Self-standing, conducting and capacitive biomimetic hybrid nanomembranes for selective molecular ion separation.

Hybrid free-standing biomimetic materials are developed by integrating the VDAC36 ß-barrel protein into robust and flexible three-layered polymer nanomembranes. The first and third layers are prepared by spin-coating a mixture of poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA). PVA nanofeatures are transformed into controlled nanoperforations by solvent-etching. The two nanoperforated PLA layers are separated by an electroactive layer, which is successfully electropolymerized by introducing a conducting sacrificial substrate under the first PLA nanosheet. Finally, the nanomaterial is consolidated by immobilizing the VDAC36 protein, active as an ion channel, into the nanoperforations of the upper layer. The integration of the protein causes a significant reduction of the material resistance, which decreases from 21.9 to 3.9 kΩ cm2. Electrochemical impedance spectroscopy studies using inorganic ions and molecular metabolites (i.e.l-lysine and ATP) not only reveal that the hybrid films behave as electrochemical supercapacitors but also indicate the most appropriate conditions to obtain selective responses against molecular ions as a function of their charge. The combination of polymers and proteins is promising for the development of new devices for engineering, biotechnological and biomedical applications.

Rapid removal of lead(II) ions from water using iron oxide-tea waste nanocomposite - a kinetic study.

Lead (Pb) ions are a major concern to the environment and human health as they are contemplated cumulative poisons. In this study, facile synthesis of magnetic iron oxide-tea waste nanocomposite is reported for adsorptive removal of lead ions from aqueous solutions and easy magnetic separation of the adsorbent afterwards. The samples were characterised by scanning electron microscopy, Fourier transform-infrared spectroscopy, X-ray diffraction, and Braunner-Emmet-Teller nitrogen adsorption study. Adsorptive removal of Pb(II) ions from aqueous solution was followed by ultraviolet-visible (UV-Vis) spectrophotometry. About 95% Pb(II) ion removal is achieved with the magnetic tea waste within 10 min. A coefficient of regression R2 ≃ 0.99 and adsorption density of 18.83 mg g-1 was found when Pb(II) ions were removed from aqueous solution using magnetic tea waste. The removal of Pb(II) ions follows the pseudo-second-order rate kinetics. External mass transfer principally regulates the rate-limiting phenomena of adsorption of Pb(II) ions on iron oxide-tea waste surface. The results strongly imply that magnetic tea waste has promising potential as an economic and excellent adsorbent for the removal of Pb(II) from water.

Salicylaldehyde derivative of nano-chitosan as an efficient adsorbent for lead(II), copper(II), and cadmium(II) ions.

In this study, a biodegradable natural polymer chitosan was modified with salicylaldehyde to prepare salicylaldehyde functionalized chitosan nanoparticles (N-Ch-Sal). The N-Ch-Sal was characterized by atomic force microscopy (AFM), scanning electron microscopy-energy-dispersive X-ray (SEM-EDX), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The salicylaldehyde functionalized chitosan nanoparticles (N-Ch-Sal) (~80 nm) were then used for the adsorption of three heavy metals viz., Cu(II), Cd(II) and Pb(II) ions. The above-mentioned techniques were also employed for evaluation of changes in N-Ch-Sal after metal adsorption. The parameters affecting the adsorption of metal ions including pH, contact time, amount of adsorbent, initial metal ion concentration and the effect of interfering ions, were studied thoroughly and optimized. The concentration of metal ions remaining in the aqueous system after adsorption experiments was analyzed by ICP-MS. At optimal conditions, sorption capacity of Pb(II) ion was found to be highest i.e., 123.67 followed by Cu(II) (84.60) and Cd(II) (63.71 mg/g). The adsorption process followed the pseudo-second-order kinetic model and fitted well with the Langmuir adsorption isotherm. The adsorption method was applied to a real tap water sample for the quantification and removal of Pb(II) ions. The concentration of Pb(II) ions in the tested sample was 4.88 ppb.

