Olefin Recovery by *BEA-Type Zeolite Membrane: Affinity-Based Separation with Olefin−Ag+ Interaction

Ag⁺ was introduced into *BEA-type zeolite membrane by an ion-exchange method to enhance olefin selectivity. Ag−*BEA membrane exhibited superior olefin separation performance for both ethylene/ethane and propylene/propane mixtures. Particularly, the separation factor for ethylene at 373 K reached 57 with the ethylene permeance of 1.6×10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹. Adsorption properties of olefin and paraffin were evaluated to discuss contribution of Ag⁺ to separation performance enhancement. A strong interaction between olefin and Ag⁺ in the membrane caused preferential adsorption of olefin against paraffin, leading to selective permeation of olefin. Ag−*BEA membrane also exhibited high olefin selectivities from olefin/N₂ mixtures. The affinity-based separation through Ag−*BEA membrane showed a high potential for olefin recovery and purification from various gas mixtures.     

Novel Potentiometric Solid-contact Electrode for the Determination of Fe2+ Ions via MWCNTs-Gemifloxacin Composite

A novel electrode was fabricated for the quantitation of Fe²⁺ ion. It was based on the covalent attachment of the gemifloxacin molecule (the recognition element) to the surface of MWCNTs to be incorporated as an electroactive material. Linear response of Fe²⁺ ions was found in the concentration range of 1×10⁻² mol L⁻¹ to 1×10⁻⁸ mol L⁻¹ with a Nernstian slope of 30.37 ±0.3 (mV/decade) and attained a stable response within 5 s. The sensor exhibited LOD value of 4.8×10⁻⁹ mol L⁻¹. It was applied in the monitoring of Fe²⁺ concentration in multi-vitamins tablets, tap water and milk samples with acceptable recovery ranged from 94.00 % to 102.00 %.     

Kinetic study of some reactions related to the Mn(II)-catalyzed bromate-saccharide oscillating reactions

In the stirred batch experiment, the Mn(II)-catalyzed bromate-saccharide reaction in aqueous H₂SO₄ or HClO₄ solution exhibits damped oscillations in the concentrations of bromide and Mn(II) ions. Peculiar multiple oscillations are observed in the system with arabinose or ribose. The apparent second-order rate constants of the Mn(III)-saccharide reactions at 25°C are (0.659, 1.03, 1.76, 2.32, and 6.95) M⁻¹ s⁻¹ in 1.00 M H₂SO₄ and (4.69, 7.51, 10.2, 13.5, and 36.2) M⁻¹ s⁻¹ in (2.00–4.00) M HClO₄ for (glucose, galactose, xylose, arabinose, and ribose), respectively. At 25°C, the observed pseudo-first-order rate constant of the Mn(III)-Br⁻ reaction is k_obs = (0.2 ± 0.1) [Br⁻] + (130 ± 5)[Br⁻]² + (2.6 ± 0.1) × 10³[Br⁻]³ + (1.2 ± 0.2) × 10⁴[Br⁻]⁴ s⁻¹ and the rate constant of the Br₂ Mn(II) reaction is less than 1 × 10⁻⁴ M⁻¹ s⁻¹. The second-order rate constants of the Br₂-saccharide reactions are (3.65 ± 0.15, 11.0 ± 0.5, 4.05, 12.5 ± 0.7, and 2.62) × 10⁻⁴ M⁻¹ s⁻¹ at 25°C for glucose, galactose, xylose, arabinose, and ribose, respectively.     

A 2D cadmium metal–organic framework: Synthesis,structure and luminescence sensing for chromate,permanganate, cupric,silver and ferric

