowire surfaces with metal-organic frameworks

    KAUST Repository

    Liu, Nian

    2011-12-28

    Metal-organic frameworks (MOFs) and silicon nanowires (SiNWs) have been extensively studied due to their unique properties; MOFs have high porosity and specific surface area with well-defined nanoporous structure, while SiNWs have valuable one-dimensional electronic properties. Integration of the two materials into one composite could synergistically combine the advantages of both materials and lead to new applications. We report the first example of a MOF synthesized on surface-modified SiNWs. The synthesis of polycrystalline MOF-199 (also known as HKUST-1) on SiNWs was performed at room temperature using a step-by-step (SBS) approach, and X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy elemental mapping were used to characterize the material. Matching of the SiNW surface functional groups with the MOF organic linker coordinating groups was found to be critical for the growth. Additionally, the MOF morphology can by tuned by changing the soaking time, synthesis temperature and precursor solution concentration. This SiNW/MOF hybrid structure opens new avenues for rational design of materials with novel functionalities. © 2011 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

  1. Structural versatility of Metal-organic frameworks: Synthesis and Characterization

    KAUST Repository

    Alsadun, Norah S.

    2017-05-01

    Metal-Organic Frameworks (MOFs), an emerging class of porous crystalline materials, have shown promising properties for diverse applications such as catalysis, gas storage and separation. The high degree of tunability of MOFs vs other solid materials enable the assembly of advanced materials with fascinating properties for specific applications. Nevertheless, the precise control in the construction of MOFs at the molecular level remains challenging. Particularly, the formation of pre-targeted multi-nuclear Molecular Building Block (MBB) precursors to unveil materials with targeted structural characteristics is captivating. The aim of my master project in the continuous quest of the group of Prof. Eddaoudi in exploring different synthetic pathways to control the assembly of Rare Earth (RE) based MOF. After giving a general overview about MOFs, I will discuss in this thesis the results of my work on the use of tri-topic oriented organic carboxylate building units with the aim to explore the assembly/construction of new porous RE based MOFs. In chapter 2 will discuss the assembly of 3-c linkers with RE metals was then evaluated based on symmetry and angularity of the three connected linkers. The focus of chapter 3 is cerium based MOFs and heterometallic system, based on 3-c ligands with different length and symmetry. Overall, the incompatibility of 3-c ligands with the 12-c cuo MBB did not allow to any formation of higher neuclearity (˃6), but it has resulted in affecting the connectivity of the cluster.

  2. Synthesis and Characterization of Functionalized Metal-organic Frameworks

    Science.gov (United States)

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

  3. Large-scale screening of hypothetical metal-organic frameworks

    Science.gov (United States)

    Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon; Farha, Omar K.; Hauser, Brad G.; Hupp, Joseph T.; Snurr, Randall Q.

    2012-02-01

    Metal-organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.

  4. Alkali-metal azides interacting with metal-organic frameworks.

    Science.gov (United States)

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto

    2013-01-14

    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored.

  5. Selective gas adsorption and separation in metal-organic frameworks.

    Science.gov (United States)

    Li, Jian-Rong; Kuppler, Ryan J; Zhou, Hong-Cai

    2009-05-01

    Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal-organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

  6. Unusual adsorption behavior on metal-organic frameworks.

    Science.gov (United States)

    Fairen-Jimenez, David; Seaton, Nigel A; Düren, Tina

    2010-09-21

    Metal-organic frameworks (MOFs) have shown adsorption behavior that is not observed in other microporous materials such as zeolites or activated carbons. This study used grand canonical Monte Carlo simulation to evaluate a particular form of behavior, which corresponds to the presence of unusual type V adsorption isotherms. Study of a series of MOFs in the IRMOF family, containing chemically similar linkers of different length, showed that the presence of type V adsorption depends on a fine balance between the strength of the fluid-fluid and fluid-solid interactions, which in turn is a strong function of the length of the linker and therefore the pore size. A transition from type V behavior to the more common type I behavior is observed as the temperature increases. The temperature at which this transition occurs increases, and the transition becomes more diffuse, as the length of the linker increases. This type V behavior leads to an interesting possibility in the design of MOF adsorbents for use in gas separation and gas storage applications.

  7. Separation of chemical reaction intermediates by metal-organic frameworks.

    Science.gov (United States)

    Centrone, Andrea; Santiso, Erik E; Hatton, T Alan

    2011-08-22

    HPLC columns custom-packed with metal-organic framework (MOF) materials are used for the separation of four small intermediates and byproducts found in the commercial synthesis of an important active pharmaceutical ingredient in methanol. In particular, two closely related amines can be separated in the methanol reaction medium using MOFs, but not with traditional C18 columns using an optimized aqueous mobile phase. Infrared spectroscopy, UV-vis spectroscopy, X-ray diffraction, and thermogravimetric analysis are used in combination with molecular dynamic simulations to study the separation mechanism for the best-performing MOF materials. It is found that separation with ZIF-8 is the result of an interplay between the thermodynamic driving force for solute adsorption within the framework pores and the kinetics of solute diffusion into the material pores, while the separation with Basolite F300 is achieved because of the specific interactions between the solutes and Fe(3+) sites. This work, and the exceptional ability to tailor the porous properties of MOF materials, points to prospects for using MOF materials for the continuous separation and synthesis of pharmaceutical compounds.

  8. Atomistic Simulation of Protein Encapsulation in Metal-Organic Frameworks.

    Science.gov (United States)

    Zhang, Haiyang; Lv, Yongqin; Tan, Tianwei; van der Spoel, David

    2016-01-28

    Fabrication of metal-organic frameworks (MOFs) with large apertures triggers a brand-new research area for selective encapsulation of biomolecules within MOF nanopores. The underlying inclusion mechanism is yet to be clarified however. Here we report a molecular dynamics study on the mechanism of protein encapsulation in MOFs. Evaluation for the binding of amino acid side chain analogues reveals that van der Waals interaction is the main driving force for the binding and that guest size acts as a key factor predicting protein binding with MOFs. Analysis on the conformation and thermodynamic stability of the miniprotein Trp-cage encapsulated in a series of MOFs with varying pore apertures and surface chemistries indicates that protein encapsulation can be achieved via maintaining a polar/nonpolar balance in the MOF surface through tunable modification of organic linkers and Mg-O chelating moieties. Such modifications endow MOFs with a more biocompatible confinement. This work provides guidelines for selective inclusion of biomolecules within MOFs and facilitates MOF functions as a new class of host materials and molecular chaperones.

  9. Governing metal-organic frameworks towards high stability.

    Science.gov (United States)

    Li, Na; Xu, Jian; Feng, Rui; Hu, Tong-Liang; Bu, Xian-He

    2016-06-30

    Metal-organic frameworks (MOFs) constructed with metal ions/clusters and organic ligands have emerged as an important family of porous materials for various applications. However, the stability of this class of materials is crucial for their practical applications, which might be improved by varying their chemical composition and/or structurally tuning them. To fabricate MOFs with high stability, several strategies for enhancing the stability of MOFs have been developed, in which the strength of metal-ligand bonds is especially considered: the use of highly charged cations and higher pKa ligands, and varying the chemical functionality of linkers. On the other hand, the regulation of their structural architectures is also investigated: interpenetrated frameworks, multi-walled frameworks, and self-strengthening of the frameworks. In addition, the surface modification can also improve the stability of the materials. In this review, we introduce and summarize these strategies from the viewpoint of structural tuning and component choosing, providing useful instructions for the further design and synthesis of MOFs with high-level stability.

  10. Large-scale screening of hypothetical metal-organic frameworks.

    Science.gov (United States)

    Wilmer, Christopher E; Leaf, Michael; Lee, Chang Yeon; Farha, Omar K; Hauser, Brad G; Hupp, Joseph T; Snurr, Randall Q

    2011-11-06

    Metal-organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.

  11. Metal-organic frameworks as sensory materials and imaging agents.

    Science.gov (United States)

    Liu, Demin; Lu, Kuangda; Poon, Christopher; Lin, Wenbin

    2014-02-17

    Metal-organic frameworks (MOFs) are a class of hybrid materials self-assembled from organic bridging ligands and metal ion/cluster connecting points. The combination of a variety of organic linkers, metal ions/clusters, and structural motifs can lead to an infinite array of new materials with interesting properties for many applications. In this Forum Article, we discuss the design and applications of MOFs in chemical sensing and biological imaging. The first half of this article focuses on the development of MOFs as chemical sensors by highlighting how unique attributes of MOFs can be utilized to enhance sensitivity and selectivity. We also discuss some of the issues that need to be addressed in order to develop practically useful MOF sensors. The second half of this article focuses on the design and applications of nanoscale MOFs (NMOFs) as imaging contrast agents. NMOFs possess several interesting attributes, such as high cargo loading capacity, ease of postmodification, tunable size and shape, and intrinsic biodegradability, to make them excellent candidates as imaging contrast agents. We discuss the use of representative NMOFs in magnetic resonance imaging (MRI), X-ray computed tomography (CT), and optical imaging. Although still in their infancy, we believe that the compositional tunability and mild synthetic conditions of NMOF imaging agents should greatly facilitate their further development for clinical translation.

  12. Preparation and applications of monolithic structures containing metal-organic frameworks.

    Science.gov (United States)

    Lv, Yongqin; Tan, Xinyi; Svec, Frantisek

    2017-01-01

    Metal-organic frameworks are a new category of advanced porous materials with large surface areas and porosities, uniform pore sizes, tunable surface chemistry, and structural diversity. In combination with monoliths, they allow the fine tuning of desired interactions required in a variety of applications. This review article summarizes results of recent studies focused on synthetic strategies enabling incorporation of metal-organic frameworks in monolithic structures. A diverse array of applications including chromatographic separation, solid-phase microextraction, sample enrichment, heterogeneous catalysis, and enzymatic catalysis are also described. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Highly oriented surface-growth and covalent dye labeling of mesoporous metal-organic frameworks.

    Science.gov (United States)

    Hinterholzinger, Florian M; Wuttke, Stefan; Roy, Pascal; Preusse, Thomas; Schaate, Andreas; Behrens, Peter; Godt, Adelheid; Bein, Thomas

    2012-04-14

    Mesoporous amino-functionalized metal-organic framework thin films with the UiO-68 topology were grown in a highly oriented fashion on two different self-assembled monolayers on gold. The oriented MOF films were covalently modified with the fluorescent dye Rhodamine B inside the pore system, as demonstrated with size-selective fluorescence quenching studies. Our study suggests that mesoporous metal-organic frameworks are promising hosts for the covalent attachment of numerous functional moieties in a molecularly designed crystalline environment.

  14. Lamellar metal-organic complex and its rod-like nanoparticles prepared with ultrasonic technique

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Metal-organic complex (H3NCH2CH2NH2)3[MoO2(OC6H4O)2] with a lamellar morphology has been syn- thesized. Its crystal structure was confirmed by single-crystal X-ray diffraction. The morphology of the crystal was observed by scanning electron microscopy (SEM). The metal-organic nanoparticles have been prepared by using an ultrasonic method. The morphology of the as-prepared nanoparticles was observed by transmission electron microscopy (TEM). The possible formation mechanism has also been proposed.

  15. Neutron powder diffraction of metal-organic frameworks for hydrogen storage

    Indian Academy of Sciences (India)

    Craig M Brown; Yun Liu; Dan A Neumann

    2008-10-01

    We review recent structural studies that we have undertaken aimed at elucidating the fundamental properties of metal-organic framework materials and their interactions with hydrogen. We have shown that exposing coordinatively unsaturated metal centers can greatly enhance the hydrogen binding energy and that they result in a significant increase of the surface packing density of adsorbed hydrogen molecules on materials' surface. We will review some of the structural aspects of these materials, especially the adsorbed hydrogen molecule surface packing density in one type of metal-organic framework, MOF-74, which can be packed even denser than that in solid hydrogen.

  16. Poly(isophthalic acid)(ethylene oxide) as a Macromolecular Modulator for Metal-Organic Polyhedra.

    Science.gov (United States)

    Chen, Teng-Hao; Wang, Le; Trueblood, Jonathan V; Grassian, Vicki H; Cohen, Seth M

    2016-08-03

    A new strategy was developed by using a polymer ligand, poly(isophthalic acid)(ethylene oxide), to modulate the growth of metal-organic polyhedra (MOP) crystals. This macromolecular modulator can effectively control the crystal habit of several different Cu24L24 (L = isophthalic acid derivatives) MOPs. The polymer also directed the formation of MOP structures under reaction conditions that only produce metal-organic frameworks in the absence of modulator. Moreover, the polymer also enabled the deposition of MOP crystals on glass surfaces. This macromolecular modulator strategy provides an innovative approach to control the morphology and assembly of MOP particles.

  17. Ab-initio Study of Known and Hypothetical Metal-Organic Frameworks

    Science.gov (United States)

    Fuentes-Cabrera, Miguel; Nicholson, Don M.

    2004-03-01

    Rosi et al. [1] have found that microporous Metal-Organic Frameworks (MOF) materials are candidates for hydrogen storage applications. In particular, MOF-5 was found to adsorb hydrogen up to 4.5 weight percent at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. We use ab-initio techniques to investigate hydrogen adsorption, stability, and the electronic properties of known and hypothetical Metal-Organic Frameworks. [1] N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, and O.M. Yaghi

  18. Targeted manipulation of metal-organic frameworks to direct sorption properties.

    Science.gov (United States)

    Schneemann, Andreas; Henke, Sebastian; Schwedler, Inke; Fischer, Roland A

    2014-04-01

    Metal-organic frameworks are promising materials for manifold applications. This Minireview highlights approaches for the fine-tuning of specific sorption properties (e.g. capacity, selectivity, and breathing behavior) of this interesting class of materials. Central aspects covered are the control over the crystal morphology, the targeted tuning of sorption properties by judicious choice of metal centers and linkers, and the preparation of host-guest systems. We want to introduce the reader to these topics on the basis of the manipulation of a handful of outstanding prototypical metal-organic frameworks.

  19. Activation of the metal-organic framework MIL-47 for selective adsorption of xylenes and other difunctionalized aromatics.

    Science.gov (United States)

    Alaerts, Luc; Maes, Michael; Jacobs, Pierre A; Denayer, Joeri F M; De Vos, Dirk E

    2008-05-28

    The capacity and selectivity of the metal-organic framework MIL-47 for liquid phase adsorption are shown to heavily depend on the pretreatment of the material, as illustrated in detail by the particular case of selective xylene adsorption. By totally removing the uncoordinated terephthalic acid from the pores and simultaneously avoiding oxidation to nonporous V(2)O(5), pore volume and uptake of xylenes can be maximized. The presence of uncoordinated terephthalic acid in the pores improves the selectivity between p- and m-xylene. Calcination bed thickness and oven geometry influence the optimal calcination procedure. The physicochemical modifications of MIL-47 during its activation are investigated in detail with XRD, SEM, nitrogen physisorption, TGA and diffuse reflectance UV-Vis spectroscopy. Using optimally pretreated MIL-47 as adsorbent for xylene, ethyltoluene, dichlorobenzene, toluidine or cresol isomers, the para-isomer is in each case preferred over the meta-isomer in pulse chromatographic and batch experiments. The role of stacking in the selective adsorption of these isomers is discussed. In the case of the dichlorobenzenes, the meta- and para-isomers can be separated in a breakthrough experiment with a selectivity of 5.0.

  20. Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

    Science.gov (United States)

    Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

    2016-05-01

    Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

  1. Glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101: a molecular simulation study

    Science.gov (United States)

    Gupta, Krishna M.; Zhang, Kang; Jiang, Jianwen

    2015-08-01

    A molecular simulation study is reported on glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101. The F atom of MIL-101 is identified to be the most favorable adsorption site. Among three MIL-101-X (X = H, NH2 or CH3), the parent MIL-101 exhibits the highest adsorption capacity and recovery efficacy. Upon functionalization by -NH2 or -CH3 group, the steric hindrance in MIL-101 increases; consequently, the interactions between glucose and framework become less attractive, thus reducing the capacity and mobility of glucose. The presence of ionic liquid, 1-ethyl-3-methyl-imidazolium acetate, as an impurity reduces the strength of hydrogen-bonding between glucose and MIL-101, and leads to lower capacity and mobility. Upon adding anti-solvent (ethanol or acetone), a similar adverse effect is observed. The simulation study provides useful structural and dynamic properties of glucose in MIL-101, and it suggests that MIL-101 might be a potential candidate for glucose recovery.

  2. Stimuli-Responsive Metal-Organic Framework (MOF) with Chemo-Switchable Properties for Colorimetric Detection of CHCl3.

    Science.gov (United States)

    Razavi, Sayed Ali Akbar; Masoomi, Mohammad Yaser; Morsali, Ali

    2017-09-12

    The ligands 3,6-di(pyridin-4-yl)-1,4-dihydro-1,2,4,5-tetrazine (H2 DPT), as a pillar spacer, and 4,4'-oxybis(benzoic acid) (H2 OBA), as a dicarboxylate linker, have been used to develop a dihydrotetrazine-functionalized pillared metal-organic framework (MOF), [Zn(OBA)(H2 DPT)0.5 ]⋅DMF (TMU-34), as a functionally convertible stimuli-responsive MOF-based sensor. Sonochemically synthesized TMU-34 powder has been employed in the sensing of volatile organic compounds (VOCs). The results show that TMU-34 can act as a solid-state, naked-eye visual chemosensor for the detection of chloroform in the liquid and gas phases. TMU-34, as a chemo-switchable MOF with rapid response, undergoes a significant color change from yellow to pink through reversible dynamic conversion of dihydrotetrazine into tetrazine upon exposure to chloroform in the presence of other VOCs. Whereas other colorimetric MOF-based sensors show a wide range of color changes in the presence of different analytes, TMU-34 undergoes a color change only in the presence of chloroform. A mechanism for the observed color change is proposed on the basis of UV/Vis and (1) H NMR spectroscopic studies. These observations reveal that TMU-34 represents one of the most promising candidates for the highly selective and sensitive detection of chloroform. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Co3O4 Electrode Prepared by Using Metal-Organic Framework as a Host for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Jiaqiang Jiang

    2015-01-01

    Full Text Available Co3O4 nanoparticles were prepared from cobalt nitrate that was accommodated in the pores of a metal-organic framework (MOF ZIF-8 (Zn(MeIM2, MeIM = 2-methylimidazole by using a simple liquid-phase method. Analysis by scanning electron microscopy (SEM and transmission electron microscopy (TEM showed that the obtained Co3O4 was composed of separate nanoparticles with a mean size of 30 nm. The obtained Co3O4 nanoparticles exhibited superior electrochemical property. Co3O4 electrode exhibited a maximum specific capacitance of 189.1 F g−1 at the specific current of 0.2 A g−1. Meanwhile, the Co3O4 electrode possessed the high specific capacitance retention ratio at the current density ranging from 0.2 to 1.0 A g−1, thereby indicating that Co3O4 electrode suited high-rate charge/discharge.

  4. Inelastic neutron scattering study of binding of para-hydrogen in an ultra-microporous metal-organic framework

    Science.gov (United States)

    Yang, Sihai; Ramirez-Cuesta, Anibal J.; Schröder, Martin

    2014-01-01

    Metal-organic framework (MOF) materials show promise for H2 storage and it is widely predicted by computational modelling that MOFs incorporating ultra-micropores are optimal for H2 binding due to enhanced overlapping potentials. We report the investigation using inelastic neutron scattering of the interaction of H2 in an ultra-microporous MOF material showing low H2 uptake capacity. The study has revealed that adsorbed H2 at 5 K has a liquid recoil motion along the channel with very little interaction with the MOF host, consistent with the observed low uptake. The low H2 uptake is not due to incomplete activation or decomposition as the desolvated MOF shows CO2 uptake with a measured pore volume close to that of the single crystal pore volume. This study represents a unique example of surprisingly low H2 uptake within a MOF material, and complements the wide range of studies on systems showing higher uptake capacities and binding interactions.

  5. Metal-Organic Frameworks at the Biointerface: Synthetic Strategies and Applications.

    Science.gov (United States)

    Doonan, Christian; Riccò, Raffaele; Liang, Kang; Bradshaw, Darren; Falcaro, Paolo

    2017-06-20

    Many living organisms are capable of producing inorganic materials of precisely controlled structure and morphology. This ubiquitous process is termed biomineralization and is observed in nature from the macroscale (e.g., formation of exoskeletons) down to the nanoscale (e.g., mineral storage and transportation in proteins). Extensive research efforts have pursued replicating this chemistry with the overarching aims of synthesizing new materials of unprecedented physical properties and understanding the complex mechanisms that occur at the biological-inorganic interface. Recently, we demonstrated that a class of porous materials termed metal-organic frameworks (MOFs) can spontaneously form on protein-based hydrogels via a process analogous to natural matrix-mediated biomineralization. Subsequently, this strategy was extended to functional biomacromolecules, including proteins and DNA, which have been shown to seed and accelerate crystallization of MOFs. Alternative strategies exploit co-precipitating agents such as polymers to induce MOF particle formation thus facilitating protein encapsulation within the porous crystals. In these examples the rigid molecular architecture of the MOF was found to form a protective coating around the biomacromolecule offering improved stability to external environments that would normally lead to its degradation. In this way, the MOF shell mimics the protective function of a biomineralized exoskeleton. Other methodologies have also been explored to encapsulate enzymes within MOF structures, including the fabrication of polycrystalline hollow MOF microcapsules that preserve the original enzyme functionality over several batch reaction cycles. The potential to design MOFs of varied pore size and chemical functionality has underpinned studies describing the postsynthesis infiltration of enzymes into MOF pore networks and bioconjugation strategies for the decoration of the MOF outer surface, respectively. These methods and

  6. Toward Developing Made-to-Order Metal-Organic Frameworks: Design, Synthesis and Applications

    KAUST Repository

    Ashri, Lubna Y.

