Liquid-liquid Diffusion Research Articles

Determination of the diffusion coefficient in sodium chloride solution at different concentrations

Phenomena of diffusion are present in several industrial phenomena and therefore need to be properly studied and understood. The study of liquid-liquid diffusion allows to perfect and model several industrial systems. The development of instruments capable of doing this study allows to create methodologies for the development of students of the most diverse engineering. This work employed the study of the diffusion phenomena in a diffusion cell constructed by the authors themselves based on materials found in laboratories, trying to calculate the diffusion coefficient of a solution of sodium chloride in water through the variation of conductivity. The diffusion coefficients obtained presented values in the same order of magnitude in relation to the experimental values reported by other authors and with low experimental error.

Crystal structure and magnetic study of the complex salt [RuCp(PTA)2-μ-CN-1κC:2κN-RuCp(PTA)2][Re(NO)Br4(EtOH)0.5(MeOH)0.5

A new RuII-ReII complex salt, μ-cyanido-κ2 C:N-bis-[(η5-cyclo-penta-dien-yl)bis(3,5,7-tri-aza-phosphaadamantane-κP)ruthenium(II)] tetra-bromido-(ethanol/methanol-κO)nitrosylrhenate(II), [Ru(CN)(C5H5)2(C6H12N3P)4][ReBr4(NO)(CH4O)0.5(C2H6O)0.5] or [RuCp(PTA)2-μ-CN-1κC:2κ2 N-RuCp(PTA)2][Re(NO)Br4(EtOH)0.5(MeOH)0.5] (PTA = 3,5,7-tri-aza-phosphaadaman-tane) was obtained and characterized by single-crystal X-ray diffraction, elemental analysis and infrared spectroscopy. The title salt was obtained by liquid-liquid diffusion of methanol/DMSO solutions of (NBu4)[Re(NO)Br4(EtOH)] and [(PTA)2CpRu-μ-CN-1κC:2κ2 N-RuCp(PTA)2](CF3SO3). The RuII and ReII independent moieties correspond to a binuclear and mononuclear complex ion, respectively. A deep geometrical parameter analysis was performed, and no significant differences were found with earlier reports containing similar mol-ecules. The magnetic properties were investigated in the temperature range 2.0-300 K, and the complex behaves as a quasi-magnetically isolated spin doublet with weak anti-ferromagnetic inter-actions.

A Zeolitic-Imidazole Framework-Derived Trifunctional Electrocatalyst for Hydrazine Fuel Cells.

Hydrazine fuel cells are promising sustainable power sources. However, the high price and limited reserves of noble metal catalysts that promote the sluggish cathodic and anodic electrochemical reactions hinder their practical applications. Reflecting the enhanced diffusion and improved kinetics of nanostructured non-noble metal electrocatalysts, we report an efficient zeolitic-imidazole framework-derived trifunctional electrocatalyst for hydrazine oxidation, oxygen, and hydrogen peroxide reduction. Experimental results and theoretical calculations corroborate that the nanocarbon architecture with abundant Co-N species enhances the electronic interaction and optimizes the energy barriers of anodic hydrazine oxidation and cathodic oxygen reduction. The resulting assembled hydrazine-oxygen fuel cell yields a cell voltage and power density of 0.74 V and 20.5 mW cm-2, respectively. Moreover, benefiting from the liquid-liquid diffusion, the hydrazine-hydrogen peroxide cell shows a boosted cell voltage and power density, corresponding to 1.68 V and 41.0 mW cm-2. This work offers a highly active non-noble metal multifunctional electrocatalyst with a pioneering diffusion philosophy in the liquid electrochemical cells.

Crystal Structure and Hirshfeld Surface Analysis of 1,4-Pentadien-3-one, (1E,4E)‑1,5-diphenyl-2-(2,4-dinitrophenyl)hydrazone

The compound 1,4-pentadien-3-one,(1E,4E)-1,5-diphenyl-2-(2,4-dinitrophenyl)hydrazone presents the molecular formula C23H18N4O4 and was prepared in an undergraduate laboratory. The hydrazone was synthesized from the condensation between dibenzalacetone and 2,4-dinitrophenylhydrazine (DNPH) and crystallized employing water/acetone liquid-liquid diffusion. The structure presents three aromatic rings connected by an unsaturated Y-shaped system. Dinitro substituted and one of the other aromatic rings are 15o out of a coplanarity, while the other phenyl group is almost orthogonal to the first (89o). The only observed classical hydrogen bonding is an intramolecular N-H···O. The supramolecular structure was analyzed employing the Hirshfeld surface and that is organized through C-H···O hydrogen bond and C-H···π, polar-π, and π-stacking. An interaction involving NO2···NO2 was also observed.

Effect of Processing Technique Factors on Structure and Photophysical Properties of Perovskite Absorption Layer by Using Two-Step Spin-Coating Method

The investigation of crystal growth is crucial for us to improve the film quality and photophysical properties of CH3NH3PbI3 (MAPbI3). In the two-step spin-coating process, the crystal structure could be modulated by controlling the growth conditions of PbI2 and CH3NH3I (MAI) layers. In this paper, the PbI2 layer was treated with annealing under different times. A liquid–liquid diffusion (LLD) mechanism is proposed to modify the deposition of MAI precursor solution and enhance the flatness of organic–inorganic hybrid perovskite film. Furthermore, the perovskite films are prepared using different concentrations of MAI. The evolution process of perovskite structure is observed by modulating the concentration of MAI. The spin-coating of moderate MAI tends to form high quality MAPbI3 films with enhanced absorption and carrier extraction capabilities. The high concentration of MAI would cause the perovskite phase transition, which provides a novel perspective to modulate the structure of organic–inorganic hybrid perovskite in the two-step spin-coating process, although it deteriorates the device performance.