A multi-responsive Cd metal–organic framework {[Cd (ttpe)(H₂O)(ip)]•4H₂O•DMAC}_n ( 1•4H ₂ O•DMAC ) was synthesized using hydrothermal method (ttpe = 1,1,2,2-tetra(4-(1H-1,2,4-triazol-1-yl)phenyl)ethylene, ip = isophthalate, DMAC = N,N-dimethylacetamide), and characterized. 1 exhibits a 2D (4,4) network. The luminescent sensing experimrnts showed that 1•4H ₂ O•DMAC as a new MOF luminescent sensor can detect Cr₂O₇²⁻, CrO₄²⁻, MnO₄⁻, Cu²⁺, Ag⁺ and Fe³⁺ in aqueous solution with simultaneously high efficiency and high sensitivity. The quenching constants K_sv for Cr₂O₇²⁻, CrO₄²⁻, MnO₄⁻, Cu²⁺, Ag⁺ and Fe³⁺ are 4.231 × 10⁴ M⁻¹, 2.471 × 10⁴ M⁻¹, 6.459 × 10³ M⁻¹, 7.617 × 10³ M⁻¹, 1.563 × 10⁴ M⁻¹ and 3.574 × 10⁴ M⁻¹, respectively. The detection limits are 0.094 μM for Cr₂O₇²⁻, 0.108 μM for CrO₄^{2 −} , 0.346 μM for MnO₄⁻, 0.302 μM for Cu²⁺, 0.221 μM for Ag ⁺ , and 0.100 μM for Fe³⁺. 1•4H ₂ O•DMAC exhibits high photocatalytic efficiency for degradation of methylene blue under visible light irradiation.     

Complex formation of Ni(II) and Fe(III) with the nitrite anion

The stepwise stabilities of the complexes formed by Ni(II) and Fe(III) with the nitrite anion have been determined potentiometrically in an aqueous sodium perchlorate medium of unit ionic strength at 25.0°C. Two fairly weak mononuclear complexes are formed in the Ni(II)-nitrite system with the overall formation constants at β₁ = 5.9±0.9 M⁻¹ and β₂ = 12±2 M⁻², while for the Fe(III)-nitrite system three mononuclear complexes of moderate strengths, namely β₁ = (3.9±0.7) × 10² M⁻¹, β₂ = (5±2) × 10³ M⁻² and β₃ = (2.8±0.6) × 10⁵ M⁻³, are found. No evidence has been found for the formation of polynuclear or acid complexes in the concentration range studied.     

Facilitated transport of olefin through solid PAAm and PAAm-graft composite membranes with silver ions

Solid poly(acrylamide) (PAAm) composite membranes containing silver ions have been investigated for olefin/paraffin separation. The propylene permeance increased significantly for a solid PAAm/AgBF₄ composite membrane with increasing loading amount of silver ions. Silver ions in solid PAAm form reversible complexes with propylene, resulting in the facilitated transport of propylene. The propylene selectivity of 100 over propane was obtained when the mole ratio of silver ions to acrylamide unit was 1. This high separation performance would be obtained predominantly because of the high loading of the propylene carrier, silver ions. PAAm-graft/AgBF₄ composite membranes were prepared in order to improve the gas permeance. Introduction of PAAm grafts on a polysulfone microporous membrane surface was confirmed by FT-IR spectroscopy. The propylene permeance was increased through the PAAm-graft/AgBF₄ membranes compared to that through of the PAAm/AgBF₄ composite membranes, indicating the formation of ultra-thin top layer.     

Coverage-Dependent Behaviors of Vanadium Oxides for Chemical Looping Oxidative Dehydrogenation

Chemical looping provides an energy- and cost-effective route for alkane utilization. However, there is considerable CO₂ co-production caused by kinetically mismatched O²⁻ bulk diffusion and surface reaction in current chemical looping oxidative dehydrogenation systems, rendering a decreased olefin productivity. Sub-monolayer or monolayer vanadia nanostructures are successfully constructed to suppress CO₂ production in oxidative dehydrogenation of propane by evading the interference of O²⁻ bulk diffusion (monolayer versus multi-layers). The highly dispersed vanadia nanostructures on titanium dioxide support showed over 90 % propylene selectivity at 500 °C, exhibiting turnover frequency of 1.9×10⁻² s⁻¹, which is over 20 times greater than that of conventional crystalline V₂O₅. Combining in situ spectroscopic characterizations and DFT calculations, we reveal the loading–reaction barrier relationship through the vanadia/titanium interfacial interaction.     