    2016-05-26

    Synthesis of materials with certain properties for targeted applications is an ongoing challenge in materials science. One of the most interesting classes of solid-state materials that have been recently introduced with the potential to address this is metal-organic frameworks (MOFs). MOFs chemistry offers a higher degree of control over materials to be synthesized utilizing various new design strategies, such as the molecular building blocks (MBBs) and the supermolecular building layers (SBLs) approaches. Depending on using predetermined building blocks, these strategies permit the synthesis of MOFs with targeted topologies and enable fine tuning of their properties. This study examines a number of aspects of the design and synthesis of MOFs while exploring their possible utilization in two diverse fields related to energy and pharmaceutical applications. Concerning MOFs design and synthesis, the work presented here explores the rational design of various MOFs with predicted topologies and tunable cavities constructed by pillaring pre-targeted 2-periodic SBLs using the ligand-to-axial and six-connected axial-to-axial pillaring strategies. The effect of expanding the confined spaces in prepared MOFs or modifying their functionalities, while preserving the underlying network topology, was investigated. Additionally, The MBBs approach was employed to discover new modular polynuclear rare earth (RE)-MBBs in the presence of different angular polytopic ligands containing carboxylate and nitrogen moieties with the aid of a modulator. The goal was to assess the diverse possible coordination modes and construct highly-connected nets for utility in the design of new MOFs and enhance the predictability of structural outcomes. The effect of adjusting ligands’ length-to-width ratio on the prepared MOFs was also evaluated. As a result, the reaction conditions amenable for reliable formation of the unprecedented octadecanuclear, octanuclear and double tetranuclear RE-MBBs were

  7. Assisted Vaginal Delivery

    Science.gov (United States)

    ... be needed. What are the risks for my baby if I have assisted vaginal delivery? Although the overall rate of injury to the baby as a result of assisted vaginal delivery is low, there still is a risk of ...

  8. eDelivery

    Data.gov (United States)

    US Agency for International Development — eDelivery provides the electronic packaging and delivery of closed and complete OPM investigation files to government agencies, including USAID, in a secure manner....

  9. Assisted delivery with forceps

    Science.gov (United States)

    ... technique your doctor may use to deliver the baby is called vacuum assisted delivery . When is a Forceps Delivery Needed? Even after ... Problems with urinating or moving your bowels after delivery For the baby, the risks are: Bumps, bruises or marks on ...

  10. Metal-organic frameworks as selectivity regulators for hydrogenation reactions

    Science.gov (United States)

    Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

    2016-11-01

    Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design

  11. Anion separation by selective crystallization of metal-organic frameworks.

    Science.gov (United States)

    Custelcean, Radu; Haverlock, Tamara J; Moyer, Bruce A

    2006-08-07

    A novel approach for the separation of anions from aqueous mixtures was demonstrated, which involves their selective crystallization with metal-organic frameworks (MOFs) containing urea functional groups. Self-assembly of Zn2+ with the N,N'-bis(m-pyridyl)urea (BPU) linker results in the formation of one-dimensional MOFs including various anions for charge balance, which interact to different extents with the zinc nodes and the urea hydrogen-bonding groups, depending on their coordinating abilities. Thus, Cl-, Br-, I-, and SO4(2-), in the presence of BPU and Zn2+, form MOFs from water, in which the anions coordinate the zinc and are hydrogen-bonded to the urea groups, whereas NO3- and ClO4- anions either do not form MOFs or form water-soluble discrete coordination complexes under the same conditions. X-ray diffraction, FTIR, and elemental analysis of the coordination polymers precipitated from aqueous mixtures containing equivalent amounts of these anions indicated total exclusion of the oxoanions and selective crystallization of the halides in the form of solid solutions with the general composition ZnCl(x)Br(y)I(z).BPU (x + y + z = 2), with an anti-Hofmeister selectivity. The concomitant inclusion of the halides in the same structural frameworks facilitates the rationalization of the observed selectivity on the basis of the diminishing interactions with the zinc and urea acidic centers in the MOFs when going from Cl- to I-, which correlates with decreasing anionic charge density in the same order. The overall crystal packing efficiency of the coordination frameworks, which ultimately determines their solubility, also plays an important role in the anion crystallization selectivity under thermodynamic equilibration.

  12. Multifunctional metal-organic frameworks: from academia to industrial applications.

    Science.gov (United States)

    Silva, Patrícia; Vilela, Sérgio M F; Tomé, João P C; Almeida Paz, Filipe A

    2015-10-01

    After three decades of intense and fundamental research on metal-organic frameworks (MOFs), is there anything left to say or to explain? The synthesis and properties of MOFs have already been comprehensively described elsewhere. It is time, however, to prove the nature of their true usability: technological applications based on these extended materials require development and implementation as a natural consequence of the up-to-known intensive research focused on their design and preparation. The current large number of reviews on MOFs emphasizes practical strategies to develop novel networks with varied crystal size, shape and topology, being mainly devoted to academic concerns. The present survey intends to push the boundaries and summarise the state-of-the-art on the preparation of promising (multi)functional MOFs in worldwide laboratories and their use as materials for industrial implementation. This review starts, on the one hand, to describe several tools and striking examples of remarkable and recent (multi)functional MOFs exhibiting outstanding properties (e.g., in gas adsorption and separation, selective sorption of harmful compounds, heterogeneous catalysis, luminescent and corrosion protectants). On the other hand, and in a second part, it intends to use these examples of MOFs to incite scientists to move towards the transference of knowledge from the laboratories to the industry. Within this context, we exhaustively review the many efforts of several worldwide commercial companies to bring functional MOFs towards the daily use, analysing the various patents and applications reported to date. Overall, this review goes from the very basic concepts of functional MOF engineering and preparation ending up in their industrial production on a large scale and direct applications in society.

  13. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve s

  14. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions.

    Science.gov (United States)

    Pereira, Carla F; Simões, Mário M Q; Tomé, João P C; Almeida Paz, Filipe A

    2016-10-12

    Porphyrin-based Metal-Organic Frameworks (Por-MOFs) constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  15. Exploiting large-pore metal-organic frameworks for separations through entropic molecular mechanisms

    NARCIS (Netherlands)

    Torres-Knoop, A.; Dubbeldam, D.

    2015-01-01

    We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the

  16. Metal-Organic Frameworks as Active Materials in Electronic Sensor Devices.

    Science.gov (United States)

    Campbell, Michael G; Dincă, Mircea

    2017-05-12

    In the past decade, advances in electrically conductive metal-organic frameworks (MOFs) and MOF-based electronic devices have created new opportunities for the development of next-generation sensors. Here we review this rapidly-growing field, with a focus on the different types of device configurations that have allowed for the use of MOFs as active components of electronic sensor devices.

  17. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    Ferbinteanu, M.; Cimpoesu, F.; Tanase, S.; Cheng, P.

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the

  18. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Stavila, Vitalie

    2017-08-01

    The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.

  19. Properties of alumina films by atmospheric pressure metal-organic chemical vapour deposition

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Corbach, van H.D.; Fransen, T.; Gellings, P.J.

    1994-01-01

    Thin alumina films were deposited at low temperatures (290–420°C) on stainless steel, type AISI 304. The deposition process was carried out in nitrogen by metal-organic chemical vapour deposition using aluminum tri-sec-butoxide. The film properties including the protection of the underlying substrat

  20. The mechanical properties of thin alumina film deposited by metal-organic chemical vapour deposition

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Gellings, P.J.; Vendel, van de D.; Metselaar, H.S.C.; Corbach, van H.D.; Fransen, T.

    1995-01-01

    Amorphous alumina films were deposited by metal-organic chemical vapour deposition (MOCVD) on stainless steel, type AISI 304. The MOCVD experiments were performed in nitrogen at low and atmospheric pressures. The effects of deposition temperature, growth rate and film thickness on the mechanical pro

  1. Luminescent metal-organic framework films as highly sensitive and fast-response oxygen sensors.

    Science.gov (United States)

    Dou, Zhongshang; Yu, Jiancan; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Yang, Deren; Qian, Guodong

    2014-04-16

    Luminescent metal-organic framework films, CPM-5⊃Tb(3+) and MIL-100(In)⊃Tb(3+), have been constructed by postfunctionalization of two porous indium-organic frameworks with different structures, respectively. The MIL-100(In)⊃Tb(3+) film shows high oxygen sensitivity (KSV = 7.59) and short response/recovery time (6 s/53 s).

  2. Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

    Science.gov (United States)

    2013-01-01

    NMR , HR -MS, elemental analysis), and crystallographic information files (CIF) for LH4, LEt4, and NU-135; PXRD, adsorption excess isotherms, BET...boron, MOF, metal?organic framework, coordination polymer , porous, hydrogen, methane Vaiva Krungleviciute, Daniel J. Clingerman, Joseph E. Mondloch...framework, coordination polymer , porous, hydrogen, methane ■ INTRODUCTION Nanoporous materials such as metal−organic frameworks (MOFs) with tailorable pore

  3. In silico screening of metal-organic frameworks in separation applications

    NARCIS (Netherlands)

    R. Krishna; J.M. van Baten

    2011-01-01

    Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO2 capture (CO2/H2, CO2/CH4, CO2/N2), CH4/H2, alkanes/alkenes, and hydrocarbon isomers. There are basicall

  4. Elucidating steric effects on enantioselective epoxidation catalyzed by (salen)Mn in metal-organic frameworks

    NARCIS (Netherlands)

    Oxford, G.A.E.; Dubbeldam, D.; Broadbelt, L.J.; Snurr, R.Q.

    2011-01-01

    The steric effects of a metal-organic framework (MOF) on the enantioselectivity of a (salen)Mn were studied using classical atomistic modeling. Rotational energy profiles for the approach of 2,2-dimethyl-2H-chromene to the active site of (salen)Mn were mapped for the homogeneous catalyst and the cat

  5. Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption

    NARCIS (Netherlands)

    Mason, J.A.; Sumida, K.; Herm, Z.R.; Krishna, R.; Long, J.R.

    2011-01-01

    Two representative metal-organic frameworks, Zn4O(BTB)2 (BTB3− = 1,3,5-benzenetribenzoate; MOF-177) and Mg2(dobdc) (dobdc4− = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temperature swing adsorption

  6. Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels

    NARCIS (Netherlands)

    Herm, Z.R.; Wiers, B.M.; Mason, J.A.; van Baten, J.M.; Hudson, M.R.; Zajdel, P.; Brown, C.M.; Masciocchi, N.; Krishna, R.; Long, J.R.

    2013-01-01

    Metal-organic frameworks can offer pore geometries that are not available in zeolites or other porous media, facilitating distinct types of shape-based molecular separations. Here, we report Fe-2(BDP)(3) (BDP2- = 1,4-benzenedipyrazotate), a highly stable framework with triangular channels that effec

  7. Metal-Organic Frameworks For Adsorption Driven Energy Transformation: From Fundamentals To Applications

    NARCIS (Netherlands)

    De Lange, M.F.

    2015-01-01

    A novel class of materials, i.e. Metal-Organic Frameworks (MOFs), has successfully been developed that is extremely suited for application in heat pumps and chillers. They have a superior performance over commercial sorbents and may potentially contribute to considerable energy savings

  8. Highly Selective Water Adsorption in a Lanthanum Metal-Organic Framework

    NARCIS (Netherlands)

    Plessius, R.; Kromhout, R.; Dantas Ramos, A.L.; Ferbinteanu, M.; Mittelmeijer-Hazeleger, M.C.; Krishna, R.; Rothenberg, G.; Tanase, S.

    2014-01-01

    We present a new metal-organic framework (MOF) built from lanthanum and pyrazine-2,5-dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)(1.5)(H2O)(2)]center dot 2H(2)O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration

  9. Elucidating steric effects on enantioselective epoxidation catalyzed by (salen)Mn in metal-organic frameworks

    NARCIS (Netherlands)

    Oxford, G.A.E.; Dubbeldam, D.; Broadbelt, L.J.; Snurr, R.Q.

    2011-01-01

    The steric effects of a metal-organic framework (MOF) on the enantioselectivity of a (salen)Mn were studied using classical atomistic modeling. Rotational energy profiles for the approach of 2,2-dimethyl-2H-chromene to the active site of (salen)Mn were mapped for the homogeneous catalyst and the

  10. From metal-organic squares to porous zeolite-like supramolecular assemblies

    KAUST Repository

    Wang, Shuang

    2010-12-29

    We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

  11. Controlling embedment and surface chemistry of nanoclusters in metal-organic frameworks.

    Science.gov (United States)

    Coupry, D E; Butson, J; Petkov, P S; Saunders, M; O'Donnell, K; Kim, H; Buckley, C; Addicoat, M; Heine, T; Szilágyi, P Á

    2016-04-14

    A combined theoretical and experimental approach demonstrates that nanocluster embedment into the pores of metal-organic frameworks (MOF) may be influenced by the chemical functionalisation of the MOF. Furthermore, this results in the surface functionalisation of the embedded nanoclusters, highlighting the potential of MOF scaffolds for the design and synthesis of novel functional materials.

  12. A highly porous metal-organic framework for large organic molecule capture and chromatographic separation.

    Science.gov (United States)

    Li, Pei-Zhou; Su, Jie; Liang, Jie; Liu, Jia; Zhang, Yuanyuan; Chen, Hongzhong; Zhao, Yanli

    2017-03-25

    A highly porous metal-organic framework (MOF) with large pores was successfully obtained via solvothermal assembly of a "click"-extended tricarboxylate ligand and Zn(ii) ions. The inherent feature of large-molecule accessible pores endows the MOF with a unique property for utilization toward large guest molecules.

  13. Metal-Organic Frameworks For Adsorption Driven Energy Transformation: From Fundamentals To Applications

    NARCIS (Netherlands)

    De Lange, M.F.

    2015-01-01

    A novel class of materials, i.e. Metal-Organic Frameworks (MOFs), has successfully been developed that is extremely suited for application in heat pumps and chillers. They have a superior performance over commercial sorbents and may potentially contribute to considerable energy savings worldwide. Gl

  14. Channeling and electromagnetic radiation of relativistic charged particles in metal-organic frameworks

    Science.gov (United States)

    Zhevago, N. K.; Glebov, V. I.

    2017-06-01

    We have developed the theory of electromagnetic interaction of relativistic charged particles with metal-organic frameworks (MOFs). The electrostatic potential and electron number density distribution in MOFs were calculated using the most accurate data for the atomic form factors. Peculiarities of axial channeling of fast charged particles and various types of electromagnetic radiation from relativistic particles has been discussed.

  15. Tuning of gate adsorption: modification of a flexible metal-organic framework by secondary organic ligands.

    Science.gov (United States)

    Kondo, Atsushi; Fujii, Takuro; Maeda, Kazuyuki

    2014-06-14

    For realizing selective adsorption of targeted molecules, a flexible metal-organic framework (MOF) was modified with monodentate secondary ligands. Although the modified MOF retains CO2 adsorptivities with a vertical adsorption uptake, the material also shows gate adsorptivities of a specific gas molecule that the pristine MOF does not adsorb.

  16. Lithium-Ion-Battery Anode Materials with Improved Capacity from a Metal-Organic Framework.

    Science.gov (United States)

    Lin, Xiao-Ming; Niu, Ji-Liang; Lin, Jia; Wei, Lei-Ming; Hu, Lei; Zhang, Gang; Cai, Yue-Peng

    2016-09-06

    We present a porous metal-organic framework (MOF) with remarkable thermal stability that exhibits a discharge capacity of 300 mAh g(-1) as an anode material for a lithium-ion battery. Pyrolysis of the obtained MOF gives an anode material with improved capacity (741 mAh g(-1)) and superior cyclic stability.

  17. Shape Controlled Hierarchical Porous Hydrophobic/Oleophilic Metal-Organic Nanofibrous Gel Composites for Oil Adsorption.

    Science.gov (United States)

    Jayaramulu, Kolleboyina; Geyer, Florian; Petr, Martin; Zboril, Radek; Vollmer, Doris; Fischer, Roland A

    2017-03-01

    A versatile and facile synthetic route toward a ultralight hierarchical poroushybrid composed of metal-organic gels and fluorinated graphene oxide is reported. The composite gels show excellent absorbency of oil and various organic solvents due to their prominent meso/macropores, notable hydrophobicity, and superoleophilicity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve

  19. In silico screening of metal-organic frameworks in separation applications

    NARCIS (Netherlands)

    Krishna, R.; van Baten, J.M.

    2011-01-01

    Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO2 capture (CO2/H2, CO2/CH4, CO2/N2), CH4/H2, alkanes/alkenes, and hydrocarbon isomers. There are

  20. Capturing neon - the first experimental structure of neon trapped within a metal-organic environment.

    Science.gov (United States)

    Wood, Peter A; Sarjeant, Amy A; Yakovenko, Andrey A; Ward, Suzanna C; Groom, Colin R

    2016-08-21

    Despite being the fifth most abundant element in the atmosphere, neon has never been observed in an organic or metal-organic environment. This study shows the adsorption of this highly unreactive element within such an environment and reveals the first crystallographic observation of an interaction between neon and a transition metal.

  1. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve s

  2. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

    Science.gov (United States)

    Liu, Wan-Ling; Yang, Ni-Shin; Chen, Ya-Ting; Lirio, Stephen; Wu, Cheng-You; Lin, Chia-Her; Huang, Hsi-Ya

    2015-01-02

    A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. High-throughput synthesis and characterization of nanocrystalline porphyrinic zirconium metal-organic frameworks.

    Science.gov (United States)

    Kelty, M L; Morris, W; Gallagher, A T; Anderson, J S; Brown, K A; Mirkin, C A; Harris, T D

    2016-06-14

    We describe and employ a high-throughput screening method to accelerate the synthesis and identification of pure-phase, nanocrystalline metal-organic frameworks (MOFs). We demonstrate the efficacy of this method through its application to a series of porphyrinic zirconium MOFs, resulting in the isolation of MOF-525, MOF-545, and PCN-223 on the nanoscale.

  4. Metal-organic scintillator crystals for X-ray, gamma ray, and neutron detection

    Science.gov (United States)

    Boatner, Lynn A [Oak Ridge, TN; Kolopus, James A [Clinton, TN; Neal, John S [Knoxville, TN; Ramey, Joanne Oxendine [Knoxville, TN; Wisniewski, Dariusz J [Torun, PL

    2012-01-03

    New metal-organic materials are useful as scintillators and have the chemical formula LX.sub.3(CH.sub.3OH).sub.4 where L is Y, Sc, or a lanthanide element, and X is a halogen element. An example of the scintillator materials is CeCl.sub.3(CH.sub.3OH).sub.4.

  5. Surface functionalization of metal-organic polyhedron for homogeneous cyclopropanation catalysis.

    Science.gov (United States)

    Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey; Zhou, Hong-Cai

    2011-05-01

    A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

  6. Exploiting large-pore metal-organic frameworks for separations through entropic molecular mechanisms

    NARCIS (Netherlands)

    A. Torres-Knoop; D. Dubbeldam

    2015-01-01

    We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the sep

  7. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Carla F. Pereira

    2016-10-01

    Full Text Available Porphyrin-based Metal-Organic Frameworks (Por-MOFs constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  8. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    M. Ferbinteanu; F. Cimpoesu; S. Tanase

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the interdisciplinar

  9. Market Liquidity and Funding Liquidity

    OpenAIRE

    Brunnermeier, Markus K; Lasse Heje Pedersen

    2007-01-01

    We provide a model that links an asset's market liquidity - i.e., the ease with which it is traded - and traders' funding liquidity - i.e., the ease with which they can obtain funding. Traders provide market liquidity, and their ability to do so depends on their availability of funding. Conversely, traders' funding, i.e., their capital and the margins they are charged, depend on the assets' market liquidity. We show that, under certain conditions, margins are destabilizing and market liquidit...

  10. Market Liquidity and Funding Liquidity

    OpenAIRE

    Markus K. Brunnermeier; Lasse Heje Pedersen

    2007-01-01

    We provide a model that links an asset's market liquidity - i.e., the ease with which it is traded - and traders' funding liquidity - i.e., the ease with which they can obtain funding. Traders provide market liquidity, and their ability to do so depends on their availability of funding. Conversely, traders' funding, i.e., their capital and the margins they are charged, depend on the assets' market liquidity. We show that, under certain conditions, margins are destabilizing and market liquidit...