Adsorptive removal of lead (Pb), copper (Cu), nickel (Ni) and mercury (Hg) ions from water using chitosan silica gel composite.

Silica gel chitosan composite was prepared to perform adsorptive experiment of different heavy metal ion solutions. The characterization of chitosan + silica gel (Ch + Sg) composite was done by FTIR and SEM-EDS to understand the presence of active sites and to have an insight on the surface morphology. The adsorption study of heavy metal ions by Ch + Sg composite gives maximum removal percent for Cu, Pb and Ni which were obtained at pH 5 and for Hg at pH 6.The trend of removal by Ch + Sg signifies that maximum removal percent was attained at 120 min. The surface of Ch + Sg is heterogeneous for the adsorption of Hg, Ni and Cu and homogeneous for Pb adsorption. The values obtained for Pb signify that its adsorption best fitted to pseudo first order with the R2 value of 0.986, whereas pseudo second order best fitted to the experimental data of Cu, Ni and Hg as R2 values which are 0.983, 0.819 and 0.957 respectively. The values of change in entropy (⊿S) obtained for Pb, Cu, Ni and Hg are - 69.33, - 118, - 63.33 and - 98.52 J/mol K respectively. Negative values of change in enthalpy, ⊿H in (kJ/mol) are in the range of - 18.2 to - 37.66 which indicates both physical and chemical adsorption involves in the process of adsorption.

Optimization of background electrolyte composition for simultaneous contactless conductivity and fluorescence detection in capillary electrophoresis of biological samples.

In this article, optimization of BGE for simultaneous separation of inorganic ions, organic acids, and glutathione using dual C4 D-LIF detection in capillary electrophoresis is presented. The optimized BGE consisted of 30 mM 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid, 15 mM 2-amino-2-hydroxymethyl-propane-1,3-diol, and 2 mM 18-crown-6 at pH 7.2 and allowed simultaneous separation of ten inorganic anions and cations, three organic acids and glutathione in 20 min. The samples were injected hydrodynamically from both capillary ends using the double-opposite end injection principle. Sensitive detection of anions, cations, and organic acids with micromolar LODs using C4 D and simultaneously glutathione with nanomolar LODs using LIF was achieved in a single run. The developed BGE may be useful in analyses of biological samples containing analytes with differing concentrations of several orders of magnitude that is not possible with single detection mode.

Synthesis of a Novel Pyrazine⁻Pyridone Biheteroaryl-Based Fluorescence Sensor and Detection of Endogenous Labile Zinc Ions in Lung Cancer Cells.

A small extent of endogenous labile zinc is involved in many vital physiological roles in living systems. However, its detailed functions have not been fully elucidated. In this study, we developed a novel biheteroaryl-based low molecular weight fluorescent sensor, 3-(phenylsulfonyl)-pyrazine-pyridone (5b), and applied it for the detection of endogenous labile zinc ions from lung cancer cells during apoptosis. The electron-withdrawing property of the sulfonyl group between the phenyl ring as an electron donor and the pyridone ring as a fluorophore inhibited the intramolecular charge transfer state, and the background fluorescence of the sensor was decreased in aqueous media. From the structure-fluorescence relationship analysis of the substituent effects with/without Zn2+, compound 5b acting as a sensor possessed favorable properties, including a longer emission wavelength, a large Stokes shift (over 100 nm), a large fluorescence enhancement in response to Zn2+ under physical conditions, and good cell membrane permeability in living cells. Fluorescence imaging studies of human lung adenocarcinoma cells (A549) undergoing apoptosis revealed that compound 5b could detect endogenous labile zinc ions. These experiments suggested that the low molecular weight compound 5b is a potential fluorescence sensor for Zn2+ toward understanding its functions in living systems.

Ion-imprinted electrospun nanofibers of chitosan/1-butyl-3-methylimidazolium tetrafluoroborate for the dynamic expulsion of thorium (IV) ions from mimicked effluents.