Isoniazid-sensing Behavior of a Hybrid Silsesquioxane and Cobalt Pentacyanonitrosylferrate-based Nanocomposite

A novel silsesquioxane and cobalt nitroprusside compound was prepared from octa(aminopropyl)silsesquioxane, resulting in a nanocomposite (ACCoN), which was then characterized by different spectroscopic techniques. The cyclic voltammograms of the ACCoN-modified graphite paste electrode indicated a redox pair with a formal potential (E^θ′)=0.38 V, assigned to the Co^(II)Fe^(II)(CN)₅NO/Co^(II)Fe^(III)(CN)₅NO redox couple. The ACCoN-modified graphite paste electrode was sensitive to isoniazid concentrations, presenting a linear response at a concentration range from 6.0×10⁻⁷ to 1.0×10⁻⁵ mol L⁻¹, with limit of detection and amperometric sensitivity of 5.53×10⁻⁷ mol L⁻¹ and 0.17 A/mol L⁻¹, respectively.     

Adsorption and diffusion of propane and propylene in Ag+-impregnated MCM-41

Equilibrium data and diffusion characteristics of propane and propylene were determined on mesoporous adsorbents modified with an organic molecule (APTES) and/or impregnated with AgNO₃, in order to obtain a separation by adsorption via π-complexation. Adsorption capacities were determined by a gravimetric technique, while diffusion characteristics were evaluated by the ZLC technique. The equilibrium isotherms data showed that the modification with an organic molecule will weaken the π-interaction between Ag⁺ and double C=C bond. On the other hand slightly higher adsorption capacities for propylene (about 1.5 mol/kg) were obtained for the sample prepared by a direct impregnation with larger amounts of AgNO₃ (M4 sample). Diffusion runs confirmed that the propane desorption rate on M4 sample was much higher compared to propylene. This evidence leads to a potential application of that adsorbent material for a kinetic separation.     

Synthetic Receptors with Micromolar Affinity for Chloride in Water

A water-soluble coordination cage was obtained by reaction of Pd(NO₃)₂ with a 1,3-di(pyridin-3-yl)benzene ligand featuring a short PEG chain. The cavity of the metal-organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is K_a=1.8(±0.1)×10⁵ M⁻¹. This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br⁻ and I⁻ compete with binding or self-assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand.     

Voltammetric Method for the Simultaneous Determination of Melatonin and Pyridoxine in Dietary Supplements Using a Cathodically Pretreated Boron‐doped Diamond Electrode

The simultaneous voltammetric determination of melatonin (MT) and pyridoxine (PY) has been carried out at a cathodically pretreated boron‐doped diamond electrode. By using cyclic voltammetry, a separation of the oxidation peak potentials of both compounds present in mixture was about 0.47 V in Britton‐Robinson buffer, pH 2. The results obtained by square‐wave voltammetry allowed a method to be developed for determination of MT and PY simultaneously in the ranges 1–100 μg mL⁻¹ (4.3×10⁻⁶–4.3×10⁻⁴ mol L⁻¹) and 10–175 μg mL⁻¹ (4.9×10⁻⁵–8.5×10⁻⁴ mol L⁻¹), with detection limits of 0.14 μg mL⁻¹ (6.0×10⁻⁷ mol L⁻¹) and 1.35 μg mL⁻¹ (6.6×10⁻⁶ mol L⁻¹), respectively. The proposed method was successfully to the dietary supplements samples containing these compounds for health‐caring purposes.     

C2 and C3 hydrocarbon separations in poly(1,5-naphthalene-2,2′-bis(3,4-phthalic) hexafluoropropane) diimide (6FDA-1,5-NDA) dense membranes