  11. Cyclodextrin-based metal-organic frameworks particles as efficient carriers for lansoprazole: Study of morphology and chemical composition of individual particles.

    Science.gov (United States)

    Li, Xue; Guo, Tao; Lachmanski, Laurent; Manoli, Francesco; Menendez-Miranda, Mario; Manet, Ilse; Guo, Zhen; Wu, Li; Zhang, Jiwen; Gref, Ruxandra

    2017-10-15

    Cyclodextrin-based metal-organic frameworks (CD-MOFs) represent an environment-friendly and biocompatible class of MOFs drawing increasing attention in drug delivery. Lansoprazole (LPZ) is a proton-pump inhibitor used to reduce the production of acid in the stomach and recently identified as an antitubercular prodrug. Herein, LPZ loaded CD-MOFs were successfully synthesized upon the assembly with γ-CD in the presence of K(+) ions using an optimized co-crystallization method. They were characterized in terms of morphology, size and crystallinity, showing almost perfect cubic morphologies with monodispersed size distributions. The crystalline particles, loaded or not with LPZ, have mean diameters of around 6μm. The payloads reached 23.2±2.1% (wt) which corresponds to a molar ratio of 1:1 between LPZ and γ-CD. It was demonstrated that even after two years storage, the incorporated drug inside the CD-MOFs maintained its spectroscopic characteristics. Molecular modelling provided a deeper insight into the interaction between the LPZ and CD-MOFs. Raman spectra of individual particles were recorded, confirming the formation of inclusion complexes within the tridimensional CD-MOF structures. Of note, it was found that each individual particle had the same chemical composition. The LPZ-loaded particles had remarkable homogeneity in terms of both drug loading and size. These results pave the way towards the use of CD-MOFs for drug delivery purposes. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Colloidal drug delivery systems in vaccine delivery.

    Science.gov (United States)

    Beg, Sarwar; Samad, Abdus; Nazish, Iram; Sultana, Ruksar; Rahman, Mahfoozur; Ahmad, Md Zaki; Akbar, Md

    2013-01-01

    Vaccines play a vital role in the field of community medicine to combat against several diseases of human existence. Vaccines primarily trigger the acquired immune system to develop long-lasting immunity against pathogens. Conventional approaches for vaccine delivery lacks potential to target a particular antigen to develop acquired immunity by specific antibodies. Recent advancements in vaccine delivery showed that inclusion of adjuvants in vaccine formulations or delivery of them in a carrier helps in achieving desired targeting ability, reducing the immunogenicity and significant augmentation in the immune response. Colloidal carriers (liposomes, niosomes, microspheres, proteosomes, virosomes and virus like particles (VLPs), antigen cochleates, dendrimers and carbon nanotubes) have been widely explored for vaccine delivery. Further, surface engineering of these carriers with ligands, functional moieties and monoclonal antibodies tend to enhance the immune recognition potential of vaccines by differentiation of antigen specific memory T-cells. The current review, therefore, provides an updated account on the recent advancements in various colloidal delivery systems in vaccine delivery, outlining the mechanism of immune response initiated by them along with potential applications and marketed instances in an explicit manner.

  13. Aptamer-Mediated Up-conversion Core/MOF Shell Nanocomposites for Targeted Drug Delivery and Cell Imaging

    Science.gov (United States)

    Deng, Kerong; Hou, Zhiyao; Li, Xuejiao; Li, Chunxia; Zhang, Yuanxin; Deng, Xiaoran; Cheng, Ziyong; Lin, Jun

    2015-01-01

    Multifunctional nanocarriers for targeted bioimaging and drug delivery have attracted much attention in early diagnosis and therapy of cancer. In this work, we develop a novel aptamer-guided nanocarrier based on the mesoporous metal-organic framework (MOF) shell and up-conversion luminescent NaYF4:Yb3+/Er3+ nanoparticles (UCNPs) core for the first time to achieve these goals. These UCNPs, chosen as optical labels in biological assays and medical imaging, could emit strong green emission under 980 nm laser. The MOF structure based on iron (III) carboxylate materials [MIL-100 (Fe)] possesses high porosity and non-toxicity, which is of great value as nanocarriers for drug storage/delivery. As a unique nanoplatform, the hybrid inorganic-organic drug delivery vehicles show great promising for simultaneous targeted labeling and therapy of cancer cells. PMID:25597762

  14. Aptamer-Mediated Up-conversion Core/MOF Shell Nanocomposites for Targeted Drug Delivery and Cell Imaging

    Science.gov (United States)

    Deng, Kerong; Hou, Zhiyao; Li, Xuejiao; Li, Chunxia; Zhang, Yuanxin; Deng, Xiaoran; Cheng, Ziyong; Lin, Jun

    2015-01-01

    Multifunctional nanocarriers for targeted bioimaging and drug delivery have attracted much attention in early diagnosis and therapy of cancer. In this work, we develop a novel aptamer-guided nanocarrier based on the mesoporous metal-organic framework (MOF) shell and up-conversion luminescent NaYF4:Yb3+/Er3+ nanoparticles (UCNPs) core for the first time to achieve these goals. These UCNPs, chosen as optical labels in biological assays and medical imaging, could emit strong green emission under 980 nm laser. The MOF structure based on iron (III) carboxylate materials [MIL-100 (Fe)] possesses high porosity and non-toxicity, which is of great value as nanocarriers for drug storage/delivery. As a unique nanoplatform, the hybrid inorganic-organic drug delivery vehicles show great promising for simultaneous targeted labeling and therapy of cancer cells.

  15. An in-vivo study for targeted delivery of copper-organic complex to breast cancer using chitosan polymer nanoparticles.

    Science.gov (United States)

    Pramanik, Arindam; Laha, Dipranjan; Dash, Sandeep Kumar; Chattopadhyay, Sourav; Roy, Somenath; Das, Dipak Kumar; Pramanik, Panchanan; Karmakar, Parimal

    2016-11-01

    We have developed a strategy for targeted delivery of metal-diketo complex, "bis(2,4-pentanedionato) copper(II)" to breast cancer cells both in-vitro and in-vivo. This metal-organic complex induced ROS and subsequently DNA damage as well as mitochondrial membrane depolarization was observed. The mitochondria rupture further triggered apoptosis. For in-vitro targeting strategies, two different approaches were employed, folic acid or her-2 specific peptide (KCCYSL) was attached to stearic acid-modified polymeric Chitosan nanoparticles loaded with metal-organic complex "bis(2,4-pentanedionato)copper(II)". This was tested on two pairs of isogenic cells (FR+/FR- MCf-7 and her2+ /her2- MCF-7) and it was observed that cells expressing the receptor were susceptible to the drug whereas non-expressing isogenic cells were almost un-affected. During in-vivo studies, mice receiving targeted delivery of bis(2,4-pentanedionato) copper (II) had increased survivability and reduced tumor volume compared to non-targeted drug delivery. During toxicity studies for liver enzymes it was also found that the mice receiving targeted drug did not show any sign of liver damage as well as other histology changes. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. A laser based reusable microjet injector for transdermal drug delivery

    Science.gov (United States)

    Han, Tae-hee; Yoh, Jack J.

    2010-05-01

    A laser based needle-free liquid drug injection device has been developed. A laser beam is focused inside the liquid contained in the rubber chamber of microscale. The focused laser beam causes explosive bubble growth, and the sudden volume increase in a sealed chamber drives a microjet of liquid drug through the micronozzle. The exit diameter of a nozzle is 125 μm and the injected microjet reaches an average velocity of 264 m/s. This device adds the time-varying feature of microjet to the current state of liquid injection for drug delivery.

  17. Microemulsion: As Excellent Drug Delivery System

    Directory of Open Access Journals (Sweden)

    Pathan Maksud

    2012-09-01

    Full Text Available Today though the oral drug delivery system is dominant still it is found to be need of ideal transdermal drug delivery system. “A micro emulsion is a system of water, oil and an amphiphile which is a single optically isotropic and thermodynamically stable liquid solution”. Microemulsions offer several advantages as drug delivery systems as these are thermodynamically stable and stability allows for self emulsification of the system with microemulsion acting as supersolvent of the drugs which are poorly or insoluble in water. They are preferred more as compared to conventional emulsions due stability. The dispersed phase mainly acts as the solvent for the water insoluble drug. Microemulsions have been proved to increase the cutaneous absorption of both lipophilic and hydrophilic API’s when compared to conventional vehicles.

  18. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production.

    Science.gov (United States)

    Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen David

    2015-03-11

    Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts.

  19. Water stable metal-organic framework packed microcolumn for online sorptive extraction and direct analysis of naproxen and its metabolite from urine sample.

    Science.gov (United States)

    Hu, Yuling; Song, Chaoyong; Liao, Jia; Huang, Zelin; Li, Gongke

    2013-06-14

    The metal-organic framework MIL-101 was fabricated in a polyetheretherketone (PEEK) tube as micro-trapping device, and applied to sorptive extraction of naproxen and its metabolite in urine samples. The remarkable water stability of the MIL-101 characterizes the material as being different from other moisture sensitive metal-organic framework. It is therefore suitable for extraction of pharmaceuticals from biological fluids. The adsorption isotherms in aqueous solution showed that the adsorption of naproxen on MIL-101 is endothermic. Additionally, MIL-101 exhibited higher extraction capacity to naproxen than that of C18-bonded silica and multi-walled nanotube. A specially designed in-tube sorptive extraction (ITSE) device endows the extraction process with the characteristic of rapidness, convenience, and easy of conjunction with high performance liquid chromatography (HPLC). Finally the MIL-101 based ITSE method coupled with HPLC and fluorescence detection was applied to analysis of naproxen and 6-O-desmethylnaproxen in urine samples. Parameters that influence the online extraction procedure, including pH of the sample solution, flow rate of extraction, sample volume, desorption solvents and time were investigated. The method is proved to be highly sensitive with the linear range of 0.05-6.0μgL(-1) and the limits of detection of 0.034 and 0.011μgL(-1) for naproxen and 6-O-desmethylnaproxen, respectively. The recoveries in urine samples were 85.3-98.3% for naproxen and 94.0-97.3% for 6-O-desmethylnaproxen with intra- and inter-day RSDs of 2.7-5.2% and 7.1-8.1%, respectively. Urine samples could be directly subjected to analysis without any additional sample pretreatment. The proposed method was demonstrated an efficient, flexible and versatile extraction tool which is ideally suitable for online conjunction with chromatographic methods.

  20. NASAL IN SITU GEL: A NOVEL DRUG DELIVERY SYSTEM

    Directory of Open Access Journals (Sweden)

    Dhrupesh panchal

    2012-06-01

    Full Text Available Over the past few decades, advances in the in situ gel technologies have spurred development in manymedical and biomedical applications including controlled drug delivery. Many novel in situ gel baseddelivery matrices have been designed and fabricated to fulfill the ever increasing needs of thepharmaceutical and medical fields. In situ gelling systems are liquid at room temperature but undergogelation when in contact with body fluids or change in pH. In situ gel forming drug delivery is a type ofmucoadhesive drug delivery system. The formation of gel depends on factors like temperaturemodulation, pH change, presence of ions and ultraviolet irradiation from which the drug gets released ina sustained and controlled manner. Nasal delivery is a promising drug delivery option where commondrug administrations such as intravenous, intramuscular or oral are inapplicable. Recently, it has beenshown that many drugs have better bioavailability by nasal route than the oral route. This has beenattributed to rich vasculature and a highly permeable structure of the nasal mucosa coupled withavoidance of hepatic first-pass elimination, gut wall metabolism and/or destruction in thegastrointestinal tract. The physiology of the nose presents obstacles but offers a promising route for noninvasivesystemic delivery of numerous therapies and debatably drug delivery route to the brain. Thusthis review focuses on nasal drug delivery, various aspects of nasal anatomy and physiology, nasal drugabsorption mechanisms, various nasal drug delivery systems and their applications in drug delivery.

  1. Developing Design Criteria and Scale Up Methods for Water-Stable Metal-Organic Frameworks for Adsorption Applications

    Science.gov (United States)

    2014-09-08

    COBALT, NICKEL, COPPER , AND ZINC- BASED WATER STABLE PILLARED METAL-ORGANIC FRAMEWORKS 121 6.1 Introduction 121 6.2 Experimental Section 126...SYNTHESIS OF NOVEL COBALT, NICKEL, COPPER , AND ZINC- BASED WATER STABLE PILLARED METAL-ORGANIC FRAMEWORKS This work was conducted in collaboration with...by synthesizing cobalt, nickel, copper , and zinc-based new water stable pillared MOFs of similar topology (Figure 6.1b, Appendix D, Figure D.1

  2. Nanoscale coordination polymers for anticancer drug delivery

    Science.gov (United States)

    Phillips, Rachel Huxford

    This dissertation reports the synthesis and characterization of nanoscale coordination polymers (NCPs) for anticancer drug delivery. Nanoparticles have been explored in order to address the limitations of small molecule chemotherapeutics. NCPs have been investigated as drug delivery vehicles as they can exhibit the same beneficial properties as the bulk metal-organic frameworks as well as interesting characteristics that are unique to nanomaterials. Gd-MTX (MTX = methotrexate) NCPs with a MTX loading of 71.6 wt% were synthesized and stabilized by encapsulation within a lipid bilayer containing anisamide (AA), a small molecule that targets sigma receptors which are overexpressed in many cancer tissues. Functionalization with AA allows for targeted delivery and controlled release to cancer cells, as shown by enhanced efficacy against leukemia cells. The NCPs were doped with Ru(bpy)32+ (bpy = 2,2'-bipyridine), and this formulation was utilized as an optical imaging agent by confocal microscopy. NCPs containing the chemotherapeutic pemetrexed (PMX) were synthesized using different binding metals. Zr-based materials could not be stabilized by encapsulation with a lipid bilayer, and Gd-based materials showed that PMX had degraded during synthesis. However, Hf-based NCPs containing 19.7 wt% PMX were stabilized by a lipid coating and showed in vitro efficacy against non-small cell lung cancer (NSCLC) cell lines. Enhanced efficacy was observed for formulations containing AA. Additionally, NCP formulations containing the cisplatin prodrug disuccinatocisplatin were prepared; one of these formulations could be stabilized by encapsulation within a lipid layer. Coating with a lipid layer doped with AA rendered this formulation an active targeting agent. The resulting formulation proved more potent than free cisplatin in NSCLC cell lines. Improved NCP uptake was demonstrated by confocal microscopy and competitive binding assays. Finally, a Pt(IV) oxaliplatin prodrug was

  3. Reaction Engineering with Metal-Organic Framework Catalysts

    Science.gov (United States)

    Melkonian, Arek Viken

    To date, there has been no comprehensive attempt to perform and/or describe catalytic reactions in the gas phase that utilize metal-organic frameworks (MOFs) as catalysts. In addition, there has been no attempt to reaction engineer these MOF catalysts in order to determine their regimes of optimal catalytic activity and possible limitations to their use. A zinc-based MOF that has been post-synthetically modified with a homogeneous palladium catalyst, Pd(CH 3CN)2Cl2, is used to catalyze the hydrogenation of propylene. The catalyst is assembled in a packed-bed reactor under a continuous flow of reactants. The reaction is optimized with respect to isoreticular metalation, reactant flow rate, and reactor temperature. Maximum catalytic conversion is found at intermediate metalations of 40% and 60%, high hydrogen flow of 50 ccm, and intermediate reactor temperatures of 100 °C and 150 °C. The MOF-60 catalyst is exposed to a traditional catalyst poison, carbon monoxide (CO). It is found that the MOF is reversibly poisoned upon introduction of CO. Upon poisoning, catalytic conversions rates of 90%-100% are dramatically reduced to less than 10%-30%, depending on the CO flow rate and the reactor temperature. The CO poisoning is shown to be reversible, a similar effect as found with palladium on carbon (Pd/C). The time scale of poisoning and recovery is very fast for both the MOF catalyst and Pd/C (approximately 10-30 seconds). Other effects of temperature on the MOF-40 are also investigated. At fixed reactant flow, the temperature grid is partitioned into finer steps of 10 °C to determine the temperature that yields the highest catalytic conversion. It is found that conversion is nearly uniform in the range between the highest conversions, i.e., conversion plateaus between the optimum temperatures. The catalyst also exhibits a weak thermal hysteresis. There is no significant improvement in conversion with thermal cycling after alternating the reactor temperature between

  4. Flexible and hydrophobic Zn-based metal-organic framework.

    Science.gov (United States)

    Hauptvogel, Ines Maria; Biedermann, Ralf; Klein, Nicole; Senkovska, Irena; Cadiau, Amandine; Wallacher, Dirk; Feyerherm, Ralf; Kaskel, Stefan

    2011-09-05

    A zinc-based metal-organic framework Zn(2)(adb)(2)(dabco)·4.5 DMF (K) (DUT-30(Zn), DUT = Dresden University of Technology, adb = 9,10-anthracene dibenzoate, dabco =1,4-diazabicyclo[2.2.2]octane, DMF = N,N-dimethylformamide) was synthesized using a solvothermal route. This MOF exhibits six crystallographic guest dependent phases. Two of them were characterized via single crystal X-ray analysis. The as-synthesized phase K crystallizes in the orthorhombic space group Fmmm, with a = 9.6349(9), b = 26.235(3), and c = 28.821(4) Å and consists of two interpenetrated pillar-layer networks with pcu topology. When the substance loses 0.5 DMF molecules per formula unit, a phase transition from the kinetic phase K to a thermodynamic phase T occurs. Zn(2)(adb)(2)(dabco)·4 DMF (T) crystallizes in the tetragonal space group I4/mmm, with a = 19.5316(8) and c = 9.6779(3) Å. During the evacuation the DUT-30(Zn) undergoes again the structural transformation to A. The activated compound A shows the gate pressure effect in the low pressure region of nitrogen physisorption isotherm and has a BET surface area of 960 m(2 )g(-1) and a specific pore volume of 0.43 cm(3) g(-1). Furthermore, DUT-30(Zn) exhibits a hydrogen storage capacity of 1.12 wt % at 1 bar, a CO(2) uptake of 200 cm(3) g(-1) at -78 °C and 0.9 bar, and a n-butane uptake of 3.0 mmol·g(-1) at 20 °C. The N(2) adsorption process was monitored in situ via X-ray powder diffraction using synchrotron radiation. A low temperature induced transformation of phase A to phase V could be observed if the compound was cooled under vacuum to -196 °C. A further crystalline phase N could be identified if the framework was filled with nitrogen at -196 °C. Additionally, the treatment of activated phase A with water leads to the new phase W.

  5. Using functional nano- and microparticles for the preparation of metal-organic framework composites with novel properties.

    Science.gov (United States)

    Doherty, Cara M; Buso, Dario; Hill, Anita J; Furukawa, Shuhei; Kitagawa, Susumu; Falcaro, Paolo

    2014-02-18

    A critical materials challenge over the next quarter century is the sustainable use and management of the world's natural resources, particularly the scarcest of them. Chemistry's ability to get more from less is epitomized by porous coordination polymers, also known as metal-organic frameworks (MOFs), which use a minimum amount of material to build maximum surface areas with fine control over pore size. Their large specific surface area and tunable porosity make MOFs useful for applications including small-molecule sensing, separation, catalysis, and storage and release of molecules of interest. Proof-of-concept projects have demonstrated their potential for environmental applications such as carbon separation and capture, water purification, carcinogen sequestration, byproduct separation, and resource recovery. To translate these from the laboratory into devices for actual use, however, will require synthesis of MOFs with new functionality and structure. This Account summarizes recent progress in the use of nano- and microparticles to control the function, location, and 3D structure of MOFs during MOF self-assembly, creating novel, hybrid, multifunctional, ultraporous materials as a first step towards creating MOF-based devices. The use of preformed ceramic, metallic, semiconductive, or polymeric particles allows the particle preparation process to be completely independent of the MOF synthesis, incorporating nucleating, luminescent, magnetic, catalytic, or templating particles into the MOF structure. We discuss success in combining functional nanoparticles and porous crystals for applications including molecular sieve detectors, repositionable and highly sensitive sensors, pollutant-sequestering materials, microfluidic microcarriers, drug-delivery materials, separators, and size-selective catalysts. In sections within the Account, we describe how functional particles can be used for (1) heterogeneous nucleation (seeding) of MOFs, (2) preparation of framework

  6. Single-step fabrication of nanolamellar structured oxide ceramic coatings by metal-organic chemical vapor deposition.

    Science.gov (United States)

    Eils, Nadine K; Mechnich, Peter; Keune, Hartmut; Wahl, Georg; Klages, Claus-Peter

    2011-09-01

    Oxide ceramic coatings in the system Y2O3-Al2O3-ZrO2 were fabricated in laboratory scale by using a MOCVD unit. A hot wall reactor was used along with different precursor feeding systems. Most experiments were carried out by using powder flash evaporation including a screw feeder for precursor powder delivery. For comparison, further samples were fabricated by using band flash evaporation and continuous evaporation from a crucible. Oxygen was used in all cases as reactant gas. Aluminium-tris-2,4-pentanedione (Al(acac)3), yttrium-tris-2,2,6,6-tetramethyl-3,5-heptanedione (Y(thd)3) and zirconium-tetrakis-2,2,6,6-tetramethyl-3,5-heptanedione (Zr(thd)4) were applied as metal-organic precursors because of their similar vaporization behaviour under the given conditions. The coating stoichiometry was varied from pure alumina to complex ternary compositions in the system Y2O3-Al2O3-ZrO2. Both kinds of ternary coatings fabricated by using flash evaporation methods show a nanolamellar microstructure in the as deposited state. Heat treating experiments at 1200 degrees C for up to 5 days enhance the lamellar character of the coating deposited by using powder flash evaporation. The lamellar microstructure is due to alternating YSZ enriched layers and YAG enriched layers in this state. However, the coating fabricated by using band flash evaporation shows a dense interpenetrating network of YSZ and YAG after heat treating instead of a lamellar microstructure observed in the as deposited state.