The present study explores the innocuous, biocompatible, and extremely competent molecularly imprinted chitosan/RTIL electrospun nanofibers having average diameter of 30 nm for the expulsion of thorium (IV) ions from the mimicked effluent waste. The extended Flory-Huggins theory and three-dimensional molecular modeling have been effectively premeditated via Materials Studio software for enumerating the inter-miscibility and compatibility (Chi parameter (χ) = 1.019, mixing energy (Emix) = 0.603 kcal/mol) of the chitosan/RTIL (1-butyl-3-methylimidazolium tetrafluoroborate). The maximum adsorption efficiency is found to be 90% at a neutral pH of 7, and a temperature of 298 K within 120 min. The adsorption process was extensively studied by two-parameter adsorption isotherms like Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) and three-parameter models like Redlich-Paterson and Sips isotherm. Pseudo-second-order kinetics model (R2 = 0.982) and Langmuir isotherm (R2 = 0.994) bestowed the best fitting on chitosan/RTIL nanofibers for the adsorption of Th (IV) ions. The thermodynamic study reveals the spontaneity and exothermic nature of the reaction. The experimental analysis conjoint with isotherm and kinetic models, and simulation study establish the applicability of chitosan/RTIL nanofibers for the expulsion of Th (IV) and other toxic metal ions from the effluents. Graphical abstract Ion-imprinted electrospun nanofiber for expulsion of thorium (IV) ion.

Preparation of chitosan composite film reinforced with cellulose isolated from oil palm empty fruit bunch and application in cadmium ions removal from aqueous solutions.

Chitosan composite films reinforced with cellulose isolated from oil palm empty fruit bunch had been successfully prepared and applied in cadmium ions removal from aqueous solutions. Cellulose particles were isolated by hydrolyzing oil palm empty fruit bunch with hydrochloric acid. Several compositions were prepared by varying the chitosan/cellulose ratio of composites. The structure and the properties of composites were investigated by Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD) and mechanical performance measurement. FTIR spectra confirmed that cellulose particles were incorporated into the chitosan matrix. Tensile test results showed that the contents of chitosan and cellulose influenced the mechanical properties of composites. The composite with 10wt% cellulose particles had the highest tensile strength. The X-ray diffraction patterns indicate the crystallinity index of composites decreased with addition of cellulose particles. This low crystallinity is important for metal ions removal in water treatment. Application of composite for cadmium removal from aqueous solutions was done by various solution pH, contact time and concentrations. The adsorption isotherm of Cd ions onto the composite was well fitted to Langmuir equation. Furthermore, the adsorbent still exhibited good adsorption performance after regeneration.

Photoluminescence light-up detection of zinc ion and imaging in living cells based on the aggregation induced emission enhancement of glutathione-capped copper nanoclusters.

In this work, we prepared glutathione (GSH)-capped copper nanoclusters (Cu NCs) with red emission by simply adjusting the pH of GSH/Cu2+ mixture at room temperature. A photoluminescence light-up method for detecting Zn2+ was then developed based on the aggregation induced emission enhancement of GSH-capped Cu NCs. Zn2+ could trigger the aggregation of Cu NCs, inducing the enhancement of luminescence and the increase of absolute quantum yield from 1.3% to 6.2%. GSH-capped Cu NCs and the formed aggregates were characterized, and the possible mechanism was also discussed. The prepared GSH-capped Cu NCs exhibited a fast response towards Zn2+ and a wider detection range from 4.68 to 2240µM. The detection limit (1.17µM) is much lower than that of the World Health Organization permitted in drinking water. Furthermore, taking advantages of the low cytotoxicity, large Stokes shift, red emission and light-up detection mode, we explored the use of the prepared GSH-capped Cu NCs in the imaging of Zn2+ in living cells. The developed luminescence light-up nanoprobe may hold the potentials for Zn2+-related drinking water safety and biological applications.

Phosphorylation of chitosan/HEMA interpenetrating polymer network prepared by γ-radiation for metal ions removal from aqueous solutions.