The transport of olefin and paraffin namely ethane, ethylene, propane and propylene in aromatic poly(1,5-naphthalene-2,2′-bis(3,4-phthalic) hexafluoropropane) diimide (6FDA-1,5-NDA) dense membranes was investigated. The gas permeability coefficients were measured at pressures from 2.5 to 16 atm for the C₂ hydrocarbon gases and pressures up to 8.4 atm for C₃ systems at 35 °C. This membrane exhibits permeabilities of 0.15, 0.87, 0.023 and 0.24 Barrer with respect to pure ethane, ethylene, propane and propylene, and shows an ideal selectivity of 5.8 for the separation of ethylene/ethane, 10 for propylene/propane, 7.6 for nitrogen/ethane and 50 for nitrogen/propane. The olefins showed a preferred permeability to paraffins and discussion were drawn to the permeability, diffusivity and solubility coefficients. The activation energies of permeation, diffusion and solution were also reported and the effect of temperature on the permeation properties was discussed for the pure gas permeability data obtained from 30 to 50 °C. The plasticisation effect was also found for propane and propylene, respectively, although it was neither detected in the saturated nor unsaturated C₂ hydrocarbons at pressures up to 16 atm.     

Propane/propylene separation by selective olefin adsorption on Cu/SBA-15 mesoporous silica

Samples of mesoporous silica, SBA-15, were prepared under hydrothermal conditions and Cu cations were incorporated into the framework by two different impregnation techniques. The corresponding adsorption/desorption isotherms of propylene, propane, and N₂ were measured to evaluate the material's effectiveness in the separation of propane/propylene mixtures. Adsorption uptake of propylene increased and that of propane decreased in Cu containing samples as compared to the uptakes observed in undoped SBA-15 samples. It was demonstrated that the presence of Cu atoms in the adsorbent lattice led to a greater selectivity towards propylene. Furthermore, the highest level of Cu(I) were obtained in samples prepared by equilibrium impregnation, which in turn improved the olefin/paraffin uptake ratio. Under some working conditions, the amount of propylene adsorbed in selected samples is totally reversible while propane uptake was negligible.     

Characterization of the chain stiffness for a mesogen-jacketed liquid crystal polymer: Poly{2,5-BIS [(4-Methoxybenzoyl)Oxy] Styrene}

Narrow-distribution fractions of poly{2,5-bis[(4-methoxybenzoyl)oxy] styrene} ranging in weight-average molecular weight Mw from 1.1 × 10⁵ to 1.96 × 10⁶ were studied by static light scattering and viscometry in THF at 25 ^° C. From Mw and the intrinsic viscosity [ η ] Mark-Houwink-Sakurada equation was formulated with K=7.54×10⁻⁴ and ≈=0.82. The relation between [ η ] and Mw was analyzed according to Bohdanecky for the Kratky-Porod wormlike chain, the ranges of the mass per unit length M_L and the persistence length q were estimated as 35 nm⁻¹ M<_L42 nm<₋₁ and 11.5 nm <13.5 nm, respectively. The values of ≈ and q indicate that the polymer, though a liquid crystal polymer of the side-chain type, has wormlike chain in dilute solution as most main chain liquid crystal polymers.     

Solid polymer electrolyte composite membranes for olefin/paraffin separation

Ethylene and propylene are produced in larger quantities than any other organic compound. Production of these olefins requires separation of the olefins from the corresponding paraffins. Distillation is currently used but this is an extremely energy-intensive process due to the very low relative volatility of the components. Previous studies have shown that facilitated transport membranes can have high selectivity for olefin/paraffin separation. However, four problems have limited the commercial application of facilitated transport membranes: (i) poor mechanical stability, (ii) the difficulty in preparing thin, high-flux composite membranes, (iii) the requirement of a water-vapor-saturated feed to provide mobility for the olefin-selective carrier, and (iv) poor chemical stability due to carrier poisoning. Solid polymer electrolytes are a novel class of facilitated transport membranes for olefin/paraffin separation. These membranes solve the first three problems listed above. Solid polymer electrolyte membranes are based on rubbery, polyether-based polymers containing a dissolved olefin-complexing metal salt. Solid polymer electrolyte composite membranes made from poly(ethylene oxide) loaded with silver tetrafluoroborate showed an ethylene/ethane selectivity of up to 240 and an ethylene permeance of 8×10⁻⁶ cm³(STP)/cm² s cmHg with a dry feed gas mixture.     