  7. Project delivery system (PDS)

    CERN Document Server

    2001-01-01

    As business environments become increasingly competitive, companies seek more comprehensive solutions to the delivery of their projects. "Project Delivery System: Fourth Edition" describes the process-driven project delivery systems which incorporates the best practices from Total Quality and is aligned with the Project Management Institute and ISO Quality Standards is the means by which projects are consistently and efficiently planned, executed and completed to the satisfaction of clients and customers.

  8. Cesarean Delivery in Adolescents.

    Science.gov (United States)

    Katz Eriksen, Jennifer L; Melamed, Alexander; Clapp, Mark A; Little, Sarah E; Zera, Chloe

    2016-10-01

    To examine the effect of maternal age on indication for primary cesarean delivery in low-risk nulliparous women. Retrospective cohort study. Urban academic tertiary care center. Nulliparous women younger than 35 years of age delivering vertex-presenting singletons at term. Participants underwent spontaneous, operative or cesarean delivery. Mode of delivery, indication, and timing of cesarean delivery. Adolescents were half as likely to undergo cesarean delivery overall (odds ratio [OR], 0.48; 95% confidence interval [CI], 0.43-0.54), and more than one-third less likely to undergo cesarean delivery in labor (OR, 0.59; 95% CI, 0.53-0.66). Adjustment for potential confounders did not alter the strength of these associations. Adolescents were half as likely to undergo cesarean delivery for failure to progress (OR, 0.49; 95% CI, 0.43-0.54). There was no difference in the odds of cesarean delivery for nonreassuring fetal status (OR, 0.91; 95% CI, 0.77-1.06), or genital herpes (OR, 1.44; 95% CI, 0.57-3.68). Induction, macrosomia, oxytocin augmentation, and any labor complication were all associated with increased risk of cesarean delivery. There was no difference in the duration of second stage for adolescents who delivered by cesarean delivery compared with adults (240.0 vs 237.7 minutes; P = .84), but adolescents who delivered vaginally had a second stage that was one-third shorter than adults (62.5 vs 100.3 minutes; P cesarean delivery overall, and 40% less likely to undergo a primary cesarean delivery in labor, even after adjustment for multiple maternal, neonatal, and labor characteristics. This difference is not explained by differences in the duration of the second stage of labor. Copyright © 2016 North American Society for Pediatric and Adolescent Gynecology. Published by Elsevier Inc. All rights reserved.

  9. Current and new strategies for the delivery of antiseptic agents.

    Science.gov (United States)

    Constant, Hélène; Falson, Françoise; Pirot, Fabrice

    2006-07-01

    The present mini-review explores the current methods used for the delivery of antiseptics and topical antimicrobials. Relevance of hand scrub with antiseptic liquid soap (e.g. chlorhexidine, PVP-iodine, triclosan) and alcohol-based hand rub is discussed and compared in terms of bactericidal activity, skin tolerance, and medical staff observance. New strategies for antibacterial delivery focus on the challenge of colloidal drug carrier such as liposomes, micro- and nanoparticles enabling sustained bactericidal effect and effective bacterial targeting.

  10. Smart polymers in nasal drug delivery

    Directory of Open Access Journals (Sweden)

    Ankita Chonkar

    2015-01-01

    Full Text Available Nasal drug delivery has now been recognized as a promising route for drug delivery due to its capability of transporting a drug to systemic circulation and central nervous system. Though nasal mucosa offers improved bioavailability and quick onset of action of the drug, main disadvantage associated with nasal drug delivery is mucocilliary clearance due to which drug particles get cleared from the nose before complete absorption through nasal mucosa. Therefore, mucoadhesive polymeric approach can be successfully used to enhance the retention of the drug on nasal mucosal surface. Here, some of the aspects of the stimuli responsive polymers have been discussed which possess liquid state at the room temperature and in response to nasal temperature, pH and ions present in mucous, can undergo in situ gelation in nasal cavity. In this review, several temperature responsive, pH responsive and ion responsive polymers used in nasal delivery, their gelling mechanisms have been discussed. Smart polymers not only able to enhance the retention of the drug in nasal cavity but also provide controlled release, ease of administration, enhanced permeation of the drug and protection of the drug from mucosal enzymes. Thus smart polymeric approach can be effectively used for nasal delivery of peptide drugs, central nervous system dugs and hormones.

  11. Melt-quenched glasses of metal-organic frameworks

    DEFF Research Database (Denmark)

    Bennett, T.D.; Yue, Yuanzheng; Li, P.

    2016-01-01

    Crystalline solids dominate the field of metal−organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand the phen...

  12. The biocompatibility of metal-organic framework coatings: an investigation on the stability of SURMOFs with regard to water and selected cell culture media.

    Science.gov (United States)

    Hanke, Maximilian; Arslan, Hasan K; Bauer, Stella; Zybaylo, Olexandra; Christophis, Christof; Gliemann, Hartmut; Rosenhahn, Axel; Wöll, Christof

    2012-05-01

    Highly porous thin films based on a [Cu(bdc)(2)](n) (bdc = benzene-1,4-dicarboxylic acid) metal-organic framework, MOF, grown using liquid-phase epitaxy (LPE) show remarkable stability in pure water as well as in artificial seawater. This opens the possibility to use these highly porous coatings for environmental and life science applications. Here we characterize in detail the stability of these SURMOF 2 thin films under aqueous and cell culture conditions. We find that the material degrades only very slowly in water and artificial seawater (ASW) whereas in typical cell culture media (PBS and DMEM) a rapid dissolution is observed. The release of Cu(2+) ions resulting from the dissolution of the SURMOF 2 in the liquids exhibits no adverse effect on the adhesion of fibroblasts, prototype eukaryotic cells, to the substrate and their subsequent proliferation, thus demonstrating the biocompatibility of SURMOF 2 surface coatings. Thus, the results are an important step toward application of these porous materials as a slow release matrix, for example, for pharmaceuticals and growth factors.

  13. Subsidizing Liquidity

    DEFF Research Database (Denmark)

    Malinova, Katya; Park, Andreas

    2015-01-01

    Facing increased competition over the last decade, many stock exchanges changed their trading fees to maker-taker pricing, an incentive scheme that rewards liquidity suppliers and charges liquidity demanders. Using a change in trading fees on the Toronto Stock Exchange, we study whether and why...

  14. Liquid pearls

    CERN Document Server

    Bremond, Nicolas; Bibette, Jérôme

    2010-01-01

    This fluid dynamics video reports how to form liquid core capsules having a thin hydrogel elastic membrane named liquid pearls. These fish-egg like structures are initially made of a millimetric liquid drop, aqueous or not, coated with an aqueous liquid film containing sodium alginate that gels once the double drop enters a calcium chloride bath. The creation of such pearls with micrometer thick membrane requires to suppress mixing until gelling takes place. Here, we show that superimposing a two dimensional surfactant precipitation at the interface confers a transient rigidity that can damp the shear induced instability at impact. Based on this, pearls containing almost any type of liquids can be created. The video focuses on the dynamics of the entry of the compound drop into the gelling bath.

  15. Prediction of preterm delivery

    NARCIS (Netherlands)

    Wilms, F.F.

    2014-01-01

    Preterm delivery is in quantity and in severity an important issue in the obstetric care in the Western world. There is considerable knowledge on maternal and obstetric risk factors of preterm delivery. Of the women presenting with preterm labor, the majority is pregnant with a male fetus and in

  16. Prediction of preterm delivery

    NARCIS (Netherlands)

    Wilms, F.F.

    2014-01-01

    Preterm delivery is in quantity and in severity an important issue in the obstetric care in the Western world. There is considerable knowledge on maternal and obstetric risk factors of preterm delivery. Of the women presenting with preterm labor, the majority is pregnant with a male fetus and in Cau

  17. Delivery by Cesarean Section

    Science.gov (United States)

    ... often when: The mother has had a previous baby by Cesarean delivery The obstetrician feels that the baby’s health might ... lost time. Don’t be surprised if your baby is still affected by the anesthesia for six to twelve hours after delivery and appears a little sleepy. If you’re ...

  18. Vacuum-assisted delivery

    Science.gov (United States)

    ... a handle on the cup to move the baby through the birth canal. When is Vacuum-assisted Delivery Needed? Even after your cervix is fully dilated ( ... delivers the baby's head, you will push the baby the rest of the way out. After delivery, you can hold your baby on your tummy ...

  19. Metal-Organic Frameworks: Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion (Small 17/2016).

    Science.gov (United States)

    Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

    2016-05-01

    On page 2334, R. Q. Zou, Y. L. Zhao, and co-workers present a porous metal-organic framework (MOF) that serves as a platform for studying the metal exchange effect on both CO2 adsorption and catalytic fixation. The effect is demonstrated by catalytic CO2 cycloaddition with propylene oxide to produce propylene carbonate. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange could influence the intrinsic properties of MOFs.

  20. Strategies for Enhancing the Catalytic Performance of Metal-Organic Frameworks in the Fixation of CO2 into Cyclic Carbonates.

    Science.gov (United States)

    Taherimehr, Masoumeh; Van de Voorde, Ben; Wee, Lik H; Martens, Johan A; De Vos, Dirk E; Pescarmona, Paolo P

    2017-03-22

    Metal-organic frameworks (MOFs) with accessible Lewis acid sites are finding increasing application in the field of heterogeneous catalysis. However, the structural instability of MOFs when they are exposed to high temperature and/or high pressure often limits their applicability. In this study, two strategies were applied to achieve a MOF catalyst with high stability, activity and selectivity in the reaction of CO2 with styrene oxide to produce styrene carbonate. In the first approach, a MOF with linkers with high connectivity as MIL-100(Cr) was studied, leading to promising activity and recyclability in consecutive catalytic runs without loss of activity. In the second strategy, a MOF with linkers with lower connectivity but with encapsulated Keggin phosphotungstic acid (MIL-101(Cr)[PTA]) was prepared. However, the activity of this catalyst decreased upon reuse as a consequence of deterioration of the MOF. Further investigations were dedicated to the enhancement of the catalytic performance of MIL-100 and included the variation of the metal centre as well as the type and loading of organic salt acting as nucleophile source. This allowed tuning the nature of the organic halide to the specific porous structure of MIL-100(Cr) to prevent diffusion limitations. The best catalytic performance was obtained for MIL-100(Cr) in combination with EMIMBr ionic liquid, which gave very high styrene carbonate yield (94 %) with complete selectivity after 18 h of reaction at mild temperature (60 °C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Route to a family of robust, non-interpenetrated metal-organic frameworks with pto-like topology.

    Science.gov (United States)

    Klein, Nicole; Senkovska, Irena; Baburin, Igor A; Grünker, Ronny; Stoeck, Ulrich; Schlichtenmayer, Maurice; Streppel, Barbara; Mueller, Uwe; Leoni, Stefano; Hirscher, Michael; Kaskel, Stefan

    2011-11-11

    A combination of topological rules and quantum chemical calculations has facilitated the development of a rational metal-organic framework (MOF) synthetic strategy using the tritopic benzene-1,3,5-tribenzoate (btb) linker and a neutral cross-linker 4,4'-bipyridine (bipy). A series of new compounds, namely [M(2)(bipy)](3)(btb)(4) (DUT-23(M), M = Zn, Co, Cu, Ni), [Cu(2)(bisqui)(0.5)](3)(btb)(4) (DUT-24, bisqui = diethyl (R,S)-4,4'-biquinoline-3,3'-dicarboxylate), [Cu(2)(py)(1.5)(H(2)O)(0.5)](3)(btb)(4) (DUT-33, py = pyridine), and [Cu(2)(H(2)O)(2)](3)(btb)(4) (DUT-34), with high specific surface areas and pore volumes (up to 2.03 m(3)  g(-1) for DUT-23(Co)) were synthesized. For DUT-23(Co), excess storage capacities were determined for methane (268 mg g(-1) at 100 bar and 298 K), hydrogen (74 mg g(-1) at 40 bar and 77 K), and n-butane (99 mg g(-1) at 293 K). DUT-34 is a non-cross-linked version of DUT-23 (non-interpenetrated pendant to MOF-14) that possesses open metal sites and can therefore be used as a catalyst. The accessibility of the pores in DUT-34 to potential substrate molecules was proven by liquid phase adsorption. By exchanging the N,N donor 4,4'-bipyridine with a substituted racemic biquinoline, DUT-24 was obtained. This opens a route to the synthesis of a chiral compound, which could be interesting for enantioselective separation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Template-Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal-Organic Frameworks.

    Science.gov (United States)

    Kim, Daeok; Coskun, Ali

    2017-04-24

    Controlling the arrangement of different metal ions to achieve ordered heterogeneity in metal-organic frameworks (MOFs) has been a great challenge. Herein, we introduce a template-directed approach, in which a 1D metal-organic polymer incorporating well-defined binding pockets for the secondary metal ions used as a structural template and starting material for the preparation of well-ordered bimetallic MOF-74s under heterogeneous-phase hydrothermal reaction conditions in the presence of secondary metal ions such as Ni(2+) and Mg(2+) in 3 h. The resulting bimetallic MOF-74s were found to possess a nearly 1:1 metal ratio regardless of their initial stoichiometry in the reaction mixture, thus demonstrating the possibility of controlling the arrangement of metal ions within the secondary building blocks in MOFs to tune their intrinsic properties such as gas affinity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Metal-organic extended 2D structures: Fe-PTCDA on Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez, Lucia; Caillard, Renaud; MartIn-Gago, Jose A; Mendez, Javier [Grupo ESISNA, Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas (CSIC), c/ Sor Juana Ines de la Cruz 3, Campus de Cantoblanco, E-28049 Madrid (Spain); Pelaez, Samuel; Serena, Pedro A, E-mail: jmendez@icmm.csic.es [Grupo de Teoria y Simulacion de Materiales, Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas (CSIC), c/ Sor Juana Ines de la Cruz 3, Campus de Cantoblanco, E-28049 Madrid (Spain)

    2010-07-30

    In this work we combine organic molecules of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) with iron atoms on an Au (111) substrate in ultra-high vacuum conditions at different temperatures. By means of scanning tunnelling microscopy (STM) we study the formation of stable 2D metal-organic structures. We show that at certain growth conditions (temperature, time and coverage) stable 'ladder-like' nanostructures are obtained. These are the result of connecting together two metal-organic chains through PTCDA molecules placed perpendicularly, as rungs of a ladder. These structures, stable up to 450 K, can be extended in a 2D layer covering the entire surface and presenting different rotation domains. STM images at both polarities show a contrast reversal between the two molecules at the unit cell. By means of density functional theory (DFT) calculations, we confirm the stability of these structures and that their molecular orbitals are placed separately at the different molecules.

  4. Tuning the ferroelectric polarization in a multiferroic metal-organic framework.

    Science.gov (United States)

    Di Sante, Domenico; Stroppa, Alessandro; Jain, Prashant; Picozzi, Silvia

    2013-12-04

    We perform density functional theory calculations on a recently synthesized metal-organic framework (MOF) with a perovskite-like topology ABX3, i.e., [CH3CH2NH3]Mn(HCOO)3, and predict a multiferroic behavior, i.e., a coexistence of ferroelectricity and ferromagnetism. A peculiar canted ordering of the organic A-cation dipole moments gives rise to a ferroelectric polarization of ~2 μC/cm(2). Starting from these findings, we show that by choosing different organic A cations, it is possible to tune the ferroelectric polarization and increase it up to 6 μC/cm(2). The possibility of changing the magnitude and/or the canting of the organic molecular dipole opens new routes toward engineering ferroelectric polarization in the new class of multiferroic metal-organic frameworks.

  5. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    Science.gov (United States)

    Butova, V. V.; Soldatov, M. A.; Guda, A. A.; Lomachenko, K. A.; Lamberti, C.

    2016-03-01

    This review deals with key methods of synthesis and characterization of metal-organic frameworks (MOFs). The modular structure affords a wide variety of MOFs with different active metal sites and organic linkers. These compounds represent a new stage of development of porous materials in which the pore size and the active site structure can be modified within wide limits. The set of experimental methods considered in this review is sufficient for studying the short-range and long-range order of the MOF crystal structure, determining the morphology of samples and elucidating the processes that occur at the active metal site in the course of chemical reactions. The interest in metal-organic frameworks results, first of all, from their numerous possible applications, ranging from gas separation and storage to chemical reactions within the pores. The bibliography includes 362 references.

  6. Doping of Metal-Organic Frameworks with Functional Guest Molecules and Nanoparticles

    Science.gov (United States)

    Schröder, Felicitas; Fischer, Roland A.

    Nanoparticle synthesis within metal-organic frameworks (MOFs) is performed by the adsorption of suitable precursor molecules for the metal component and subsequent decomposition to the composite materials nanoparticles@MOF. This chapter will review different approaches of loading MOFs with more complex organic molecules and metal-organic precursor molecules. The related reactions inside MOFs are discussed with a focus on stabilizing reactive intermediates in the corresponding cavities. The syntheses of metal and metal oxide nanoparticles inside MOFs are reviewed, and different synthetic routes compared. Emphasis is placed on the micro structural characterization of the materials nanoparticles@MOF with a particular focus on the location of embedded nanoparticles using TEM methods. Some first examples of applications of the doped MOFs in heterogeneous catalysis and hydrogen storage are described.

  7. Molecular dynamics simulations of gas diffusion in metal-organic frameworks: argon in CuBTC.

    Science.gov (United States)

    Skoulidas, Anastasios I

    2004-02-11

    The class of coordination polymers known as metal-organic frameworks (MOFs) has three-dimensional porous structures that are considered as a promising alternative to zeolites and other nanoporous materials for catalysis, gas adsorption, and gas separation applications. In this paper, we present the first study of gas diffusion inside an MOF and compare the observed diffusion to known behaviors in zeolites. Using grand canonical Monte Carlo and equilibrium molecular dynamics, we calculate the adsorption isotherm and self-, corrected, and transport diffusivities for argon in the CuBTC metal-organic framework. Our results indicate that diffusion of Ar in CuBTC is very similar to Ar diffusion in silica zeolites in magnitude, concentration, and temperature dependence. This conclusion appears to apply to a broad range of MOF structures.

  8. Interplay between defects, disorder and flexibility in metal-organic frameworks

    Science.gov (United States)

    Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.; Coudert, François-Xavier

    2017-01-01

    Metal-organic frameworks are a novel family of chemically diverse materials, which are of interest across engineering, physics, chemistry, biology and medicine-based disciplines. Since the development of the field in its current form more than two decades ago, priority has been placed on the synthesis of new structures. However, more recently, a clear trend has emerged in shifting the emphasis from material design to exploring the chemical and physical properties of structures already known. In particular, although such nanoporous materials were traditionally seen as rigid crystalline structures, there is growing evidence that large-scale flexibility, the presence of defects and long-range disorder are not the exception in metal-organic frameworks, but the rule. Here we offer some perspective into how these concepts are perhaps inescapably intertwined, highlight recent advances in our understanding and discuss how a consideration of the interfaces between them may lead to enhancements of the materials' functionalities.

