Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State.

The solid-state properties of organic radicals depend on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4-dimethoxyphenylene), which associates in its bisradical dicationic redox state with the methyl viologen radical cation (MV•+) to give a 1:1 inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments reveal that the methoxy substituents on the p-phenylene linkers do not influence binding of the cyclophane toward small neutral guests-such as dimethoxybenzene and tetrathiafulvalene-whereas binding of larger radical cationic guests such as MV•+ by the reduced cyclophane decreases 10-fold. X-ray diffraction analysis reveals that the solid-state superstructure of the 1:1 complex constitutes a discrete entity with weak intermolecular orbital overlap between neighboring complexes. Transient nutation EPR experiments and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap, while the quartet-state spin configuration is higher in energy and inaccessible at ambient temperature. Superconducting quantum interference device (SQUID) measurements reveal that the trisradical tricationic complexes interact antiferromagnetically and form a one-dimensional Heisenberg antiferromagnetic chain along the a-axis of the crystal. These results offer insights into the design and synthesis of organic magnetic materials based on host-guest complexes.

Organically modified layered magnesium silicates to improve rheology of reservoir drilling fluids.

Petroleum well drilling fluids are one of the most significant constituents in the subterranean drilling processes to meet an increasing global demand for oil and gas. Drilling fluids experience exceptional wellbore conditions, e.g. high temperature and high pressure that adversely affect the rheology of these fluids. Gas and oil well drilling operations have to adjourn due to changes in fluid rheology, since the drilling fluids may lose their effectiveness to suspend heavy particles and to carry drilled cuttings to the surface. The rheological properties of drilling fluids can be controlled by employing viscosifiers that should have exceptional stability in downhole environments. Here, we have developed next-generation viscosifiers-organically modified magnesium silicates (MSils)-for reservoir drilling fluids where organic functionalities are directly linked through the Si-C bond, unlike the industry's traditional viscosifier, organoclay, that has electrostatic linkages. The successful formation of covalently-linked hexadecyl and phenyl functionalized magnesium silicates (MSil-C16 and MSil-Ph) were confirmed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). Identical drilling fluid formulations were designed for comparison using MSils and a commercial viscosifier. The rheological properties of fluids were measured at ambient conditions as well as at high temperatures (up to 150 °C) and high pressure (70 MPa). Owing to strong covalent linkages, drilling fluids that were formulated with MSils showed a 19.3% increase in yield point (YP) and a 31% decrease in apparent viscosity (AV) at 150 °C under 70 MPa pressure, as compared to drilling fluids that were formulated with traditional organoclay. The higher yield point and lower apparent viscosity are known to facilitate and increased drilling rate of penetration of the fluids and an enhanced equivalent circulation density (ECD), the dynamic density condition, for efficient oil and gas wells drilling procedures.

Discrete Dimers of Redox-Active and Fluorescent Perylene Diimide-Based Rigid Isosceles Triangles in the Solid State.

The development of rigid covalent chiroptical organic materials, with multiple, readily available redox states, which exhibit high photoluminescence, is of particular importance in relation to both organic electronics and photonics. The chemically stable, thermally robust, and redox-active perylene diimide (PDI) fluorophores have received ever-increasing attention owing to their excellent fluorescence quantum yields in solution. Planar PDI derivatives, however, generally suffer from aggregation-caused emission quenching in the solid state. Herein, we report on the design and synthesis of two chiral isosceles triangles, wherein one PDI fluorophore and two pyromellitic diimide (PMDI) or naphthalene diimide (NDI) units are arranged in a rigid cyclic triangular geometry. The optical, electronic, and magnetic properties of the rigid isosceles triangles are fully characterized by a combination of optical spectroscopies, X-ray diffraction (XRD), cyclic voltammetry, and computational modeling techniques. Single-crystal XRD analysis shows that both isosceles triangles form discrete, nearly cofacial PDI-PDI π-dimers in the solid state. While the triangles exhibit fluorescence quantum yields of almost unity in solution, the dimers in the solid state exhibit very weak-yet at least an order of magnitude higher-excimer fluorescence yield in comparison with the almost completely quenched fluorescence of a reference PDI. The triangle containing both NDI and PDI subunits shows superior intramolecular energy transfer from the lowest excited singlet state of the NDI to that of the PDI subunit. Cyclic voltammetry suggests that both isosceles triangles exhibit multiple, easily accessible, and reversible redox states. Applications beckon in arenas related to molecular optoelectronic devices.