Interpenetrating polymer network (IPN) hydrogels, based on chitosan (CS) and 2-hydroxyethyl methacrylate (HEMA), have been prepared by γ-radiation followed by chemical modification via phosphorylation reaction and used for adsorption of Ca(II), Cu(II) and Zn(II) ions from their aqueous solutions. The gel content (%) increases with increasing the HEMA concentration. The maximum swelling (%) observed at the ratio (70/30) (CS/HEMA). CS/pHEMA IPN showed a higher thermal stability than CS. The phosphorylated hydrogel, Phos-(CS/pHEMA), characterized by XRD, EDS, SEM, DSC and TGA techniques. FT-IR spectra before and after adsorption of metal ions have been studied. Factors affecting the maximum adsorption capacity were also investigated. The maximum adsorption capacity using 0.01g Phos-(CS/pHEMA) was 66.3, 57.6 and 48.7 (mg/g) for Cu(II), Zn(II) and Ca(II) ions, respectively. The adsorption isotherms were simulated by Langmuir and Freundlich models and the adsorption kinetics were simulated by the pseudo-first-order and pseudo-second-order kinetics. The adsorption follows Langmuir models and pseudo-second order. The IPN hydrogels showed effective adsorption of the three metal ions from aqueous solution.

Removal of metal ions from aqueous solutions using carboxymethyl cellulose/sodium styrene sulfonate gels prepared by radiation grafting.

Sodium Carboxymethyl Cellulose (CMCNa)/Sodium Styrene Sulfonate (SSS) hydrogels with grafted and crosslinked polymeric networks were prepared by γ-radiation at atmosphere condition. The obtained hydrogels were characterized by gel fraction, swelling ratio, TGA and FTIR spectroscopy. The results showed the ratio of CMC and SSS 1:0 gave the highest gel fraction, compared with other ratios. The swelling capacity increased by increasing SSS content due to the presence of SO3Na, OH groups in gel structure. The FTIR spectrum of CMC/SSS gel showed the new absorption peaks at 1034 and 1012cm-1 corresponds to SO3Na group. The metal ion adsorption capacity of CMC/SSS gel was investigated. The grafted gel effectively removed metal ions, especially Cr and Pb. The effects of hydrogel composition, contact time, and initial concentration on the adsorption capacity of the grafted hydrogels were studied. The adsorption kinetics and equilibrium isotherms were investigated using pseudo-second-order model and Langmuir model.

Solid phase extraction, separation and preconcentration of rare elements thorium(IV), uranium(VI), zirconium(IV), cerium(IV) and chromium(III) amid several other foreign ions with eriochrome black T anchored to 3-D networking silica gel.

The present work reports the systematic studies on extraction, separation and preconcentration of Th(IV), U(VI), Zr(IV), Ce(IV) and Cr(III) amid several other foreign ions using EBT anchored {SiO2}n3-D microarray. The effect of various sorption parameters, such as pH, concentration, temperature, sample volume, flow-rate and co-existing foreign ions were investigated. Quantitative sorption was ensured at solution pH: 6.0-6.5 for Th(IV), Ce(IV), Cr(III) and pH: 2.75-3.0 for Zr(IV), U(VI) couple. Analysis on extracted species and extraction sites reveals that [Th4(µ(2)-OH)8(H2O)4](8+), [Ce6(µ(2)-OH)12(H2O)5](12+), [Cr3(µ(2)-OH)4(H2O)](5+), [(UO2)3(µ(2)-OH)5(H2O)3](+) and [Zr4(µ(2)-OH)8(H2O)0.5](8+) for the respective metal ions gets extracted at HOMO of the extractor. HOMO-{metal ion species} was found to be 1:1 complexation. Sorption was endothermic, entropy-gaining, instantaneous and spontaneous in nature. A density functional theory (DFT) calculation has been performed to analyze the 3-D structure and electronic distribution of the synthesized extractor.