Scalings of fluorine‐containing polyimides in cyclopentanone

Eight 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride‐4,4′‐diamino‐3,3′‐dimethylbiphenyl (6FDA‐OTOL) fractions and seven 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl] propane dianhydride‐4,4′‐diamino‐3,3′‐dimethylbiphenyl (BISADA‐OTOL) fractions in cyclopentanone at 30 °C were characterized by a combination of viscometry and static and dynamic laser light scattering (LLS). In static LLS, the angular dependence of the absolute scattered intensity led to the weight‐average molar mass (M_w), the z‐average root mean square radius of gyration, and the second virial coefficient. In dynamic LLS, the Laplace inversion of each measured intensity–intensity time correlation function resulted in a corresponding translational diffusion coefficient distribution [G(D)]. The scalings of 〈D〉 (cm²/s) = 8.13 × 10⁻⁵ M_w^−0.47 and [η] (dL/g) = 2.36 × 10⁻³ M_w^0.54 for 6FDA‐OTOL and 〈D〉 (cm²/s) = 3.02 × 10⁻⁴ M_w^−0.60 and [η] (dL/g) = 2.32 × 10⁻³ M_w^0.53 for BISADA‐OTOL were established. With these scalings, we successfully converted each G(D) value into a corresponding molar mass distribution. At 30 °C, cyclopentanone is a good solvent for BISADA‐OTOL but a poor solvent for 6FDA‐OTOL; this can be attributed to an ether linkage in BISADA‐OTOL. Therefore, BISADA‐OTOL has a more extended chain conformation than 6FDA‐OTOL in cyclopentanone. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2077–2080, 2000     

Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene

Developing hydrogen-bonded organic frameworks (HOFs) that combine functional sites, size control, and storage capability for targeting gas molecule capture is a novel and challenging venture. However, there is a lack of effective strategies to tune the hydrogen-bonded network to achieve high-performance HOFs. Here, a series of HOFs termed as HOF-ZSTU-M (M=1, 2, and 3) with different pore structures are obtained by introducing structure-directing agents (SDAs) into the hydrogen-bonding network of tetrakis (4-carboxyphenyl) porphyrin (TCPP). These HOFs have distinct space configurations with pore channels ranging from discrete to continuous multi-dimensional. Single-crystal X-ray diffraction (SCXRD) analysis reveals a rare diversity of hydrogen-bonding models dominated by SDAs. HOF-ZSTU-2 , which forms a strong layered hydrogen-bonding network with ammonium (NH₄⁺) through multiple carboxyl groups, has a suitable 1D “pearl-chain” channel for the selective capture of propylene (C₃H₆). At 298 K and 1 bar, the C₃H₆ storage density of HOF-ZSTU-2 reaches 0.6 kg L⁻¹, representing one of the best C₃H₆ storage materials, while offering a propylene/propane (C₃H₆/C₃H₈) selectivity of 12.2. Theoretical calculations and in situ SCXRD provide a detailed analysis of the binding strength of C₃H₆ at different locations in the pearl-chain channel. Dynamic breakthrough tests confirm that HOF-ZSTU-2 can effectively separate C₃H₆ from multi-mixtures.     

Functionalized Hydrocarbon Belts: Synthesis,Structure and Properties

Hydrocarbon belts have drawn great attention because of their unique structures and tantalizing properties. Although a few belts and heteroatom-doped analogs have been synthesized, belt molecules containing non-hexagonal rings remain rare. Herein we report the construction and application of unprecedented zigzag-type hydrocarbon belts which contain functionalized eight-membered rings. The synthesis features fourfold intramolecular acylation reactions of resorcin[4]arene-derived intermediates, which affords C₄-symmetric tetrabenzobelt[4]arene[4]cyclooctatrienones. Stereoselective ketone reduction with LiAlH₄ and nucleophilic addition with alkynyllithiums provide the corresponding tetrahydroxylated belts. The tetraol and its methyl ether are powerful and selective hosts to form 2 : 1 and 1 : 1 complexes with cesium ion, respectively, with binding constants up to (1.71±0.33)×10¹¹ M⁻² and (1.50±0.16)×10⁶ M⁻¹. In addition, enantiopure C₄-symmetric belts can emit CPL with |g_lum| being around 0.01.     