  9. Homochiral helical metal-organic frameworks of group 1 metals.

    Science.gov (United States)

    Reger, Daniel L; Leitner, Andrew; Smith, Mark D; Tran, T Thao; Halasyamani, P Shiv

    2013-09-01

    The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HL(ala)) and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HL(ser)), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center, and a 1,8-naphthalimide π···π stacking supramolecular tecton and in the case of HL(ser) an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(L(ala))(MeOH) (1), K(L(ala))(H2O) (2), Na(L(ala))(H2O) (3), KL(ser) (4), CsL(ser) (5), and CsL(ala) (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod secondary building unit (SBU) central cores. In addition to the bonding of the carboxylate and solvent (in the case of L(ser) the ligand alcohol) to the metals, both oxygens on the 1,8-naphthalimide act as donor groups. One naphthalimide oxygen bonds to the same helical rod SBU as the carboxylate group of that ligand forming a chelate ring. The other naphthalimide oxygen bonds to adjacent SBUs. In complexes 1-3, this inter-rod link has a square arrangement bonding four other rods forming a three-dimensional enantiopure metal-organic framework (MOF) structure, whereas in 4-6 this link has a linear arrangement bonding two other rods forming a two-dimensional, sheet structure. In the latter case, the third dimension is supported exclusively by interdigitated π···π stacking interactions of the naphthalimide supramolecular tecton, forming enantiopure supramolecular MOF solids. Compounds 1-3 lose the coordinated solvent when heating above 100 °C. For 1, the polycrystalline powder reverts to 1 only by recrystallization from methanol, whereas compounds 2 and 3 undergo gas/solid, single-crystal to single-crystal transformations to form dehydrated compounds 2* and 3*, and rehydration occurs when crystals of these new complexes are left out in air. The reversible single

  10. Quantification of Temozolomide in Nonhuman Primate Fluids by Isocratic Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry to Study Brain Tissue Penetration Following Intranasal or Intravenous Delivery

    Directory of Open Access Journals (Sweden)

    Cody J. Peer

    2016-02-01

    Full Text Available A sensitive and selective ultra-high performance liquid chromatography-tandem mass spectrometric method was developed for the quantification of temozolomide (TMZ in nonhuman primate (NHP plasma, cerebrospinal fluid (CSF, and brain extracellular fluid (ECF following microdialysis. Ethyl acetate was used to extract the plasma and CSF samples, using theophylline as the internal standard (IS. ECF samples were diluted with acetonitrile prior to analysis. TMZ was separated on a Waters UPLC® BEH C18 column with an isocratic mobile phase of ammonium acetate (10 mM-0.1% formic acid/acetonitrile (30:70, v/v in a positive-ion multiple reaction monitoring mode (m/z 195.5→137.6 for TMZ; m/z 181.5→124.2 for IS. The retention time of TMZ and theophylline was 0.45 min with a total run time of 2.5 min. The method was validated over the range from 5–2000 ng/mL in NHP plasma, CSF, and ECF with respect to linearity, accuracy, precision, selectivity, and stability. This method was successfully applied toward the measurement of pharmacokinetic samples following various routes of drug administration.

  11. Validation and Application of an Ultra High-Performance Liquid Chromatography Tandem Mass Spectrometry Method for Yuanhuacine Determination in Rat Plasma after Pulmonary Administration: Pharmacokinetic Evaluation of a New Drug Delivery System.

    Science.gov (United States)

    Li, Man; Liu, Xiao; Cai, Hao; Shen, Zhichun; Xu, Liu; Li, Weidong; Wu, Li; Duan, Jinao; Chen, Zhipeng

    2016-12-16

    Yuanhuacine was found to have significant inhibitory activity against A-549 human lung cancer cells. However, there would be serious adverse toxicity effects after systemic administration of yuanhuacine, such as by oral and intravenous ways. In order to achieve better curative effect and to alleviate the adverse toxicity effects, we tried to deliver yuanhuacine directly into the lungs. Ultra high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was used to detect the analyte and IS. After extraction (ether:dichloromethane = 8:1), the analyte and IS were separated on a Waters BEH-C18 column (100 mm × 2.1 mm, 1.7 μm) under a 5 min gradient elution using a mixture of acetonitrile and 0.1% formic acid aqueous solution as mobile phase at a flow rate of 0.3 mL/min. ESI positive mode was chosen for detection. The method was fully validated for its selectivity, accuracy, precision, stability, matrix effect, and extraction recovery. This new method for yuanhuacine concentration determination in rat plasma was reliable and could be applied for its preclinical and clinical monitoring purpose.

  12. A microporous metal-organic framework for selective C2H2 and CO2 separation

    Science.gov (United States)

    Lin, Rong-Guang; Lin, Rui-Biao; Chen, Banglin

    2017-08-01

    A quartzlike metal-organic framework with interesting one dimensional channel has been synthesized. It exhibits considerable acetylene and carbon dioxide uptake of 41.5 and 24.6 cm3 g-1, respectively, and relatively high selectivity for separation of C2H2/C2H4, C2H2/CH4, CO2/CH4 and CO2/N2 at ambient condition.

  13. Self-assembly of metal-organic coordination structures on surfaces

    Science.gov (United States)

    Dong, Lei; Gao, Zi'Ang; Lin, Nian

    2016-08-01

    Metal-organic coordination structures are materials comprising reticular metal centers and organic linkers in which the two constituents bind with each other via metal-ligand coordination interaction. The underlying chemistry is more than a century old but has attracted tremendous attention in the last two decades owing to the rapidly development of metal-organic (or porous coordination) frameworks. These metal-coordination materials exhibit extraordinarily versatile topologies and many potential applications. Since 2002, this traditionally three-dimensional chemistry has been extended to two-dimensional space, that is, to synthesize metal-organic coordination structures directly on solid surfaces. This endeavor has made possible a wide range of so-called surface-confined metal-organic networks (SMONs) whose topology, composition, property and function can be tailored by applying the principle of rational design. The coordination chemistry manifests unique characteristics at the surfaces, and in turn the surfaces provide additional control for design structures and properties that are inaccessible in three-dimensional space. In this review, our goal is to comprehensively cover the progress made in the last 15 years in this rapidly developing field. The review summarizes (1) the experimental and theoretical techniques used in this field including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, density functional theory, and Monte Carlo and kinetic Monte Carlo simulation; (2) molecular ligands, metal atoms, substrates, and coordination motifs utilized for synthesizing SMON; (3) representative SMON structures with different topologies ranging from finite-size discrete clusters to one-dimensional chains, two-dimensional periodical frameworks and random networks; and (4) the properties and potential applications of SMONs. We conclude the review with some perspectives.

  14. Integrated DFB-DBR laser modulator grown by selective area metalorganic vapor phase epitaxy growth technique

    Science.gov (United States)

    Tanbun-Ek, T.; Chen, Y. K.; Grenko, J. A.; Byrne, E. K.; Johnson, J. E.; Logan, R. A.; Tate, A.; Sergent, A. M.; Wecht, K. W.; Sciortine, P. F.; Chu, S. N. G.

    1994-12-01

    A device quality of selective epitaxy growth of InGaAsP/InP multiple quantum well (MQW) structure using low-pressure metalorganic vapor phase epitaxy (MOVPE) technique is described. The technique is applied to a monolithically integrated electroabsorption modulator with distributed feedback (DFB) and distributed Bragg reflector (DBR) lasers. Superior device characteristics such as efficient modulation, low threshold current and high efficiency operation of the integrated devices are obtained.

  15. Metal-organic frameworks with high capacity and selectivity for harmful gases

    OpenAIRE

    Britt, David; Tranchemontagne, David; Yaghi, Omar M.

    2008-01-01

    Benchmarks have been established for the performance of six metal-organic frameworks (MOFs) and isoreticular MOFs (IRMOFs, which have the same underlying topology as MOF-5), MOF-5, IRMOF-3, MOF-74, MOF-177, MOF-199, and IRMOF-62, as selective adsorbents for eight harmful gases: sulfur dioxide, ammonia, chlorine, tetrahydrothiophene, benzene, dichloromethane, ethylene oxide, and carbon monoxide. Kinetic breakthrough measurements are used to determine the calculated dynamic adsorption capacity ...

  16. Lithographic deposition of patterned metal-organic framework coatings using a photobase generator.

    Science.gov (United States)

    Keitz, Benjamin K; Yu, Chung Jui; Long, Jeffrey R; Ameloot, Rob

    2014-05-26

    A photobase generator was used to induce metal-organic framework (MOF) nucleation upon UV irradiation. This method was further developed into a simple, one-step method for depositing patterned MOF films. Furthermore, the ability of our method to coat a single substrate with MOF films having different chemical compositions is illustrated. The method is an important step towards integrating MOF deposition with existing lithographic techniques and the incorporation of these materials into sensors and other electronic devices.

  17. Application of CO2-TPD in the Synthesis of Composite Oxides from Metal-Organic Precursors

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    CO2-TPD was demonstrated an effective way to investigate the phase formation during pyrolysis for the preparation of composite oxides using metal-organic molecules as precursors. Based on the CO2-TPD results, it was found that calcination condition had deep effect on the carbonate formation and the minimum firing temperature to acquire pure phase composite oxide. An optimized calcination schedule was then developed.

  18. In Situ Synthesis of Metal Sulfide Nanoparticles Based on 2D Metal-Organic Framework Nanosheets.

    Science.gov (United States)

    Lu, Qipeng; Zhao, Meiting; Chen, Junze; Chen, Bo; Tan, Chaoliang; Zhang, Xiao; Huang, Ying; Yang, Jian; Cao, Feifei; Yu, Yifu; Ping, Jianfeng; Zhang, Zhicheng; Wu, Xue-Jun; Zhang, Hua

    2016-09-01

    A facile in situ synthetic method is developed to synthesize metal sulfide nanoparticles based on 2D M-TCPP (M = Cu, Cd, or Co, TCPP = tetrakis(4-carboxyphenyl)porphyrin)) metal-organic framework nanosheets. The obtained CuS/Cu-TCPP composite nanosheet is used as the active material in photoelectrochemical cells, showing notably increased photocurrent due to the improved exciton separation and charge carrier transport.

  19. New Cerium-Based Metal-Organic Scintillators for Radiation Detection

    Energy Technology Data Exchange (ETDEWEB)

    Boatner, Lynn A [ORNL; Neal, John S [ORNL; Ramey, Joanne Oxendine [ORNL; Chakoumakos, Bryan C [ORNL; Custelcean, Radu [ORNL; Van Loef, Edgar [Radiation Monitoring Devices, Watertown, MA; Markosyan, G [Radiation Monitoring Devices, Watertown, MA

    2013-01-01

    We have previously shown that a new class of scintillating materials can be developed based on the synthesis and crystal growth of rare-earth metal-organic compounds. The first scintillator of this type consisted of single crystals of CeCl3(CH3OH)4 that were grown from a methanol solution. These crystals were shown to be applicable to both gamma-ray and fast neutron detection. Subsequently, metal-organic scintillators consisting of the compound LaBr3(CH3OH)4 activated with varying levels of Ce3+ and of CeBr3(CH3OH)4 were grown in single crystal form. We have now extended the development of this new class of scintillators to more complex organic components by reacting rare-earth halides such as CeCl3 or CeBr3 with different isomers of propanol and butanol including 1-propanol, isobutanol, n-butanol, and tert-butanol. The reaction of CeCl3 or CeBr3 with these organics results in the formation of new and relatively complex molecular crystals whose structures were determined using single-crystal X-ray diffraction. These new metal-organic scintillating materials were grown in single crystal form from solution, and their scintillation characteristics have been investigated using X-ray-excited luminescence plus energy spectra obtained with gamma-ray and alpha-particle sources. If the reactions between the inorganic and organic components are not carried out under very dry and highly controlled conditions, molecular structures can be formed that incorporate waters of hydration. The present observation of scintillation in these hydrated rare-earth metal-organic compounds is apparently an original finding, since we are not aware of any previous reports of scintillation being observed in a material that incorporates waters of hydration

  20. Combining UV lithography and an imprinting technique for patterning metal-organic frameworks.

    Science.gov (United States)

    Doherty, Cara M; Grenci, Gianluca; Riccò, Raffaele; Mardel, James I; Reboul, Julien; Furukawa, Shuhei; Kitagawa, Susumu; Hill, Anita J; Falcaro, Paolo

    2013-09-14

    Thin metal-organic framework (MOF) films are patterned using UV lithography and an imprinting technique. A UV lithographed SU-8 film is imprinted onto a film of MOF powder forming a 2D MOF patterned film. This straightforward method can be applied to most MOF materials, is versatile, cheap, and potentially useful for commercial applications such as lab-on-a-chip type devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Metal-Organic and Organic TADF-Materials: Status, Challenges and Characterization.

    Science.gov (United States)

    Bergmann, Larissa; Zink, Daniel M; Bräse, Stefan; Baumann, Thomas; Volz, Daniel

    2016-06-01

    This section covers both metal-organic and organic materials that feature thermally activated delayed fluorescence (TADF). Such materials are especially useful for organic light-emitting diodes (OLEDs), a technology that was introduced in commercial displays only recently. We compare both material classes to show commonalities and differences, highlighting current issues and challenges. Advanced spectroscopic techniques as valuable tools to develop solutions to those issues are introduced. Finally, we provide an outlook over the field and highlight future trends.

  2. High index of refraction films for dielectric mirrors prepared by metal-organic chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Brusasco, R.M.

    1989-01-01

    A wide variety of metal oxides with high index of refraction can be prepared by Metal-Organic Chemical Vapor Deposition. We present some recent optical and laser damage results on oxide films prepared by MOCVD which could be used in a multilayer structure for highly reflecting (HR) dielectric mirror applications. The method of preparation affects both optical properties and laser damage threshold. 10 refs., 8 figs., 4 tabs.

  3. Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

    Science.gov (United States)

    Chang, Ting-Hsiang; Kung, Chung-Wei; Chen, Hsin-Wei; Huang, Tzu-Yen; Kao, Sheng-Yuan; Lu, Hsin-Che; Lee, Min-Han; Boopathi, Karunakara Moorthy; Chu, Chih-Wei; Ho, Kuo-Chuan

    2015-11-25

    Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell.

  4. Collaborative interactions to enhance gas binding energy in porous metal-organic frameworks.

    Science.gov (United States)

    Lin, Rui-Biao; Chen, Banglin

    2017-03-01

    Metal-organic frameworks (MOFs) are potentially useful materials for hydrogen and methane storage. However, the weak interactions between the MOF host and gas guest molecules have limited their storage capacities at elevated temperatures. In this issue, Alkordi et al. [IUCrJ (2017), 4, 131-135] illustrate an example of a porous MOF with a suitable pore size and unique pore surface for enhanced interaction with hydrogen molecules, providing the promise of further increasing the gas binding affinity through collaborative interactions.

  5. Van der Waals density functional study of water binding in metal-organic frameworks

    Science.gov (United States)

    Lee, Kyuho; Smit, Berend; Neaton, Jeffrey B.

    2013-03-01

    Metal-organic frameworks (MOFs) are promising candidate materials for gas storage, gas separation and catalysis. However, MOFs are vulnerable to humid air and effective surface area drops dramatically on an exposure to water. In this theoretical study, we investigate the interaction of single water molecule with MOF-74 on different binding sites by using van der Waals density functionals. We also explore how different type of metal cations affect the interaction.

  6. Variation of Pore Metrics in Metal-Organic Frameworks for Enhanced Storage and Catalytic Applications

    OpenAIRE

    Brown, Jonathan Ward

    2015-01-01

    With the principles of reticular chemistry, metal-organic frameworks (MOFs)with enhanced storage and catalytic capabilities have been prepared. This dissertationpresents the synthesis of azo-IRMOF-74-III for controllable release of cargomolecules as well as the catalytic testing of MOF-525-Mn and an isoreticular seriesof MOFs based on the MOF-5 framework. The variation of pore metrics inthese frameworks show the versatility of reticular chemistry and their applicationin catalytic reactions.Fi...

  7. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    OpenAIRE

    Hyunho Kim; H. Jeremy Cho; Shankar Narayanan; Sungwoo Yang; Hiroyasu Furukawa; Scott Schiffres; Xiansen Li; Yue-Biao Zhang; Juncong Jiang; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of ads...

  8. Formation of Fe Cluster Superlattice in a Metal-Organic Quantum-Box Network

    OpenAIRE

    Pivetta, Marina; Pacchioni, Giulia E.; Schlickum, Uta; Barth, Johannes V.; Brune, Harald

    2013-01-01

    We report on the self-assembly of Fe adatoms on a Cu(111) surface that is patterned by a metal-organic honeycomb network, formed by coordination of dicarbonitrile pentaphenyl molecules with Cu adatoms. Fe atoms landing on the metal surface are mobile and steered by the quantum confinement of the surface state electrons towards the center of the network hexagonal cavities. In cavities hosting more than one Fe, preferential interatomic distances are observed. The adatoms in each hexagon aggrega...

  9. Wavelength-Tunable Microlasers Based on the Encapsulation of Organic Dye in Metal-Organic Frameworks.

    Science.gov (United States)

    Wei, Yanhui; Dong, Haiyun; Wei, Cong; Zhang, Wei; Yan, Yongli; Zhao, Yong Sheng

    2016-09-01

    A wavelength-tunable microlaser is realized based on the controlled intramolecular charge transfer (ICT) process in dye-encapsulated metal-organic framework (MOF) material. The confinement effect of the MOFs is beneficial for low-threshold lasing. By effectively controlling the polarity of the MOF pores, the population distribution between the locally excited and ICT states is continuously modulated, thus achieving broadband tunable MOF-based microlasers.

  10. Metal-organic frameworks reactivate deceased diatoms to be efficient CO(2) absorbents.

    Science.gov (United States)

    Liu, Dingxin; Gu, Jiajun; Liu, Qinglei; Tan, Yongwen; Li, Zhuo; Zhang, Wang; Su, Yishi; Li, Wuxia; Cui, Ajuan; Gu, Changzhi; Zhang, Di

    2014-02-26

    Diatomite combined with certain metal-organic frameworks (MOFs) is shown to be an effective CO2 absorbent, although diatomite alone is regarded as inert with respect to CO2 absorption. This finding opens the prospect of reactivating millions of tons of diatomite for CO2 absorption. It also shows for the first time that diatom frustules can act as CO2 buffers, an important link in a successive biological CO2 concentration mechanism chain that impacts on global warming.

  11. Photoswitchable Adsorption in Metal-Organic Frameworks Based on Polar Guest-Host Interactions.

    Science.gov (United States)

    Wang, Zhengbang; Grosjean, Sylvain; Bräse, Stefan; Heinke, Lars

    2015-12-21

    Reversible remote-controlled switching of the properties of nanoporous metal-organic frameworks (MOFs) is enabled by incorporating photoswitchable azobenzene. The interaction of the host material with different guest molecules, which is crucial for all applications, is precisely studied using thin MOF films of the type Cu2 (BDC)2 (AzoBipyB). A molecule-specific effect of the photoswitching, based on dipole-dipole interactions, is found.

  12. Metal-organic framework templated inorganic sorbents for rapid and efficient extraction of heavy metals.

    Science.gov (United States)

    Abney, C W; Gilhula, J C; Lu, K; Lin, W

    2014-12-17

    An innovative wet-treatment with Na2 S transforms two indium metal-organic frameworks (MOFs) into a series of porous inorganic sorbents. These MOF-templated materials display remarkable affinity for heavy metals with saturation occurring in less than 1 h. The saturation capacity for Hg(II) exceeds 2 g g(-1) , more than doubling the best thiol-functionalized sorbents in the literature.

  13. Shape assisted fabrication of fluorescent cages of squarate based metal-organic coordination frameworks.

    Science.gov (United States)

    Jayaramulu, Kolleboyina; Krishna, Katla Sai; George, Subi J; Eswaramoorthy, Muthuswamy; Maji, Tapas Kumar

    2013-05-11

    Micronic cage structures of squarate based metal-organic coordination frameworks (MOCFs) have been fabricated for the first time by specific anion selective etching of metal squarate cubes. Time and stoichiometry dependent synthesis and the corresponding microscopic studies have provided mechanistic insight into the cage formation. Furthermore, a non-covalent post-synthetic strategy has been adopted to functionalize the micronic cubes or cages with chromophores rendering the resulting hybrids green fluorescent.

  14. Managing liquidity

    DEFF Research Database (Denmark)

    Pokutta, Sebastian; Schmaltz, Christian

    2011-01-01

    Large banking groups face the question of how to optimally allocate and generate liquidity: in a central liquidity hub or in many decentralized branches. We translate this question into a facility location problem under uncertainty. We show that volatility is the key driver behind (de...... above which it is advantageous to open a liquidity center and show that it is a function of the volatility and the characteristic of the bank network. Finally, we discuss the n-branch model for real-world banking groups (10-60 branches) and show that it can be solved with high granularity (100 scenarios...

  15. Integration of Biomolecules with Metal-Organic Frameworks.

    Science.gov (United States)

    Zhuang, Jia; Young, Allison P; Tsung, Chia-Kuang

    2017-08-01

    Owing to the progressive development of metal-organic-frameworks (MOFs) synthetic processes and considerable potential applications in last decade, integrating biomolecules into MOFs has recently gain considerable attention. Biomolecules, including lipids, oligopeptides, nucleic acids, and proteins have been readily incorporated into MOF systems via versatile formulation methods. The formed biomolecule-MOF hybrid structures have shown promising prospects in various fields, such as antitumor treatment, gene delivery, biomolecular sensing, and nanomotor device. By optimizing biomolecule integration methods while overcoming existing challenges, biomolecule-integrated MOF platforms are very promising to generate more practical applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps.