Rapid and efficient removal of fluoride ions from aqueous solution using a polypyrrole coated hydrous tin oxide nanocomposite.

Polypyrrole/hydrous tin oxide nanocomposites (PPy/HSnO NC 1, 2, 3, 4 and 5) were synthesized through encapsulating HSnO by the PPy via an in situ polymerization for fluoride removal. The optimized adsorbent i.e. PPy/HSnO NC 3 was characterized using FE-SEM, HR-TEM, ATR-FTIR, XRD, BET, TGA and zeta sizer. Microscopic images revealed the encapsulation of HSnO by precipitating PPy during polymerization. The FTIR and XRD studies confirmed the presence of both constituents. The BET surface area and pHpzc of the adsorbent were estimated to be 65.758m(2)/g and 7.6, respectively. The fluoride adsorption followed pseudo-second-order model and was commendably rapid. The monolayer adsorption capacity was found to be 26.16-28.99mg/g at pH 6.5±0.1. The thermodynamic parameters indicated the sorption of F(-) was spontaneous, endothermic and that physisorption occurred. The calculated activation energy (Ea∼20.05kJ/mol) provided further evidence of a physisorption mechanism. Moreover, the adsorbent performed very well over a considerably wide pH range of 3.5-8.5 and in the presence of other co-existing ions. The regeneration of the F(-) laden PPy/HSnO NC 3 showed a high desorption efficiency of 95.81% up to 3 cycles. Ground water tested results also demonstrate the potential utility of the PPy/HSnO NC as an effective adsorbent.

Ion Mobility Separation of Peptide Isotopomers.

Differential or field asymmetric waveform ion mobility spectrometry (FAIMS) operating at high electric fields fully resolves isotopic isomers for a peptide with labeled residues. The naturally present isotopes, alone and together with targeted labels, also cause spectral shifts that approximately add for multiple heavy atoms. Separation qualitatively depends on the gas composition. These findings may enable novel strategies in proteomic and metabolomic analyses using stable isotope labeling.

Gas-Phase Chemical Separation of Phosphatidylcholine and Phosphatidylethanolamine Cations via Charge Inversion Ion/Ion Chemistry.

The [M + H](+) cations formed upon electrospray ionization of the glycerophospholipids phosphatidylcholine (PC) and phosphatidylethanolamine (PE) show distinct reactivities upon gas-phase reactions with doubly deprotonated 1,4-phenylenedipropionic acid (PDPA). PC cations undergo charge inversion via adduct formation with subsequent methyl cation and proton transfer to the acid to yield [PC - CH3](-) anions. These demethylated PC anions fragment upon ion trap collision-induced dissociation (CID) to yield products that reveal fatty acid chain lengths and degrees of unsaturation. PE cations, on the other hand, undergo charge inversion via double proton transfer to the two carboxylate moieties in doubly deprotonated PDPA to yield [PE - H](-) anions. These anions also fragment upon ion trap CID to yield product ions indicative of chain lengths and degrees of unsaturation in the fatty acyl moieties. Advantage is taken of this distinct reactivity to separate isomeric and isobaric PC and PE cations present in mass spectra of lipid mixtures. A cation precursor ion population containing a mixture of PE and PC cations is mass-selected and subjected to ion/ion charge inversion reactions that result in separation of PC and PE anions into different mass-to-charge ratios. Mass selection and subsequent ion trap CID of the lipid anions allows for the characterization of the isomeric lipids within each subclass. The charge inversion approach described here is demonstrated to provide increased signal-to-noise ratios for detection of PCs and PEs relative to the standard negative ionization approach as well as improved mixture analysis performance.

Cryogenic molecular separation system for radioactive (11)C ion acceleration.