Proton Conduction in Tröger's Base-Linked Poly(crown ether)s.

Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host-guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers-poly(TBL-DB18C6)- t and poly(TBL-DB18C6)- c-synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)- t, which is found to be 1.4 × 10-4 mS cm-1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

Noninvasive Substitution of K+ Sites in Cyclodextrin Metal-Organic Frameworks by Li+ Ions.

Co-crystallization of K+ and Li+ ions with γ-cyclodextrin (γ-CD) has been shown to substitute the K+ ion sites partially by Li+ ions, while retaining the structural integrity and accessible porosity of CD-MOF-1 (MOF, metal-organic framework). A series of experiments, in which the K+/Li+ ratio was varied with respect to that of γ-CD, have been conducted in order to achieve the highest possible proportion of Li+ ions in the framework. Attempts to obtain a CD-MOF containing only Li+ ions resulted in nonporous materials. The structural occupancy on the part of the Li+ ions in the new CD-MOF has been confirmed by single-crystal X-ray analysis by determining the vacancies of K+-ion sites and accounting for the cation/γ-CD ratio in CD-MOF-1. The proportion of Li+ ions has also been confirmed by elemental analysis, whereas powder X-ray diffraction has established the stability of the extended framework. This noninvasive synthetic approach to generating mixed-metal CD-MOFs is a promising method for obtaining porous framework unattainable de novo. Furthermore, the CO2 and H2 capture capacities of the Li+-ion-substituted CD-MOF have been shown to exceed the highest sorption capacities reported so far for CD-MOFs.

Selective removal of heavy metal ions by disulfide linked polymer networks.

Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions-copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

Carbon Dioxide Capture Adsorbents: Chemistry and Methods.

Excess carbon dioxide (CO2 ) emissions and their inevitable consequences continue to stimulate hard debate and awareness in both academic and public spaces, despite the widespread lack of understanding on what really is needed to capture and store the unwanted CO2 . Of the entire carbon capture and storage (CCS) operation, capture is the most costly process, consisting of nearly 70 % of the price tag. In this tutorial review, CO2 capture science and technology based on adsorbents are described and evaluated in the context of chemistry and methods, after briefly introducing the current status of CO2 emissions. An effective sorbent design is suggested, whereby six checkpoints are expected to be met: cost, capacity, selectivity, stability, recyclability, and fast kinetics.

Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks.

Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.

Superacidity in Nafion/MOF Hybrid Membranes Retains Water at Low Humidity to Enhance Proton Conduction for Fuel Cells.

A hybrid membrane of superacid sulfated Zr-MOF (SZM) and Nafion shows much superior performance to Nafion, particularly for fuel cell operating under low humidity. The Brønsted acidic sites in SZM networks retain an ample amount of water which facilitated proton conduction under low humidity. The water retention properties of Nafion-SZM hybrid membranes with 1 wt % loading of SZM increased at 35% relative humidity and outperformed commercial unfilled Nafion membrane. The proton conductivity increases by 23% for Nafion-SZM hybrid compared to unfilled Nafion membrane. The Nafion-SZM membrane also shows higher performance stability at 35% relative humidity than Nafion, as confirmed by close monitoring of the change of open circuit voltage for 24 h.

Influence of hydrodynamic cavitation on the rheological properties and microstructure of formulated Greek-style yogurts.