    Science.gov (United States)

    Li, Baiyan; Dong, Xinglong; Wang, Hao; Ma, Dingxuan; Tan, Kui; Jensen, Stephanie; Deibert, Benjamin J; Butler, Joseph; Cure, Jeremy; Shi, Zhan; Thonhauser, Timo; Chabal, Yves J; Han, Yu; Li, Jing

    2017-09-07

    Effective capture of radioactive organic iodides from nuclear waste remains a significant challenge due to the drawbacks of current adsorbents such as low uptake capacity, high cost, and non-recyclability. We report here a general approach to overcome this challenge by creating radioactive organic iodide molecular traps through functionalization of metal-organic framework materials with tertiary amine-binding sites. The molecular trap exhibits a high CH3I saturation uptake capacity of 71 wt% at 150 °C, which is more than 340% higher than the industrial adsorbent Ag(0)@MOR under identical conditions. These functionalized metal-organic frameworks also serve as good adsorbents at low temperatures. Furthermore, the resulting adsorbent can be recycled multiple times without loss of capacity, making recyclability a reality. In combination with its chemical and thermal stability, high capture efficiency and low cost, the adsorbent demonstrates promise for industrial radioactive organic iodides capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li and co-workers fabricate a stable metal-organic framework functionalized with tertiary amine groups that exhibits high capacities for radioactive organic iodides uptake.

  17. Surfactant-thermal method to prepare two new cobalt metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xianglin [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430074 (China); Toh, Yong Siang [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Zhao, Jun [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Nie, Lina [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ye, Kaiqi; Wang, Yue [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012 (China); Li, Dongsheng [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Zhang, Qichun, E-mail: qczhang@ntu.edu.sg [School of Materials Science and Engineering and School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)

    2015-12-15

    Employing surfactants as reaction media, two new metal-organic frameworks (MOFs):(HTEA){sub 3}[Co{sub 3}(BTC){sub 3}] (NTU-Z33) and (HTEA)[Co{sub 3}(HBTC){sub 2}(BTC)] (NTU-Z34) (H{sub 3}BTC=1,3,5-benzenetricarboxylic acid, TEA=trimethylamine, and NTU=Nanyang Technological University), have been successfully synthesized and fully characterized. Note that NTU-Z33 has an unusual trimeric [Co{sub 3}(COO){sub 9}] secondary building unit (SBU). Magnetic characterization suggests that both compounds have weak antiferromagnetic behaviors. Our success in preparing new crystalline Co-BTC based MOFs under different surfactant media could provide a new road to prepare new diverse MOFs through various combinations of surfactants. - Graphical abstract: Employing surfactants as reaction media, two new metal-organic frame-works (MOFs) have been successfully synthesized and magnetic study suggests that both compounds have weak antiferromagnetic behaviors. - Highlights: • Two novel metal-organic frame-works (MOFs). • Synthesis through surfactant-thermal condition. • weak antiferromagnetic behaviors for both compounds.

  18. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    Science.gov (United States)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2016-12-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  19. Ultrathin metal-organic framework array for efficient electrocatalytic water splitting

    Science.gov (United States)

    Duan, Jingjing; Chen, Sheng; Zhao, Chuan

    2017-06-01

    Two-dimensional metal-organic frameworks represent a family of materials with attractive chemical and structural properties, which are usually prepared in the form of bulk powders. Here we show a generic approach to fabricate ultrathin nanosheet array of metal-organic frameworks on different substrates through a dissolution-crystallization mechanism. These materials exhibit intriguing properties for electrocatalysis including highly exposed active molecular metal sites owning to ultra-small thickness of nanosheets, improved electrical conductivity and a combination of hierarchical porosity. We fabricate a nickel-iron-based metal-organic framework array, which demonstrates superior electrocatalytic performance towards oxygen evolution reaction with a small overpotential of 240 mV at 10 mA cm-2, and robust operation for 20,000 s with no detectable activity decay. Remarkably, the turnover frequency of the electrode is 3.8 s-1 at an overpotential of 400 mV. We further demonstrate the promise of these electrodes for other important catalytic reactions including hydrogen evolution reaction and overall water splitting.

  20. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    Science.gov (United States)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2017-03-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  1. Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps

    KAUST Repository

    Li, Baiyan

    2017-09-01

    Effective capture of radioactive organic iodides from nuclear waste remains a significant challenge due to the drawbacks of current adsorbents such as low uptake capacity, high cost, and non-recyclability. We report here a general approach to overcome this challenge by creating radioactive organic iodide molecular traps through functionalization of metal-organic framework materials with tertiary amine-binding sites. The molecular trap exhibits a high CH3I saturation uptake capacity of 71 wt% at 150 °C, which is more than 340% higher than the industrial adsorbent Ag0@MOR under identical conditions. These functionalized metal-organic frameworks also serve as good adsorbents at low temperatures. Furthermore, the resulting adsorbent can be recycled multiple times without loss of capacity, making recyclability a reality. In combination with its chemical and thermal stability, high capture efficiency and low cost, the adsorbent demonstrates promise for industrial radioactive organic iodides capture from nuclear waste. The capture mechanism was investigated by experimental and theoretical methods.Capturing radioactive organic iodides from nuclear waste is important for safe nuclear energy usage, but remains a significant challenge. Here, Li and co-workers fabricate a stable metal-organic framework functionalized with tertiary amine groups that exhibits high capacities for radioactive organic iodides uptake.

  2. Tuning hydrogen sorption properties of metal-organic frameworks by postsynthetic covalent modification.

    Science.gov (United States)

    Wang, Zhenqiang; Tanabe, Kristine K; Cohen, Seth M

    2010-01-04

    Postsynthetic modification is presented as a means to tune the hydrogen adsorption properties of a series of metal-organic frameworks (MOFs). IRMOF-3 (isoreticular metal-organic framework), UMCM-1-NH(2) (University of Michigan crystalline material), and DMOF-1-NH(2) (DABCO metal-organic framework) have been covalently modified with a series of anhydrides or isocyanates and the hydrogen sorption properties have been studied. Both the storage capacities and isosteric heats of adsorption clearly show that covalent postsynthetic modification can significantly enhance the sorption affinity of MOFs with hydrogen and in some cases increase both gravimetric and volumetric uptake of the gas as much as 40 %. The significance of the present study is illustrated by: 1) the nature of the substituents introduced by postsynthetic modification result in different effects on the binding of hydrogen; 2) the covalent postsynthetic modification approach allows for systematic modulation of hydrogen sorption properties; and 3) the ease of postsynthetic modification of MOFs allows a direct evaluation of the interplay between MOF structure, hydrogen uptake, and heat of adsorption. The findings presented herein show that postsynthetic modification is a powerful method to manipulate and better understand the gas sorption properties of MOFs.

  3. Melt-quenched glasses of metal-organic frameworks

    DEFF Research Database (Denmark)

    Bennett, T.D.; Yue, Yuanzheng; Li, P.

    2016-01-01

    Crystalline solids dominate the field of metal−organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand the phen......Crystalline solids dominate the field of metal−organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand...... the phenomenon of the melting of 3D MOFs, linking crystal chemistry to framework melting temperature and kinetic fragility of the glass-forming liquids. Here we show that melting temperatures can be lowered by altering the chemistry of the crystalline MOF state, which provides a route to facilitate the melting...... of other MOFs. The glasses formed upon vitrification are chemically and structurally distinct from the three other existing categories of melt-quenched glasses (inorganic nonmetallic, organic, and metallic), and retain the basic metal−ligand connectivity of crystalline MOFs, which connects their mechanical...

  4. Hydrostable and Nitryl/Methyl-Functionalized Metal-Organic Framework for Drug Delivery and Highly Selective CO2 Adsorption.

    Science.gov (United States)

    Ma, De-Yun; Li, Zhi; Xiao, Jun-Xia; Deng, Rong; Lin, Pei-Feng; Chen, Rui-Qun; Liang, Yun-Qiu; Guo, Hai-Fu; Liu, Bei; Liu, Jian-Qiang

    2015-07-20

    By using a strategy of introducing hydrophobic groups to the linkers, a hydrostable MOF was constructed based on 5-nitroisophthalate and 2,2'-dimethyl-4,4'-bipyridine coligands, revealing a 3D dia topology structure with a 1D channel parallel to the c axis. TGA, PXRD, and water vapor sorption results show high thermal and water stability for the framework. The framework is very porous and possesses not only high busulfan payloads with an encapsulation efficiency up to 21.5% (17.2 wt %) but also very high CO2 selective capture compared with that of other small gases (i.e., CH4, N2, O2, CO, and H2) at 298 K based on molecular simulations due to the pore surface being populated by methyl and nitryl groups. Furthermore, in vitro MTT assays were conducted on four different cells lines with increasing concentrations of the framework, and the results showed that the framework was nontoxic (cell viability >80%) in spite of the concentrations up to 500 μg/mL.

  5. Global Delivery Models

    DEFF Research Database (Denmark)

    Manning, Stephan; Larsen, Marcus M.; Bharati, Pratyush

    2013-01-01

    This article examines antecedents and performance implications of global delivery models (GDMs) in global business services. GDMs require geographically distributed operations to exploit both proximity to clients and time-zone spread for efficient service delivery. We propose and empirically show...... that service providers who differentiate based on speed of service delivery are likely to set up GDM structures, and that these structures positively affect deal renewal rates if speed is important for clients in selecting vendors. Findings imply that, as co-location becomes less necessary for providing...... digitalized services, time zones increasingly affect....

  6. Global Delivery Models

    DEFF Research Database (Denmark)

    Manning, Stephan; Møller Larsen, Marcus; Bharati, Pratyush

    We investigate antecedents and contingencies of location configurations supporting global delivery models (GDMs) in global outsourcing. GDMs are a new form of IT-enabled client-specific investment promoting services provision integration with clients by exploiting client proximity and time......-zone spread allowing for 24/7 service delivery and access to resources. Based on comprehensive data we show that providers are likely to establish GDM configurations when clients value access to globally distributed talent pools and speed of service delivery, and in particular when services are highly...

  7. Global Delivery Models

    DEFF Research Database (Denmark)

    Manning, Stephan; Møller Larsen, Marcus; Bharati, Pratyush

    We investigate antecedents and contingencies of location configurations supporting global delivery models (GDMs) in global outsourcing. GDMs are a new form of IT-enabled client-specific investment promoting services provision integration with clients by exploiting client proximity and time......-zone spread allowing for 24/7 service delivery and access to resources. Based on comprehensive data we show that providers are likely to establish GDM configurations when clients value access to globally distributed talent pools and speed of service delivery, and in particular when services are highly...... commoditized. Findings imply that coordination across time zones increasingly affects international operations in business-to-business and born-global industries....

  8. Focus on Delivery

    DEFF Research Database (Denmark)

    Hasman, Kirsten; Barfoed, Anne

    2016-01-01

    (2). It is, however, not clarified which of the multifaceted aspects of preventing perineal injury that might explain the decrease (3). Aims: We hypothesized that the use of structured reflection on a clinical practice by midwives and midwifery students would increase both parts’ knowledge on how...... attended a delivery. The tool was developed based on five categories: communication, pace, ergonomic positions, perineal support in the chosen birth position and delivery of the shoulders, and five predefined questions guided an overall reflection upon practice. After a delivery a project midwife, who had...

  9. Liquid explosives

    CERN Document Server

    Liu, Jiping

    2015-01-01

    The book drawing on the author's nearly half a century of energetic materials research experience intends to systematically review the global researches on liquid explosives. The book focuses on the study of the conception, explosion mechanism, properties and preparation of liquid explosives. It provides a combination of theoretical knowledge and practical examples in a reader-friendly style. The book is likely to be interest of university researchers and graduate students in the fields of energetic materials, blasting engineering and mining.

  10. Metal-organic frameworks for analytical chemistry: from sample collection to chromatographic separation.

    Science.gov (United States)

    Gu, Zhi-Yuan; Yang, Cheng-Xiong; Chang, Na; Yan, Xiu-Ping

    2012-05-15

    In modern analytical chemistry researchers pursue novel materials to meet analytical challenges such as improvements in sensitivity, selectivity, and detection limit. Metal-organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as high surface area, good thermal stability, uniform structured nanoscale cavities, and the availability of in-pore functionality and outer-surface modification are attractive for diverse analytical applications. This Account summarizes our research on the analytical applications of MOFs ranging from sampling to chromatographic separation. MOFs have been either directly used or engineered to meet the demands of various analytical applications. Bulk MOFs with microsized crystals are convenient sorbents for direct application to in-field sampling and solid-phase extraction. Quartz tubes packed with MOF-5 have shown excellent stability, adsorption efficiency, and reproducibility for in-field sampling and trapping of atmospheric formaldehyde. The 2D copper(II) isonicotinate packed microcolumn has demonstrated large enhancement factors and good shape- and size-selectivity when applied to on-line solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. We have explored the molecular sieving effect of MOFs for the efficient enrichment of peptides with simultaneous exclusion of proteins from biological fluids. These results show promise for the future of MOFs in peptidomics research. Moreover, nanosized MOFs and engineered thin films of MOFs are promising materials as novel coatings for solid-phase microextraction. We have developed an in situ hydrothermal growth approach to fabricate thin films of MOF-199 on etched stainless steel wire for solid-phase microextraction of volatile benzene homologues with large enhancement factors and wide linearity. Their high thermal stability and easy-to-engineer nanocrystals make MOFs attractive as new stationary phases to fabricate MOF

  11. Microemulsões e fases líquidas cristalinas como sistemas de liberação de fármacos Microemulsion and liquid cristals as drug delivery systems

    Directory of Open Access Journals (Sweden)

    Thalita Pedroni Formariz

    2005-09-01

    Full Text Available A mistura de tensoativos com água, em determinadas proporções, na ausência ou na presença de substâncias lipofílicas pode formar diferentes tipos de agregados, entre os quais agregados polimorfos representados pelas microemulsões (ME e mesofases liotrópicas - os cristais líquidos (LC, que estão intimamente ligados com a proporção e a natureza dos componentes da mistura. Nesse trabalho, foi discutido o papel desses sistemas na incorporação de fármacos com diferentes propriedades físico-químicas, influenciando fortemente a liberação, assim como a biodisponibilidade dos fármacos. Aspectos sobre a formação e a caracterização de microemulsões e cristais líquidos também foram discutidos. A análise da literatura indicou que, dependendo da polaridade do fármaco, o efeito da ME ou LC pode ser usado para otimizar o efeito terapêutico por meio do controle da velocidade ou do mecanismo de liberação do fármaco.Depending on the proportions, the mixture of surfactants with water, in the presence or absence of oil, may form different types of supramolecular aggregates. Among these, polymorphic structures represented by microemulsions (ME and lyotropic mesophases-liquid crystals (LC, closely related with the nature and the proportion of the constituents, can exist. In this work, the role of these systems in the incorporation of drugs with different physico-chemical properties, influencing strongly the drug release as well as the bioavailability of the drugs, was discussed. Aspects about the formation and the characterization of ME and LC were also discussed. The analysis of the literature indicate that depending on the drug polarity the effect of ME or LC can be used to optimizes therapeutic effects through the control of rates and the drug release mechanisms.

  12. Transdermal delivery of proteins.

    Science.gov (United States)

    Kalluri, Haripriya; Banga, Ajay K

    2011-03-01

    Transdermal delivery of peptides and proteins avoids the disadvantages associated with the invasive parenteral route of administration and other alternative routes such as the pulmonary and nasal routes. Since proteins have a large size and are hydrophilic in nature, they cannot permeate passively across the skin due to the stratum corneum which allows the transport of only small lipophilic drug molecules. Enhancement techniques such as chemical enhancers, iontophoresis, microneedles, electroporation, sonophoresis, thermal ablation, laser ablation, radiofrequency ablation and noninvasive jet injectors aid in the delivery of proteins by overcoming the skin barrier in different ways. In this review, these enhancement techniques that can enable the transdermal delivery of proteins are discussed, including a discussion of mechanisms, sterility requirements, and commercial development of products. Combination of enhancement techniques may result in a synergistic effect allowing increased protein delivery and these are also discussed.

  13. Microencapsulation of indocyanine green for potential applications in image-guided drug delivery.

    Science.gov (United States)

    Zhu, Zhiqiang; Si, Ting; Xu, Ronald X

    2015-02-07

    We present a novel process to encapsulate indocyanine green (ICG) in liposomal droplets at high concentration for potential applications in image-guided drug delivery. The microencapsulation process follows two consecutive steps of droplet formation by liquid-driven coaxial flow focusing (LDCFF) and solvent removal by oil phase dewetting. These biocompatible lipid vesicles may have important applications in drug delivery and fluorescence imaging.

  14. Solvent-switchable continuous-breathing behaviour in a diamondoid metal-organic framework and its influence on CO2 versus CH4 selectivity

    Science.gov (United States)

    Carrington, Elliot J.; McAnally, Craig A.; Fletcher, Ashleigh J.; Thompson, Stephen P.; Warren, Mark; Brammer, Lee

    2017-09-01

    Understanding the behaviour of flexible metal-organic frameworks (MOFs)—porous crystalline materials that undergo a structural change upon exposure to an external stimulus—underpins their design as responsive materials for specific applications, such as gas separation, molecular sensing, catalysis and drug delivery. Reversible transformations of a MOF between open- and closed-pore forms—a behaviour known as 'breathing'—typically occur through well-defined crystallographic transitions. By contrast, continuous breathing is rare, and detailed characterization has remained very limited. Here we report a continuous-breathing mechanism that was studied by single-crystal diffraction in a MOF with a diamondoid network, (Me2NH2)[In(ABDC)2] (ABDC, 2-aminobenzene-1,4-dicarboxylate). Desolvation of the MOF in two different solvents leads to two polymorphic activated forms with very different pore openings, markedly different gas-adsorption capacities and different CO2 versus CH4 selectivities. Partial desolvation introduces a gating pressure associated with CO2 adsorption, which shows that the framework can also undergo a combination of stepped and continuous breathing.

  15. MUCOSAL DRUG DELIVERY SYSTEM

    OpenAIRE

    Madan Jyotsana; Banode Sagar; Dangi Mahesh

    2010-01-01

    The process of mucoadhesion involving a polymeric drug delivery system is a complex one that includes processes such as wetting, adsorption and interpenetration of polymer chains. The success and degree of mucoadhesion bonding is influenced by various polymer-based properties such as the degree of cross-linking, chain length and the presence of various functional groupings. The attractiveness of mucosal-targeted controlled drug delivery of active pharmaceutical ingredients, has led formulatio...

  16. Studies of gas adsorption in flexible Metal-Organic frameworks

    Science.gov (United States)

    Sircar, Sarmishtha

    Flexible Metal-Organic frameworks that exhibit a gate-opening (GO) adsorption mechanism have potential for gas separations and gas storage. The GO phenomenon occurs when molecular gates in the structure expand/contract in response to the activation/de-activation of a system variable e.g. temperature, pressure or gas. Sharp discontinuities in the isotherm leading to S-shapes and large adsorption-desorption hysteresis are typical of this phenomenon. This study investigates the kinetics and thermodynamics of the GO behavior by combining adsorption measurements and analytical modeling of adsorption kinetics and capacity as a function of adsorbate, GO pressure, and temperature. Basic understanding of GO mechanism will help harness GO-MOF's as adsorbents for gas separations and storage. Experiments were performed on two precharacterized MOFs with verified GO behavior. These are (1) Zn2(bpdc)2(bpee), which expands from a relative amorphous to crystalline structure and (2) Cu[(dhbc) 2(4,4f-bpy)]H2O, a mutually interdigitated 2-D structure (bpdc = biphenyldicarboxylate, bpee = 1,2]bipyridylethene; DMF = N,N-dimethyl formamide, dhbc= 2,5-dihydroxybenzoic acid, bpy=bipyridine). Both sub- and super-critical adsorption data were collected using three adsorption units: a standard low-pressure volumetric adsorption unit, a commercial high-pressure gravimetric analyzer and a custom-built high-pressure differential volumetric unit. Collected laboratory data were combined with published adsorption rate and isotherm data for analysis to broaden the range of data collection. The accuracy of the high-pressure differential unit was improved by over 300-fold by changing analytical methods of processing data to establish a reliable null correction. A pronounced effect of the allowed experimental time was found at cryogenic temperatures on (1). Tightening the stability criteria used by the adsorption equipment to determine equilibration increased the experimental time from the order of

  17. A novel three-dimensional CdII metal-organic framework based on [Cd6(malonate)6] metallomacrocycles with zeolite SOD (sodalite) topology: poly[ammine-μ3-malonato-cadmium(II)].