A (11)C molecular production/separation system (CMPS) has been developed as part of an isotope separation on line system for simultaneous positron emission tomography imaging and heavy-ion cancer therapy using radioactive (11)C ion beams. In the ISOL system, (11)CH4 molecules will be produced by proton irradiation and separated from residual air impurities and impurities produced during the irradiation. The CMPS includes two cryogenic traps to separate specific molecules selectively from impurities by using vapor pressure differences among the molecular species. To investigate the fundamental performance of the CMPS, we performed separation experiments with non-radioactive (12)CH4 gases, which can simulate the chemical characteristics of (11)CH4 gases. We investigated the separation of CH4 molecules from impurities, which will be present as residual gases and are expected to be difficult to separate because the vapor pressure of air molecules is close to that of CH4. We determined the collection/separation efficiencies of the CMPS for various amounts of air impurities and found desirable operating conditions for the CMPS to be used as a molecular separation device in our ISOL system.

Drastic nickel ion removal from aqueous solution by curcumin-capped Ag nanoparticles.

A completely green synthesis protocol has been adopted to obtain silver nanoaggregates capped by the natural compound (1E, 6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-diene), also known as curcumin. The synthesis has been monitored by infrared, Raman, visible and fluorescence spectroscopies. Characterization confirms that curcumin reduces and caps the nanoparticles, and such a procedure allows its solubility in water and drastically increases curcumin stability. Silver nanoparticles (AgNPs)/curcumin complex has been dispersed in a water solution containing a known nickel ion concentration. After three days, a grey precipitate is observed and nickel concentration in the solution is reduced by about 70%.

Application of poly 1,8-diaminonaphthalene/multiwalled carbon nanotubes-COOH hybrid material as an efficient sorbent for trace determination of cadmium and lead ions in water samples.

Poly 1,8-diaminonaphthalene/multiwalled carbon nanotubes-COOH hybrid material as an effective sorbents in solid phase extraction has been developed for the separation and preconcentration of Cd(II) and Pb(II) at trace levels in environmental water samples. The results indicate that the novel nanocomposite show a high affinity for these heavy metals due to the presence of several good extractive sites, which are introduced to the synthesized nanocomposite The maximum adsorption capacity of the synthesized sorbent for cadmium and lead ions was found to be 101.2 and 175.2 mg g(-1) , respectively. The detection limits of this method were 0.09 and 0.7 ng ml(-1) for Cd(II) and Pb(II), respectively.

Differential ion mobility separations in up to 100% helium using microchips.

The performance of differential IMS (FAIMS) analyzers is much enhanced by gases comprising He, especially He/N2 mixtures. However, electrical breakdown has limited the He fraction to ~50%-75%, depending on the field strength. By the Paschen law, the threshold field for breakdown increases at shorter distances. This allows FAIMS using chips with microscopic channels to utilize much stronger field intensities (E) than "full-size" analyzers with wider gaps. Here we show that those chips can employ higher He fractions up to 100%. Use of He-rich gases improves the resolution and resolution/sensitivity balance substantially, although less than for full-size analyzers. The optimum He fraction is ~80%, in line with first-principles theory. Hence, one can now measure the dependences of ion mobility on E in pure He, where ion-molecule cross section calculations are much more tractable than in other gases that form deeper and more complex interaction potentials. This capability may facilitate quantitative modeling of high-field ion mobility behavior and, thus, FAIMS separation properties, which would enable a priori extraction of structural information about the ions.

Polyionic and cysteine-containing fusion peptides as versatile protein tags.

In response to advances in proteomics research and the use of proteins in medical and biotechnological applications, recombinant protein production and the design of specific protein characteristics and functions has become a widely used technology. In this context, protein fusion tags have been developed as indispensable tools for protein expression, purification, and the design of functionalized surfaces or artificially bifunctional proteins. Here we summarize how positively or negatively charged polyionic fusion peptides with or without an additional cysteine can be used as protein tags for protein expression and purification, for matrix-assisted refolding of aggregated protein, and for coupling of proteins either to technologically relevant matrices or to other proteins. In this context we used cysteine-containing polyionic fusion peptides for the design of immunotoxins. In general, polyionic fusion tags can be considered as a multifunctional module in protein technology.