With limited applications of acid whey generated during the manufacture of Greek yogurts, an alternate processing technology to sidestep the dewheying process was developed. Milk protein concentrate (MPC) and carbon dioxide-treated milk protein concentrate (TMPC) were used as sources of protein to fortify skim milk to 9% (wt/wt) protein for the manufacture of Greek-style yogurts (GSY). The GSY bases were inoculated and fermented with frozen direct vat set yogurt culture to a pH of 4.6. Owing to the difference in buffering of MPC and TMPC, GSY with TMPC and MPC exhibited different acidification kinetics, with GSY containing TMPC having a lower fermentation time. The GSY with TMPC had a titratable acidity of 1.45% lactic acid and was comparable to acidity of commercial Greek yogurt (CGY). Hydrodynamic cavitation at 4 different rotor speeds (0, 15, 30, and 60 Hz) as a postfermentation tool reduced the consistency coefficient (K) of GSY containing TMPC from 79.4 Pa·sn at 0 Hz to 17.59 Pa·sn at 60 Hz. Similarly for GSY containing MPC, K values decreased from 165.74 Pa·sn at 0 Hz to 53.04 Pa·sn at 60 Hz. The apparent viscosity (η100) was 0.25 Pa·s for GSY containing TMPC and 0.66 Pa·s for GSY containing MPC at 60 Hz. The CGY had a η100 value of 0.74 Pa·s. Small amplitude rheological analysis performed on GSY indicated a loss of elastic modulus dependency on frequency caused by the breakdown of protein interactions with increasing cavitator rotor speeds. A steady decrease in hardness and adhesiveness values of GSY was observed with increasing cavitational intensities. Numbers of grains with a perimeter of >1mm of cavitated GSY with TMPC and MPC were 35 and 13 grains/g of yogurt, respectively, and were lower than 293 grains/g observed in CGY. The water-holding capacity of GSY was higher than that observed for a commercial strained Greek yogurt. The ability to scale up the process of hydrodynamic cavitation industrially, and the ease of controlling events of cavitation that can influence final textural properties of the product, make this technology promising for large-scale industrial application. Overall, the current set of experiments employed in the manufacture of GSY, which included the use of TMPC as a protein source in conjunction with hydrodynamic cavitation, could help achieve comparable titratable acidity values, rheological properties, and microstructure to that of a commercial strained Greek yogurt.

Systematic Investigation of the Effect of Polymerization Routes on the Gas-Sorption Properties of Nanoporous Azobenzene Polymers.

Functional-group-oriented polymerization strategies have contributed significantly to the initial development of porous polymers and have led to the utilization of several well-known organic transformations in the synthesis of these polymers. Because there are multiple polymerization routes that can be used to introduce the same chemical functionality, it is very important to demonstrate the effect of different polymerization routes on the gas-sorption properties of these chemically similar polymers. Herein, we have studied the rich chemistry of azobenzenes and synthesized four chemically similar nanoporous azobenzene polymers (NABs) with surface areas of up to 1021 m(2) g(-1) . The polymerization routes have a significant impact on the pore-size distributions of the NABs, which directly affects the temperature dependence of the CO2 /N2 selectivity. A pore-width maximum of 6-8 Å, narrow pore-size distribution, and small particle size (20-30 nm) were very critical for high CO2 /N2 selectivity and N2 phobicity, which is associated with azo linkages and realized at warm temperatures. Our findings collectively suggest that an investigation of different polymerization routes for the same chemical functionalization is critical to understand fully the combined effect of textural properties, local environment, and chemical functionalization on the gas-sorption properties of nanoporous polymers.

Geriatric Respondents and Non-Respondents to Probiotic Intervention Can be Differentiated by Inherent Gut Microbiome Composition.

SCOPE: Probiotic interventions are known to have been shown to influence the composition of the intestinal microbiota in geriatrics. The growing concern is the apparent variation in response to identical strain dosage among human volunteers. One factor that governs this variation is the host gut microbiome. In this study, we attempted to define a core gut metagenome, which could act as a predisposition signature marker of inherent bacterial community that can help predict the success of a probiotic intervention. METHODS AND RESULTS: To characterize the geriatric gut microbiome, we designed primers targeting the 16S rRNA hypervariable region V2-V3 followed by semiconductor sequencing using Ion Torrent PGM. Among respondents and non-respondents, the chief genera of phylum Firmicutes that showed significant differences are Lactobacillus, Clostridium, Eubacterium, and Blautia (q < 0.002), while in the genera of phylum Proteobacteria included Shigella, Escherichia, Burkholderia and Camphylobacter (q < 0.002). CONCLUSION: We have identified potential microbial biomarkers and taxonomic patterns that correlate with a positive response to probiotic intervention in geriatric volunteers. Future work with larger cohorts of geriatrics with diverse dietary influences could reveal the potential of the signature patterns of microbiota for personalized nutrition.