    Science.gov (United States)

    Yuan, Shuai; Liu, Mei-Jiao; Xie, Han-Yi; Xu, Meng-Zhen; Sun, Di

    2012-03-01

    A novel Cd(II) metal-organic framework, [Cd(C(3)H(2)O(4))(NH(3))](n), was synthesized by liquid diffusion conducted in the presence of ammonia. The Cd(II) atom has seven-coordinate O(6)N pentagonal-bipyramidal geometry. Six Cd(II) centers are joined by six malonate ligands to form an S(6)-symmetric [Cd(6)(malonate)(6)] metallomacrocycle, which is further extended through a side-on chelating malonate ligand to form a three-dimensional network. Topologically, each Cd(II) center is connected to four others to yield an infinite three-periodic four-coordinated SOD (sodalite) network with point symbol {4(2)·6(4)}. The overall network structure in the crystal is maintained and stabilized by the presence of N-H...O hydrogen bonds.

  18. Efficient dermal delivery of retinyl palmitate: Progressive polarimetry and Raman spectroscopy to evaluate the structure and efficacy.

    Science.gov (United States)

    Lee, Jun Bae; Lee, Dong Ryeol; Choi, Nak Cho; Jang, Jihui; Park, Chun Ho; Yoon, Moung Seok; Lee, Miyoung; Won, Kyoungae; Hwang, Jae Sung; Kim, B Moon

    2015-10-12

    Over the past decades, there has been a growing interest in dermal drug delivery. Although various novel delivery devices and methods have been developed, dermal delivery is still challenging because of problems such as poor drug permeation, instability of vesicles and drug leakage from vesicles induced by fusion of vesicles. To solve the vesicle instability problems in current dermal delivery systems, we developed materials comprised of liquid crystals as a new delivery vehicle of retinyl palmitate and report the characterization of the liquid crystals using a Mueller matrix polarimetry. The stability of the liquid-crystal materials was evaluated using the polarimeter as a novel evaluation tool along with other conventional methods. The dermal delivery of retinyl palmitate was investigated through the use of confocal Raman spectroscopy. The results indicate that the permeation of retinyl palmitate was enhanced by up to 106% compared to that using an ordinary emulsion with retinyl palmitate.

  19. Unsteady jet in designing innovative drug delivery system

    Science.gov (United States)

    Wang, Cong; Mazur, Paul; Cosse, Julia; Rider, Stephanie; Gharib, Morteza

    2014-11-01

    Micro-needle injections, a promising pain-free drug delivery method, is constrained by its limited penetration depth. This deficiency can be overcome by implementing fast unsteady jet that can penetrate sub-dermally. The development of a faster liquid jet would increase the penetration depth and delivery volume of micro-needles. In this preliminary work, the nonlinear transient behavior of an elastic tube balloon in providing fast discharge is analyzed. A physical model that combines the Mooney Rivlin Material model and Young-Lapalce's Law was developed and used to investigate the fast discharging dynamic phenomenon. A proof of concept prototype was constructed to demonstrate the feasibility of a simple thumb-sized delivery system to generate liquid jet with desired speed in the range of 5-10 m/s. This work is supported by ZCUBE Corporation.

  20. Current progress in pulmonary delivery of measles vaccine.

    Science.gov (United States)

    Griffin, Diane E

    2014-06-01

    Due to the high infectivity of measles virus, achieving sufficient population immunity to interrupt transmission requires two doses of live attenuated measles virus vaccine. Subcutaneous delivery of vaccine by injection requires trained personnel, maintenance of a cold chain and safe disposal of used needles and syringes. Pulmonary vaccine delivery offers the opportunity for cost-savings and improved coverage, but requires re-licensure. Two aerosol vaccine formulations, nebulized liquid and dry powder, and multiple delivery devices have been evaluated in humans and macaques. Nebulized liquid vaccine is effective for a second dose of vaccine in older children, but less effective for primary vaccination of infants. Dry powder vaccine provides solid protection in macaques and boosts responses in immune adults, but has not yet been tested in infants.

  1. Thermodynamics of the spin Luttinger liquid in a model ladder material.

    Science.gov (United States)

    Rüegg, Ch; Kiefer, K; Thielemann, B; McMorrow, D F; Zapf, V; Normand, B; Zvonarev, M B; Bouillot, P; Kollath, C; Giamarchi, T; Capponi, S; Poilblanc, D; Biner, D; Krämer, K W

    2008-12-12

    The phase diagram in temperature and magnetic field of the metal-organic, two-leg, spin-ladder compound (C5H12N)2CuBr4 is studied by measurements of the specific heat and the magnetocaloric effect. We demonstrate the presence of an extended spin Luttinger-liquid phase between two field-induced quantum critical points and over a broad range of temperature. Based on an ideal spin-ladder Hamiltonian, comprehensive numerical modeling of the ladder specific heat yields excellent quantitative agreement with the experimental data across the entire phase diagram.

  2. Issues associated with the metalorganic chemical vapor deposition of ScGaN and YGaN alloys.

    Energy Technology Data Exchange (ETDEWEB)

    Koleske, Daniel David; Knapp, James Arthur; Lee, Stephen Roger; Crawford, Mary Hagerott; Creighton, James Randall; Cross, Karen Charlene; Thaler, Gerald

    2009-07-01

    The most energy efficient solid state white light source will likely be a combination of individually efficient red, green, and blue LED. For any multi-color approach to be successful the efficiency of deep green LEDs must be significantly improved. While traditional approaches to improve InGaN materials have yielded incremental success, we proposed a novel approach using group IIIA and IIIB nitride semiconductors to produce efficient green and high wavelength LEDs. To obtain longer wavelength LEDs in the nitrides, we attempted to combine scandium (Sc) and yttrium (Y) with gallium (Ga) to produce ScGaN and YGaN for the quantum well (QW) active regions. Based on linear extrapolation of the proposed bandgaps of ScN (2.15 eV), YN (0.8 eV) and GaN (3.4 eV), we expected that LEDs could be fabricated from the UV (410 nm) to the IR (1600 nm), and therefore cover all visible wavelengths. The growth of these novel alloys potentially provided several advantages over the more traditional InGaN QW regions including: higher growth temperatures more compatible with GaN growth, closer lattice matching to GaN, and reduced phase separation than is commonly observed in InGaN growth. One drawback to using ScGaN and YGaN films as the active regions in LEDs is that little research has been conducted on their growth, specifically, are there metalorganic precursors that are suitable for growth, are the bandgaps direct or indirect, can the materials be grown directly on GaN with a minimal defect formation, as well as other issues related to growth. The major impediment to the growth of ScGaN and YGaN alloys was the low volatility of metalorganic precursors. Despite this impediment some progress was made in incorporation of Sc and Y into GaN which is detailed in this report. Primarily, we were able to incorporate up to 5 x 10{sup 18} cm{sup -3} Y atoms into a GaN film, which are far below the alloy concentrations needed to evaluate the YGaN optical properties. After a no-cost extension was

  3. Liquid Crystals

    Science.gov (United States)

    1990-01-01

    Thermochromic liquid crystals, or TLCs, are a type of liquid crystals that react to changes in temperature by changing color. The Hallcrest/NASA collaboration involved development of a new way to visualize boundary layer transition in flight and in wind tunnel testing of aircraft wing and body surfaces. TLCs offered a new and potentially better method of visualizing the boundary layer transition in flight. Hallcrest provided a liquid crystal formulation technique that afforded great control over the sensitivity of the liquid crystals to varying conditions. Method is of great use to industry, government and universities for aerodynamic and hydrodynamic testing. Company's principal line is temperature indicating devices for industrial use, such as non-destructive testing and flaw detection in electric/electronic systems, medical application, such as diagnostic systems, for retail sale, such as room, refrigerator, baby bath and aquarium thermometers, and for advertising and promotion specials. Additionally, Hallcrest manufactures TLC mixtures for cosmetic applications, and liquid crystal battery tester for Duracell batteries.

  4. Facile preparation of hierarchically porous carbons from metal-organic gels and their application in energy storage

    Science.gov (United States)

    Xia, Wei; Qiu, Bin; Xia, Dingguo; Zou, Ruqiang

    2013-06-01

    Porous carbon materials have numerous applications due to their thermal and chemical stability, high surface area and low densities. However, conventional preparing porous carbon through zeolite or silica templates casting has been criticized by the costly and/or toxic procedure. Creating three-dimensional (3D) carbon products is another challenge. Here, we report a facile way to prepare porous carbons from metal-organic gel (MOG) template, an extended metal-organic framework (MOF) structure. We surprisingly found that the carbon products inherit the highly porous nature of MOF and combine with gel's integrated character, which results in hierarchical porous architectures with ultrahigh surface areas and quite large pore volumes. They exhibit considerable hydrogen uptake and excellent electrochemical performance as cathode material for lithium-sulfur battery. This work provides a general method to fast and clean synthesis of porous carbon materials and opens new avenues for the application of metal-organic gel in energy storage.

  5. Liquid acrobatics

    CERN Document Server

    Bird, James C

    2008-01-01

    We experiment with injecting a continuous stream of gas into a shallow liquid, similar to how one might blow into a straw placed at the bottom of a near-empty drink. By varying the angle of the straw (here a metal needle), we observe a variety of dynamics, which we film using a high-speed camera. Most noteworthy is an intermediate regime in which cyclical jets erupt from the air-liquid interface and breakup into air-born droplets. These droplets trace out a parabolic trajectory and bounce on the air-liquid interface before eventually coalescing. The shape of each jet, as well as the time between jets, is remarkably similar and leads to droplets with nearly identical trajectories. The following article accompanies the linked fluid dynamics video submitted to the Gallery of Fluid Motion in 2008.

  6. Macromolecular liquids

    Energy Technology Data Exchange (ETDEWEB)

    Safinya, C.R.; Safran, S.A. (Exxon Research and Engineering Co., Annandale, NJ (US)); Pincus, P.A. (Univ. of California at Santa Barbara, Santa Barbara, CA (US))

    1990-01-01

    Liquids include a broad range of material systems which are of high scientific and technological interest. Generally speaking, these are partially ordered or disordered phases where the individual molecular species have organized themselves on length scales which are larger than simple fluids, typically between 10 Angstroms and several microns. The specific systems reported on in this book include membranes, microemulsions, micelles, liquid crystals, colloidal suspensions, and polymers. They have a major impact on a broad spectrum of technological industries such as displays, plastics, soap and detergents, chemicals and petroleum, and pharmaceuticals.

  7. Investigation of molecule properties from electronic absorption spectra of solid and liquid crystals

    Science.gov (United States)

    Klimusheva, G. V.

    2004-12-01

    Among the achievements of 20th century, there is the origin and violent development of the low-temperature technique and low-temperature spectroscopy of molecular crystals in the polarized light. Many obtained results became possible due to the close cooperation between experiment investigators and theorists. This short review traces the evolution of only one trend in the physics of molecular crystals, namely, the investigation of energetic and spatial structure of molecules from the analysis of electronic spectra of molecular crystals. First, for this purpose the possibilities of using the electronic spectra of molecular crystals at low temperatures benzene derivatives and the electronic spectra of liquid ionic crystals are considered. The results of investigations of the electronic absorption spectra for the new class of liquid crystals, namely, ionic metal-organic smectics are presented. Changes in the structure of doping molecules in the ionic liquid crystals under the influence of the dc electric field are analyzed.

  8. Nanoemulsion: A new concept of delivery system

    Directory of Open Access Journals (Sweden)

    Nitin Sharma

    2010-01-01

    Full Text Available Nanoemulsion has been identified as a promising delivery system for various drugs including biopharmaceuticals. Nanoemulsion is a heterogeneous system composed of one immiscible liquid dispersed as droplets within another liquid. The droplets size of nano emulsion is between 20 to 500 nm. Diameter and surface properties of droplets of nanoemulsion plays an important role in the biological behavior of the formulation. Small droplet sizes lead to transparent emulsions so that product appearance is not altered by the addition of an oil phase. In this paper various aspects of nanoemulsion have been discussed including advantages, disadvantages and methods of preparation. Furthermore new approaches of stability of formulation, effect of types and concentration of surfactant, process variables and method are also discussed to improve the stability of nanoemulsion formulation

  9. Nanoscale Fluorescent Metal-Organic Framework@Microporous Organic Polymer Composites for Enhanced Intracellular Uptake and Bioimaging.

    Science.gov (United States)

    Wang, Lei; Wang, Weiqi; Zheng, Xiaohua; Li, Zhensheng; Xie, Zhigang

    2017-01-26

    Polymer-modified metal-organic frameworks combine the advantages of both soft polymers and crystalline metal-organic frameworks (MOFs). It is a big challenge to develop simple methods for surface modification of MOFs. In this work, MOF@microporous organic polymer (MOP) hybrid nanoparticles (UNP) have been synthesized by epitaxial growth of luminescent boron-dipyrromethene (BODIPYs)-imine MOPs on the surface of UiO-MOF seeds, which exhibit low cytotoxicity, smaller size distribution, well-retained pore integrity, and available functional sites. After folic acid grafting, the enhanced intracellular uptake and bioimaging was validated.

  10. Blanket and Patterned Growth of CdTe on (211)Si Substrates by Metal-Organic Vapor Phase Epitaxy

    Science.gov (United States)

    2012-05-15

    REPORT Blanket and Patterned Growth Of CdTE On (211)Si Substrates By Metal-Organic Vapor Phase Epitaxy 14. ABSTRACT 16. SECURITY CLASSIFICATION OF...Metalorganic vapor phase epitaxy (MOVPE) of (211)B CdTe on (211)Si using intermediate Ge and ZnTe layers has been achieved for use as substrates for the...growth of HgCdTe infrared detector materials. The best (211)B CdTe films grown in this study display a low X-ray diffraction (XRD) rocking-curve

  11. Magnetic porous carbon derived from Co-doped metal-organic frameworks for the magnetic solid-phase extraction of endocrine disrupting chemicals.

    Science.gov (United States)

    Hao, Lin; Wei, Jiayi; Zheng, Ruixue; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2017-08-10

    Metal-organic frameworks-5 (MOF-5) was explored as a template to prepare porous carbon due to its high surface area, large pore volume, and permanent nanoscale porosity. Magnetic porous carbon, Co@MOF-5-C, was fabricated by the one-step direct carbonization of Co-doped MOF-5. After carbonization, the magnetic cobalt nanoparticles are well dispersed in the porous carbon matrix, and Co@MOF-5-C displays strong magnetism (with the saturation magnetization intensity of 70.17emu/g), high-specific surface area, and large pore volume. To evaluate its extraction performance, the Co@MOF-5-C was applied as an adsorbent for the magnetic solid-phase extraction of endocrine disrupting chemicals, followed by their analysis with high-performance liquid chromatography. The developed method exhibits a good linear response in the range of 0.5-100 ng/mL for pond water and 1.0-100 ng/mL for juice samples. The limits of detection (S/N = 3) for the analytes were in the range of 0.1-0.2 ng/mL. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Magnetic metal-organic framework MIL-100(Fe) microspheres for the magnetic solid-phase extraction of trace polycyclic aromatic hydrocarbons from water samples.

    Science.gov (United States)

    Du, Fuyou; Qin, Qun; Deng, Jianchao; Ruan, Guihua; Yang, Xianqing; Li, Laihao; Li, Jianping

    2016-06-01

    In this work, a magnetic metal-organic framework designated as MIL-100(Fe) was prepared and applied as a magnetic solid-phase extraction sorbent for the determination of trace polycyclic aromatic hydrocarbons in environmental water samples by coupling with high-performance liquid chromatography and fluorescence detection. The magnetic microspheres exhibited large surface areas and high extraction ability, making them excellent candidates as sorbents for enrichment of trace polycyclic aromatic hydrocarbons. Under the optimized experimental conditions, good sensitivity levels were achieved with low detection limits ranging from 32 to 2110 pg/mL and good linearities with correlation coefficients higher than 0.9990 for the investigated 13 polycyclic aromatic hydrocarbons. The proposed method has been validated in the analysis of real water samples with mean recoveries in the range of 81.4-126.9% at four spiked levels and the relative standard deviations in the range of 1.3-17.0%. The magnetic MIL-100(Fe) microspheres were stable enough for 150 extractions without a significant loss of extraction performance.

  13. Magnetic metal-organic framework-titanium dioxide nanocomposite as adsorbent in the magnetic solid-phase extraction of fungicides from environmental water samples.

    Science.gov (United States)

    Su, Hao; Lin, Yunliang; Wang, Zhenhua; Wong, Y-L Elaine; Chen, Xiangfeng; Chan, T-W Dominic

    2016-09-30

    In this work, a core-shell Fe3O4@SiO2@MOF/TiO2 nanocomposite was synthesized and used to as adsorbent for magnetic solid-phase extraction (MSPE) of triazole fungicides from environmental water samples. Five triazole fungicides, namely, triadimenol, hexaconazole, diniconazole, myclobutanil, and tebuconazole, were selected as target analytes for MSPE. These analytes were quantitatively adsorbed on microspheres, and the sorbents were separated from the solution by using a magnet. The analytes were desorbed by methanol and determined through liquid-chromatography coupled with tandem mass spectrometry. The extraction parameters affecting the extraction efficiency were optimized through response surface methodology. The limits of detection and limits of quantification for the selected fungicides were 0.19-1.20ngL(-1) and 0.61-3.62ngL(-1), respectively. The proposed method was applied to determine the concentration of fungicides in actual environmental water samples. The accuracy of the proposed method was evaluated by measuring the recovery of the spiked samples. The satisfying recoveries of the four water samples ranged from 90.2% to 104.2%. Therefore, the magnetic metal-organic framework/TiO2 nanocomposite based MSPE is a potential approach to analyze fungicides in actual water samples.

  14. Core-Shell Metal-Organic Frameworks/Molecularly Imprinted Nanoparticles as Absorbents for the Detection of Pyrraline in Milk and Milk Powder.

    Science.gov (United States)

    Liu, Huilin; Mu, Lin; Chen, Xiaomo; Wang, Jing; Wang, Shuo; Sun, Baoguo

    2017-02-01

    A novel core-shell metal-organic framework coated with a dummy template molecularly imprinted polymer (MOF@DMIP) was synthesized by one-pot bulk polymerization for the detection of pyrraline in food samples. The pyrraline analogue pyrrolidine-3-carboxylic acid was used as the template because of its lower cost, and MIL-101 was used as the MOF core owing to its numerous inherent advantages, including high chemical and hydrothermal stabilities. MIL-101@DMIP was used to detect trace pyrraline in foods by solid-phase extraction combined with high-performance liquid chromatography. It exhibited the advantages of faster mass transport, excellent sensitivity, and selectivity. Under optimum conditions, the detection limit of this system was 40.7 μg L(-1), and a linear range was from 5 × 10(-7) to 2 × 10(-3) mol L(-1), within relative standard deviations of 4.46-6.87%. The recoveries ranged from 92.23 to 103.87%, indicating the excellent ability of the prepared MIL-101@DMIP to recognize pyrraline in complex food matrices and its potential for application in pyrraline detection.

  15. Adsorptive denitrogenation of model fuels with porous metal-organic framework (MOF) MIL-101 impregnated with phosphotungstic acid: effect of acid site inclusion.

    Science.gov (United States)

    Ahmed, Imteaz; Khan, Nazmul Abedin; Hasan, Zubair; Jhung, Sung Hwa

    2013-04-15

    A metal-organic framework (MOF) MIL-101 was impregnated with phosphotungstic acid (PWA) and used as an adsorbent in liquid phase adsorption of nitrogen-containing compounds (NCCs) from a model fuel. The model fuel contained one sulfur-containing compound (SCC), benzothiophene (BT); one basic NCC, quinoline (QUI); and one neutral NCC, indole (IND). In both MIL-101 and PWA-impregnated MIL-101s, NCC adsorption selectivity was very high compared to the SCC selectivity. Additionally, the adsorption capacity of basic QUI increased by 20% with only 1% PWA impregnation in MIL-101. The adsorption of a neutral compound, IND, was slightly reduced with PWA impregnation in the MOF. The adsorption capacity/selectivity can be remarkably improved by a slight modification of MOFs, for example, to impart acidity. The MOF impregnated with PWA may be very interesting in commercial denitrogenation, especially for coal-derived fuels which contain mainly basic NCCs, by adsorption since the selectivity for NCCs (compared to SCCs) over the adsorbent is very high and the adsorbent can be reused many times. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. In situ gelation of Al(III)-4-tert-butylpyridine based metal-organic gel electrolyte for efficient quasi-solid-state dye-sensitized solar cells

    Science.gov (United States)

    Dong, Yu-Jie; Rao, Hua-Shang; Cao, Yang; Chen, Hong-Yan; Kuang, Dai-Bin; Su, Cheng-Yong

    2017-03-01

    A novel Al(III)-4-tert-butylpyridine (TBP) gel electrolyte is successfully achieved by a simple and facile in situ gelation method and applied as quasi-solid-state electrolyte for dye-sensitized solar cells (DSSCs). Through directly adding Al3+ into the TBP solution, the induced hydrolysis of Al3+ and the coordination interaction between Al3+ and TBP facilitates the formation of metal-organic gels(MOGs), in which such bi-functional TBP molecules will act as both gelators and active additives to tailor the performance of electrolytes. In addition, the gel electrolytes can largely preserve the properties of liquid electrolyte and penetrate well into the TiO2 photoanode film. Both Al3+ and TBP in the gel electrolytes affect the performance of cells. The Jsc of gel electrolytes decrease with the increasing concentration of gelators due to the enhanced strength and viscosity of the gel electrolytes, while the competition between Al3+ and TBP causes conduction band edge shift and electron recombination, leading to a variation of Voc. Herein, by tuning the molar ratio of Al3+/TBP, an impressive conversion efficiency of 8.25% is obtained, indicating a promising protocol of preparing MOGs not only to achieve high performance in solar cells, but also opens up extended scopes in other energy-related fields such as catalysis.