Fluorescence quenching in molecular recognition by hydrogen bonding

Steady-state fluorescence and single photon timing have been used to study the effect of the presence of hydrogen bonding on the intermolecular quenching of pyrene covalently linked to a guanine-like receptor I by an aliphatic amine (N,N-dimethylpropylamine) covalently linked to cytosine derivative II. By comparing the fluorescence quenching of I by II with that of 10methylpyrene (1-MP) by triethylamine (TEA), as a model system in which no hydrogen bonding can occur, one could possibly analyze the effect of the hydrogen bonding between receptor and substrate as a quenching as it leads to a higher local concentration of donor and acceptor. While the quenching of I by II was observed with an apparent rate constant k_q of (1.78 ± 0.10) × 10⁹ M⁻¹ s⁻¹ and (8.72 ± 0.42) × 10⁸ M⁻¹ s⁻¹ in toluene and acetonitrile, respectively, no quenching could be observed in methanol. Upon excitation of 1-MP, no quenching by II could be detected in the same concentration range as used in the quenching of I. Quenching of I and of 1-MP by TEA (⩾ 10⁻² M) in toluene leads to exciplex formation with maxima centred at 540 and 514 nm, respectively. The rate constants of exciplex formation and dissociation of I with TEA were analyzed using a global compartmental analysis. The following values were obtained for the rate constants: k₀₁ = (9.70 ± 0.01) × 10⁶ s⁻¹, k₂₁ = (1.12 ± 0.003) × 10⁹ M⁻¹ s⁻¹, k₀₂ = (5.24 ± 0.01) × 10⁷ s⁻¹ and k₁₂ = (7.74 ± 0.08) × 10⁶ s⁻¹. Quenching of I by TEA in the presence of III, a hydrogen-bonding system without an alkyl amine substituent, leads to exciplex formation centred at 538 nm. The rate constant values for the exciplex formation and dissociation of I with TEA in the presence of III were: k₀₁ = (9.32 ± 0.08) × 10⁶ s⁻¹, k₂₁ = (9.32 ± 0.003) × 10⁸ M⁻¹ s⁻¹, k₀₂ = (6.16 ± 0.03) × 10⁷ s⁻¹ and k₁₂ = (21.90 ± 0.3) × 10⁶ s⁻¹. The apparent rate constants k_q for this system was (7.26 ± 0.56) × 10⁶ M⁻¹ s⁻¹. The observed decrease in the rate of exciplex formation of I with TEA in the presence of III could suggest that the guanine-like moiety in I forms hydrogen bonds with the cytosine-like moiety and this could decrease the electron affinity of I. The rate constant of exciplex dissociation increased, indicating that the exciplex is less stable in the presence of III. Because of the single exponential decay of I in the presence and absence of II and of the agreement between steady-state and transient fluorescence measurements, the information available for quantitative analysis of the association between I and II is limited.     

Quenching of I(2P½) by R-OH compounds. Influence of the alkyl group on the quenching efficiency

The deactivation of I(²P_½) by R-OH compounds (R = H, C_nH_2n+1) was studied using time-resolved atomic absorption at 206.2 nm. The second-order quenching rate constants determined for H₂O, CH₃OH, C₂H₅OH, n-C₃H₇OH, i-C₃H₇OH, n-C₄H₉OH, i-C₄H₉OH, s-C₄H₉OH, t-C₄H₉OH, are respectively, 2.4 ± 0.3 × 10⁻¹², 5.5 ± 0.8 × 10⁻¹², 8 ± 1 × 10⁻¹², 10 ± 1 × 10⁻¹², 10 ± 1 × 10⁻¹², 11.1 ± 0.9 × 10⁻¹², 9.8 ± 0.9 × 10⁻¹², 7.1 ± 0.7 × 10⁻¹², and 4.1 ± 0.4× 10⁻¹² cm³ molec⁻¹ s⁻¹ at room temperature. It is believed that a quasi-resonant electronic to vibrational energy transfer mechanism accounts for most of the features of the quenching process. The influence of the alkyl group and its role in the total quenching rate is also discussed. © 1997 John Wiley & Sons, Inc.