Highly optimized CO2 capture by inexpensive nanoporous covalent organic polymers and their amine composites.

Carbon dioxide (CO2) storage and utilization requires effective capture strategies that limit energy penalties. Polyethylenimine (PEI)-impregnated covalent organic polymers (COPs) with a high CO2 adsorption capacity are successfully prepared in this study. A low cost COP with a high specific surface area is suitable for PEI loading to achieve high CO2 adsorption, and the optimal PEI loading is 36 wt%. Though the adsorbed amount of CO2 on amine impregnated COPs slightly decreased with increasing adsorption temperature, CO2/N2 selectivity is significantly improved at higher temperatures. The adsorption of CO2 on the sorbent is very fast, and a sorption equilibrium (10% wt) was achieved within 5 min at 313 K under the flow of simulated flue gas streams. The CO2 capture efficiency of this sorbent is not affected under repetitive adsorption-desorption cycles. The highest CO2 capture capacity of 75 mg g(-1) at 0.15 bar is achieved under dry CO2 capture however it is enhanced to 100 mg g(-1) in the mixed gas flow containing humid 15% CO2. Sorbents were found to be thermally stable up to at least 200 °C. TGA and FTIR studies confirmed the loading of PEIs on COPs. This sorbent with high and fast CO2 sorption exhibits a very promising application in direct CO2 capture from flue gas.

An Ultrahigh Pore Volume Drives Up the Amine Stability and Cyclic CO2 Capacity of a Solid-Amine@Carbon Sorbent.

Carbon monoliths of ultrahigh pore volume (5.35 cm(3) g(-1) ) and high surface area (2700 m(2) g(-1) ) accommodate a record high level of amine(tetraethylenepentamine), up to 5 g g(-1) within its hierarchically networked micro-/mesopores over a wide range. Thus, this solid-amine@carbon shows exceptional CO2 sorption and stable cyclic capacities at simulated flue-gas conditions.

Synthesis of nanoporous 1,2,4-oxadiazole networks with high CO2 capture capacity.

Developing an adsorbent to mitigate carbon dioxide without large energy penalty is highly desired. Here, we present a silylation synthetic route to form a processable and otherwise impossible porous 1,2,4-oxadiazole network, which achieves 2 mmol g(-1) of CO2 capacity owing to a nitrogen-rich structure. This network shows high CO2-N2 selectivity, thermal stability up to 450 °C, and low heat of adsorption (26.4 kJ mol(-1)), facilitating easy regeneration.

Directing the structural features of N(2)-phobic nanoporous covalent organic polymers for CO(2) capture and separation.

A family of azo-bridged covalent organic polymers (azo-COPs) was synthesized through a catalyst-free direct coupling of aromatic nitro and amine compounds under basic conditions. The azo-COPs formed 3D nanoporous networks and exhibited surface areas up to 729.6 m(2) g(-1) , with a CO2 -uptake capacity as high as 2.55 mmol g(-1) at 273 K and 1 bar. Azo-COPs showed remarkable CO2 /N2 selectivities (95.6-165.2) at 298 K and 1 bar. Unlike any other porous material, CO2 /N2 selectivities of azo-COPs increase with rising temperature. It was found that azo-COPs show less than expected affinity towards N2 gas, thus making the framework "N2 -phobic", in relative terms. Our theoretical simulations indicate that the origin of this unusual behavior is associated with the larger entropic loss of N2 gas molecules upon their interaction with azo-groups. The effect of fused aromatic rings on the CO2 /N2 selectivity in azo-COPs is also demonstrated. Increasing the π-surface area resulted in an increase in the CO2 -philic nature of the framework, thus allowing us to reach a CO2 /N2 selectivity value of 307.7 at 323 K and 1 bar, which is the highest value reported to date. Hence, it is possible to combine the concepts of "CO2 -philicity" and "N2 -phobicity" for efficient CO2 capture and separation. Isosteric heats of CO2 adsorption for azo-COPs range from 24.8-32.1 kJ mol(-1) at ambient pressure. Azo-COPs are stable up to 350 °C in air and boiling water for a week. A promising cis/trans isomerization of azo-COPs for switchable porosity is also demonstrated, making way for a gated CO2 uptake.