  17. Encapsulation of Bimetallic Metal Nanoparticles into Robust Zirconium-Based Metal-Organic Frameworks: Evaluation of the Catalytic Potential for Size-Selective Hydrogenation.

    Science.gov (United States)

    Rösler, Christoph; Dissegna, Stefano; Rechac, Victor L; Kauer, Max; Guo, Penghu; Turner, Stuart; Ollegott, Kevin; Kobayashi, Hirokazu; Yamamoto, Tomokazu; Peeters, Daniel; Wang, Yuemin; Matsumura, Syo; Van Tendeloo, Gustaaf; Kitagawa, Hiroshi; Muhler, Martin; Llabrés I Xamena, Francesc X; Fischer, Roland A

    2017-03-13

    The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal-organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core-shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core-shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquid-phase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Controlling morphology and optical properties of self-catalyzed, mask-free GaN rods and nanorods by metal-organic vapor phase epitaxy

    Science.gov (United States)

    Tessarek, C.; Bashouti, M.; Heilmann, M.; Dieker, C.; Knoke, I.; Spiecker, E.; Christiansen, S.

    2013-10-01

    A simple self-catalyzed and mask-free approach will be presented to grow GaN rods and nanorods based on the metal-organic vapor phase epitaxy technique. The growth parameter dependent adjustment of the morphology of the structures will be discussed. Rods and nanorods with diameters reaching from a few μm down to 100 nm, heights up to 48 μm, and densities up to 8ṡ107 cm-2 are all vertically aligned with respect to the sample surface and exhibiting a hexagonal shape with smooth sidewall facets. Optical properties of GaN nanorods were determined using cathodoluminescence. It will be shown that the optical properties can be improved just by reducing the Ga precursor flow. Furthermore, for regular hexagonal shaped rods and nanorods, whispering gallery modes with quality factors up to 500 were observed by cathodoluminescence pointing out high morphological quality of the structures. Structural investigations using transmission electron microscopy show that larger GaN nanorods (diameter > 500 nm) contain threading dislocations in the bottom part and vertical inversion domain boundaries, which separate a Ga-polar core from a N-polar shell. In contrast, small GaN nanorods (˜200 nm) are largely free of such extended defects. Finally, evidence for a self-catalyzed, Ga-induced vapor-liquid-solid growth will be discussed.

  19. Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting

    Directory of Open Access Journals (Sweden)

    Tatjana Ladnorg

    2013-10-01

    Full Text Available Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE. The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy.

  20. Liquid Marbles

    KAUST Repository

    Khalil, Kareem

    2012-12-01

    Granulation, the process of formation of granules from a combination of base powders and binder liquids, has been a subject of research for almost 50 years, studied extensively for its vast applications, primarily to the pharmaceutical industry sector. The principal aim of granulation is to form granules comprised of the active pharmaceutical ingredients (API’s), which have more desirable handling and flowability properties than raw powders. It is also essential to ensure an even distribution of active ingredients within a tablet with the goal of achieving time‐controlled release of drugs. Due to the product‐specific nature of the industry, however, data is largely empirical [1]. For example, the raw powders used can vary in size by two orders of magnitude with narrow or broad size distributions. The physical properties of the binder liquids can also vary significantly depending on the powder properties and required granule size. Some significant progress has been made to better our understanding of the overall granulation process [1] and it is widely accepted that the initial nucleation / wetting stage, when the binder liquid first wets the powders, is key to the whole process. As such, many experimental studies have been conducted in attempt to elucidate the physics of this first stage [1], with two main mechanisms being observed – classified by Ivenson [1] as the “Traditional description” and the “Modern Approach”. See Figure 1 for a graphical definition of these two mechanisms. Recent studies have focused on the latter approach [1] and a new, exciting development in this field is the Liquid Marble. This interesting formation occurs when a liquid droplet interacts with a hydrophobic (or superhydrophobic) powder. The droplet can become encased in the powder, which essentially provides a protective “shell” or “jacket” for the liquid inside [2]. The liquid inside is then isolated from contact with other solids or liquids and has some

  1. Metal-Organic Coordination Network Thin Film by Surface-Induced Assembly.

    Science.gov (United States)

    Laokroekkiat, Salinthip; Hara, Mitsuo; Nagano, Shusaku; Nagao, Yuki

    2016-07-01

    The growth of metal-organic coordination network thin films on surfaces has been pursued extensively and intensively to manipulate the molecular arrangement. For this study, the oriented multilayer thin films based on porphyrinic nanoarchitecture were synthesized toward metal-organic coordination networks using surface-induced assembly (SIA). Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion and porphyrin building blocks as precursors. Stepwise growth with a highly uniform layer was characterized using UV-vis, AFM, IR, and XPS studies. The grazing incidence small-angle X-ray scattering and X-ray reflectivity results remarkably suggested a periodic structure in in-plane direction with constant and high mass density (ca. 1.5 g/cm(3)) throughout the multilayer formation. We propose that orientation of the porphyrin macrocycle plane with a hexagonal packed model by single anchoring mode was tilted approximately 60° with respect to the surface substrate. It is noteworthy that the well-organized structure of porphyrin-based macrocyclic framework on the amine-terminated surface substrate can be achieved efficiently using a simple SIA approach under mild synthetic conditions. The synthesized thin film provides a different structure from that obtained using bulk synthesis. This result suggests that the SIA technique can control not only the film thickness but also the structural arrangement on the surface. This report of our research provides insight into the ordered porphyrin-based metal-organic coordination network thin films, which opens up opportunities for exploration of unique thin film materials for diverse applications.

  2. Rational design, synthesis, purification, and activation of metal-organic framework materials.

    Science.gov (United States)

    Farha, Omar K; Hupp, Joseph T

    2010-08-17

    The emergence of metal-organic frameworks (MOFs) as functional ultrahigh surface area materials is one of the most exciting recent developments in solid-state chemistry. Now constituting thousands of distinct examples, MOFs are an intriguing class of hybrid materials that exist as infinite crystalline lattices with inorganic vertices and molecular-scale organic connectors. Useful properties such as large internal surface areas, ultralow densities, and the availability of uniformly structured cavities and portals of molecular dimensions characterize functional MOFs. Researchers have effectively exploited these unusual properties in applications such as hydrogen and methane storage, chemical separations, and selective chemical catalysis. In principle, one of the most attractive features of MOFs is the simplicity of their synthesis. Typically they are obtained via one-pot solvothermal preparations. However, with the simplicity come challenges. In particular, MOF materials, especially more complex ones, can be difficult to obtain in pure form and with the optimal degree of catenation, the interpenetration or interweaving of identical independent networks. Once these two issues are satisfied, the removal of the guest molecules (solvent from synthesis) without damaging the structural integrity of the material is often an additional challenge. In this Account, we review recent advances in the synthetic design, purification, and activation of metal-organic framework materials. We describe the rational design of a series of organic struts to limit framework catenation and thereby produce large pores. In addition, we demonstrate the rapid separation of desired MOFs from crystalline and amorphous contaminants cogenerated during synthesis based on their different densities. Finally, we discuss the mild and efficient activation of initially solvent-filled pores with supercritical carbon dioxide, yielding usable channels and high internal surface areas. We expect that the

  3. RECENT ADVANCES IN NOVEL DRUG DELIVERY SYSTEMS

    Directory of Open Access Journals (Sweden)

    Manivannan Rangasamy

    2010-12-01

    Full Text Available Drug delivered can have significant effect on its efficacy. Some drugs have an optimum concentration range with in which maximum benefit is derived and concentrations above (or below the range can be toxic or produce no therapeutic effect. Various drug delivery and drug targeting systems are currently under development. The main goal for developing such delivery systems is to minimize drug degradation and loss, to prevent harmful side effects and to increase bioavailability. Targeting is the ability to direct the drug loaded system to the site of interest. Among drug carrier one can name soluble polymers, microparticles made of insoluble (or biodegradable natural and synthetic polymers, microcapsules, cells, cell ghosts, lipoproteins, liposomes and micelles. Two major mechanisms can be distinguished for addressing the desired sites for drug release, (a Passive and (b Active targeting. Controlled drug carrier systems such as micellar solutions, vescicles and liquid crystal dispersions, as well as nanoparticle dispersions consisting of small particles of 10 – 400 nm show great promise as drug delivery systems. Hydrogels are three dimensional, hydrophilic, polymer networks capable of imbibing large amounts of water or biological fluids. Buckyballs, a novel delivery system with 60 carbon atoms formed in the shape of hollow ball. They are other type’s namely bucky babies, fuzzy balls, gadofullereness, and giant fullerenes. Nanoparticles can be classified as nano tubes, nano wires, nano cantilever, nanoshells, quantum dots, nano pores. Researchers at north western university using gold particles to develop ultra sensitive detection systems for DNA and protein markers associated with many forms of cancer, including breast and prostrate cancer. Drug loaded erythrocytes is one of the growing and potential systems for delivery of drugs and enzymes.

  4. Global Delivery Models

    DEFF Research Database (Denmark)

    Manning, Stephan; Møller Larsen, Marcus; Bharati, Pratyush M.

    2015-01-01

    Global delivery models (GDMs) are transforming the global IT and business process outsourcing industry. GDMs are a new form of client-specific investment promoting service integration with clients by combining client proximity with time-zone spread for 24/7 service operations. We investigate...... antecedents and contingencies of setting up GDM structures. Based on comprehensive data we show that providers are likely to establish GDM location configurations when clients value access to globally distributed talent and speed of service delivery, in particular when services are highly commoditized...

  5. Ethical issues in cesarean delivery.

    Science.gov (United States)

    Chervenak, Frank A; McCullough, Laurence B

    2017-08-01

    Cesarean delivery is the most common and important surgical intervention in obstetric practice. Ethics provides essential guidance to obstetricians for offering, recommending, recommending against, and performing cesarean delivery. This chapter provides an ethical framework based on the professional responsibility model of obstetric ethics. This framework is then used to address two especially ethically challenging clinical topics in cesarean delivery: patient-choice cesarean delivery and trial of labor after cesarean delivery. This chapter emphasizes a preventive ethics approach, designed to prevent ethical conflict in clinical practice. To achieve this goal, a preventive ethics approach uses the informed consent process to offer cesarean delivery as a medically reasonable alternative to vaginal delivery, to recommend cesarean delivery, and to recommend against cesarean delivery. The limited role of shared decision making is also described. The professional responsibility model of obstetric ethics guides this multi-faceted preventive ethics approach. Copyright © 2017. Published by Elsevier Ltd.

  6. Metal-Organic Frameworks for Sensing Applications in the Gas Phase

    OpenAIRE

    Sabine Achmann; Gunter Hagen; Jaroslaw Kita; Malkowsky, Itamar M.; Christoph Kiener; Ralf Moos

    2009-01-01

    Several metal-organic framework (MOF) materials were under investigated to test their applicability as sensor materials for impedimetric gas sensors. The materials were tested in a temperature range of 120 °C - 240 °C with varying concentrations of O2, CO2, C3H8, NO, H2, ethanol and methanol in the gas atmosphere and under different test gas humidity conditions. Different sensor configurations were studied in a frequency range of 1 Hz -1 MHz and time-continuous measurements were performed at ...

  7. The direct heat measurement of mechanical energy storage metal-organic frameworks.

    Science.gov (United States)

    Rodriguez, Julien; Beurroies, Isabelle; Loiseau, Thierry; Denoyel, Renaud; Llewellyn, Philip L

    2015-04-07

    In any process, the heat exchanged is an essential property required in its development. Whilst the work related to structural transitions of some flexible metal-organic frameworks (MOFs) has been quantified and linked with potential applications such as molecular springs or shock absorbers, the heat related to such transitions has never been directly measured. This has now been carried out with MIL-53(Al) using specifically devised calorimetry experiments. We project the importance of these heats in devices such as molecular springs or dampers.

  8. Photochromic metal-organic frameworks: reversible control of singlet oxygen generation.

    Science.gov (United States)

    Park, Jihye; Feng, Dawei; Yuan, Shuai; Zhou, Hong-Cai

    2015-01-07

    The controlled generation of singlet oxygen is of great interest owing to its potential applications including industrial wastewater treatment, photochemistry, and photodynamic therapy. Two photochromic metal-organic frameworks, PC-PCN and SO-PCN, have been developed. A photochromic reaction has been successfully realized in PC-PCN while maintaining its single crystallinity. In particular, as a solid-state material which inherently integrates the photochromic switch and photosensitizer, SO-PCN has demonstrated reversible control of (1)O2 generation. Additionally, SO-PCN shows catalytic activity towards photooxidation of 1,5-dihydroxynaphthalene.

  9. A porous Cu(II) metal-organic framework: Synthesis, crystal structure and gas adsorption properties

    Science.gov (United States)

    Li, Wu-Wu; Guo, Ying; Zhang, Wei-Hong

    2017-09-01

    Presented here is a new porous Cu(II) metal-organic framework, namely [Cu(tdc)(H2O)]n·n(DMA) (1 H2tdc = thiophene-2,5-dicarboxylic acid, DMA = N,N‧-dimethylacetamide), which was obtained by the self-assembly reaction of CuCl2 and H2tdc under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that compound 1 features a 3D porous framework based on 1D chain structure subunits, and the 1D rhombohedral channels are occupied by the lattice DMA molecules. Gas adsorption studies reveal that this desolvated sample exhibit high uptake capacity for light hydrocarbons.

  10. Fluorous Metal-Organic Frameworks with Enhanced Stability and High H2/CO2 Storage Capacities

    Science.gov (United States)

    Zhang, Da-Shuai; Chang, Ze; Li, Yi-Fan; Jiang, Zhong-Yi; Xuan, Zhi-Hong; Zhang, Ying-Hui; Li, Jian-Rong; Chen, Qiang; Hu, Tong-Liang; Bu, Xian-He

    2013-01-01

    A new class of metal-organic frameworks (MOFs) has been synthesized by ligand-functionalization strategy. Systematic studies of their adsorption properties were performed at low and high pressure. Importantly, when fluorine was introduced into the framework via the functionalization, both the framework stabilities and adsorption capacities towards H2/CO2 were enhanced significantly. This consequence can be well interpreted by theoretical studies of these MOFs structures. In addition, one of these MOFs TKL-107 was used to fabricate mixed matrix membranes, which exhibit great potential for the application of CO2 separation. PMID:24264725

  11. Metal-organic frameworks and their applications in catalysis; Redes metalorganicas e suas aplicacoes em catalise

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, Andre Luis Dantas, E-mail: aldramos@ufs.br [Universidade Federal de Sergipe (UFSE), Sao Cristovao, SE (Brazil). Departamento de Engenharia Quimica; Tanase, Stefania; Rothenberg, Gadi [Van' t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam (Netherlands)

    2014-07-01

    Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science. (author)

  12. High efficiency AIGaAs/Si monolithic tandem solar cell grown by metalorganic chemical vapor deposition

    OpenAIRE

    Tetsuo, Soga; T.", "Kato; M., Yang; Masayoshi, Umeno; Takashi, Jimbo

    1995-01-01

    The improvements of the AlGaAs solar cell grown on the Si substrate and the AlGaAs/Si tandem solar cell by metalorganic chemical vapor deposition have been investigated. The active‐area conversion efficiency of the Al0.1Ga0.9As solar cell on the Si substrate as high as 12.9% has been obtained by improving the growth sequence and adopting an Al compositionally graded band emitter layer. A high efficiency monolithic AlGaAs/Si tandem solar cell with the active‐area conversion efficiency of 19.9%...

  13. Surface organization of homoepitaxial InP films grown by metalorganic vapor-phase epitaxy

    OpenAIRE

    Gocalinska, A.; Manganaro, M.; Vvedensky, D. D.; Pelucchi, E.

    2012-01-01

    We present a systematic study of the morphology of homoepitaxial InP films grown by metalorganic vapor-phase epitaxy which are imaged with ex situ atomic force microscopy. These films show a dramatic range of different surface morphologies as a function of the growth conditions and substrate (growth temperature, V/III ratio, and miscut angle < 0.6deg and orientation toward A or B sites), ranging from stable step flow to previously unreported strong step bunching, over 10 nm in height. These o...

  14. Postsynthetic modification of metal-organic framework for hydrogen sulfide detection

    Science.gov (United States)

    Zhang, Xin; Zhang, Jianmin; Hu, Quan; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2015-11-01

    Hydrogen sulfide (H2S) has recently been identified as the third biological gaseous messenger (gasotransmitter) that is involved in regulating many important physiological processes. The detection of H2S is thus essential for its roles but remain challenging in living systems. We report herein a novel turn-on fluorescent probe for H2S detection based on azide functionalized metal-organic framework (MOF). The MOF probe displayed high sensitivity (detection limit, 28.3 μM), excellent selectivity, and fast response (MOF probe can be employed as a useful tool to further elucidate the biological roles of H2S.

  15. Use of the PIXEL method to investigate gas adsorption in metal-organic frameworks.

    Science.gov (United States)

    Maloney, Andrew G P; Wood, Peter A; Parsons, Simon

    2016-05-14

    PIXEL has been used to perform calculations of adsorbate-adsorbent interaction energies between a range of metal-organic frameworks (MOFs) and simple guest molecules. Interactions have been calculated for adsorption between MOF-5 and Ar, H2, and N2; Zn2(BDC)2(TED) (BDC = 1,4-benzenedicarboxylic acid, TED = triethylenediamine) and H2; and HKUST-1 and CO2. The locations of the adsorption sites and the calculated energies, which show differences in the Coulombic or dispersion characteristic of the interaction, compare favourably to experimental data and literature energy values calculated using density functional theory.

  16. A Versatile Al(III) -Based Metal-Organic Framework with High Physicochemical Stability.

    Science.gov (United States)

    Wang, Zhuo-Wei; Chen, Min; Liu, Chun-Sen; Wang, Xi; Zhao, Hui; Du, Miao

    2015-11-23

    A unique Al(III) -based metal-organic framework (467-MOF) with two types of square channels has been designed and synthesized by using a flexible tricarboxylate ligand under solvothermal conditions. 467-MOF exhibits superior thermal and chemical stability and, moreover, shows high CO2 sorption selectivity over H2 , with a selectivity, based on the ideal adsorbed solution theory (IAST) of approximately 45 at 273 or 293 K. Furthermore, its solvent-dependent photoluminescence makes it an applicable sensor in the detection of nitrobenzene explosives through fluorescence quenching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A Rigid Nested Metal-Organic Framework Featuring a Thermoresponsive Gating Effect Dominated by Counterions.

    Science.gov (United States)

    Gao, Qiang; Xu, Jian; Cao, Dapeng; Chang, Ze; Bu, Xian-He

    2016-11-21

    We herein report a rigid nested metal-organic framework (MOF) featuring a unique thermoresponsive gating adsorption behavior, which, in contrast to any known flexibility modes for stimuli-responsive MOFs, depends on the thermal motion of the extra-framework counterions. In addition, this MOF also exhibits adsorption selectivity of CO2 over N2 , H2 , and Ar at 273 K, thus enabling a strategic separation and encapsulation of CO2 . © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Hierarchical Pore Development by Plasma Etching of Zr-Based Metal-Organic Frameworks.

    Science.gov (United States)

    DeCoste, Jared B; Rossin, Joseph A; Peterson, Gregory W

    2015-12-07

    The typically stable Zr-based metal-organic frameworks (MOFs) UiO-66 and UiO-66-NH2 were treated with tetrafluoromethane (CF4 ) and hexafluoroethane (C2 F6 ) plasmas. Through interactions between fluoride radicals from the perfluoroalkane plasma and the zirconium-oxygen bonds of the MOF, the resulting materials showed the development of mesoporosity, creating a hierarchical pore structure. It is anticipated that this strategy can be used as a post-synthetic technique for developing hierarchical networks in a variety of MOFs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Metal-organic framework templated synthesis of porous inorganic materials as novel sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L.; Lin, Wenbin; Abney, Carter W.

    2017-03-21

    A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.

  20. [Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers].

    Science.gov (United States)

    Qi, Xiaoyue; Li, Xianjiang; Bai, Yu; Liu, Huwei

    2016-01-01

    Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development, agricultural chemistry, pharmacology, environmental science, biology and many other fields. Chiral metal-organic frameworks (MOFs) are a new group of porous materials with special topology and designable pore structures, as well as their high specific surface area, porosity, excellent thermal stability, solvent resistance, etc. Thus, chiral MOFs are promising with various applications in the field of analytical chemistry. This review summarizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers, as well as related mechanism.