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers.

Post-combustion CO(2) capture and air separation are integral parts of the energy industry, although the available technologies remain inefficient, resulting in costly energy penalties. Here we report azo-bridged, nitrogen-rich, aromatic, water stable, nanoporous covalent organic polymers, which can be synthesized by catalyst-free direct coupling of aromatic nitro and amine moieties under basic conditions. Unlike other porous materials, azo-covalent organic polymers exhibit an unprecedented increase in CO(2)/N(2) selectivity with increasing temperature, reaching the highest value (288 at 323 K) reported to date. Here we observe that azo groups reject N(2), thus making the framework N(2)-phobic. Monte Carlo simulations suggest that the origin of the N(2) phobicity of the azo-group is the entropic loss of N(2) gas molecules upon binding, although the adsorption is enthalpically favourable. Any gas separations that require the efficient exclusion of N(2) gas would do well to employ azo units in the sorbent chemistry.

Noninvasive functionalization of polymers of intrinsic microporosity for enhanced CO2 capture.

Modifying sorbents for the purpose of improving carbon dioxide capture often results in the loss of surface area or accessible pores, or both. We report the first noninvasive functionalization of the polymers of intrinsic microporosity (PIMs) where inclusion of the amidoxime functionality in PIM-1 increases carbon dioxide capacity up to 17% and micropore surface area by 20% without losing its film forming ability.

Montmorillonite-alginate nanocomposites as a drug delivery system: intercalation and in vitro release of vitamin B1 and vitamin B6.

Sustained intestinal delivery of thiamine hydrochloride (Vitamin B(1); VB(1)) and pyridoxine hydrochloride (Vitamin B(6); VB(6)) seems to be a feasible alternative to existing therapy. The vitamins (VB(1)/VB(6)) intercalated in montmorillonite (MMT) and intercalated VB(1)/VB(6)-MMT hybrid is further used for synthesis of VB(1)/VB(6)-MMT-alginate nanocomposite beads by gelation method and in vitro release in the intestinal environment. The structure and surface morphology of the synthesized VB(1)/VB(6)-MMT hybrid, VB(1)/VB(6)-alginate and VB(1)/VB(6)-MMT-alginate nanocomposite beads were characterized by XRD, FT-IR, TGA and SEM. In vitro release experiments revealed that the VB(1)/VB(6) releases suddenly from VB(1)/VB(6)-MMT hybrid and is pH dependent. The controlled release of VB(1)/VB(6) from VB(1)/VB(6)-MMT-alginate nanocomposite beads was observed to be controlled as compared to their release from VB(1)/VB(6)-MMT hybrid and VB(1)/VB(6)-alginate beads.

Synthesis of highly dispersed gold and silver nanoparticles anchored on surfactant intercalated montmorillonite.

Gold and silver nanoparticles anchored on surfactant intercalated montmorillonite were prepared by two methodologies. In the first case, gold and silver nanoparticles were synthesized by reduction of gold and silver salt in hexadecyltrimethylammonium bromide (HDTA) and dioctadecyldimethylammonium chloride (DODA), followed by exchange of HDTA and DODA solution containing gold and silver nanoparticles into montmorillonite (MMT). In second case, HDTA and DODA with gold and silver salt was exchanged with MMT, and then reduced to obtain gold and silver nanoparticles. The particle size of gold and silver varies with the path of reduction as well as type of surfactant used for the modification of MMT. Gold and silver nanoparticles synthesized using quaternary ammonium salt with two long alkyl chain resulted into finer particles than a single long alkyl chain. The present study demonstrates the effect of reduction path, type of surfactants, and concentration of gold and silver on the particle size of gold and silver nanoparticles anchored on organoclay. Gold and silver nanoparticles supported organoclay were characterized by High resolution transmission electron microscopy (HRTEM), powdered X-ray diffraction (PXRD) and Inductive coupled plasma-atomic emission spectroscopy (ICP-AES).