Dielectric Relaxation and Beyond Limiting Behavior of Alternating-Current Conductivity in a Supermolecular Ferroelectric.

A cyclen-based hybrid supermolecule crystal, [(FeCl2 )(cyclen)]Cl (1), where cyclen=1,4,7,10-tetraazacyclododecane, was prepared using a liquid-liquid diffusion approach. The variable crystal structures exhibit that compound 1 belongs to an orthorhombic crystal system, Pna21 space group (point group C2V ) in the temperature range of 150-400 K. This hybrid supermolecule shows a dielectric relaxation behavior around room temperature, and the ferroelectric nature of 1 has been directly verified by hysteresis measurements. In addition, the AC (alternating current) conductivity study reveals that the 1 displays a beyond limiting behavior. These interesting findings are for the first time reported in the field of supermolecular ferroelectrics. This study may open a new way to construct supermolecular ferroelectrics and give insights into their conductor behavior.

Protein Crystallization.

Protein crystallization was discovered by chance nearly 200 years ago and was developed in the late nineteenth century as a powerful purification tool, and a demonstration of chemical purity. The crystallization of proteins, nucleic acids, and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule, but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by manipulation of various parameters that include temperature, ionic strength, and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors, or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch, and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years due to the advent of practical, easy-to-use screening kits, and the application of laboratory robotics.

Structural Invariance of a ZnII Coordination Polymer with 5-Aminoisophthalic Acid under Different Synthetic Conditions

A same coordination polymer [Zn(aip)(DMSO)] (aip: 5-aminoisophthalate and DMSO: dimethylsulfoxide) was synthesized using the same reactants (ZnSO4, aip and H2O/DMSO) but in different conditions, in which the stoichiometry (1:1-4:1 metal:ligand ratio), temperature (70 and 100 °C) and synthetic method (liquid-liquid diffusion, solvothermal and conventional with stirring) varied. A liquid assisted mechanochemical approach using ZnO as ZnII source instead ZnSO4, but keeping DMSO as milling liquid, also resulted in the same compound. This new coordination polymer was investigated using single-crystal X-ray diffraction technique, revealing a two-dimensional honeycomb-type network formation. The crystal structure was compared with either similar or isostructural compounds reported in the literature. Our studies show that the synthetic method and other synthetic variables do not affect the formation of [Zn(aip)(DMSO)] coordination polymers and probe the high stability (thermodynamic and kinetic) and structural invariance of this structure.

Improved Quality of Liquefied Petroleum Gas via Non-Stirred Blending

Liquefied Petroleum Gas (LPG) which contains more than 0.1% mole of butadiene is classified as a carcinogen and mutagen and regulatory have set the limit of butadiene to be below 0.5 % mole in LPG mixture. LPG suppliers in Malaysia are facing problem since butadiene level from one port exceeded 0.5 % mole. By blending of LPG from other ports might produce LPG products which satisfy the regulatory limit. The study focused on homogeneous blending time in a 17.28 m3 tank without artificial mechanical equipment through simulation modelling by Fluent 6.2.16 with two sources of LPG which were Ports A and B. The results showed that as the volume of LPG with butadiene increased, the butadiene level in mixed LPG also increased. The mass fraction between Ports A and B was below than 93% and 7% produced mixed LPG product within the regulatory limit. The blending time is approximately 3.98 hours to achieve homogeneous product mixture with a constant flow rate of 0.52 kg/s. Numerical modelling reveals that the effect of liquid-liquid diffusion by Wilke-Chang correlation does not significantly affect the blending time for homogeneous mixture. In fact the required blending time is shorter compared to blending time estimated by numerical modeling.

Lock-arm supramolecular ordering: a molecular construction set for cocrystallizing organic charge transfer complexes.

Organic charge transfer cocrystals are inexpensive, modular, and solution-processable materials that are able, in some instances, to exhibit properties such as optical nonlinearity, (semi)conductivity, ferroelectricity, and magnetism. Although the properties of these cocrystals have been investigated for decades, the principal challenge that researchers face currently is to devise an efficient approach which allows for the growth of high-quality crystalline materials, in anticipation of a host of different technological applications. The research reported here introduces an innovative design, termed LASO-lock-arm supramolecular ordering-in the form of a modular approach for the development of responsive organic cocrystals. The strategy relies on the use of aromatic electronic donor and acceptor building blocks, carrying complementary rigid and flexible arms, capable of forming hydrogen bonds to amplify the cocrystallization processes. The cooperativity of charge transfer and hydrogen-bonding interactions between the building blocks leads to binary cocrystals that have alternating donors and acceptors extending in one and two dimensions sustained by an intricate network of hydrogen bonds. A variety of air-stable, mechanically robust, centimeter-long, organic charge transfer cocrystals have been grown by liquid-liquid diffusion under ambient conditions inside 72 h. These cocrystals are of considerable interest because of their remarkable size and stability and the promise they hold when it comes to fabricating the next generation of innovative electronic and photonic devices.

Introduction to protein crystallization.

Protein crystallization was discovered by chance about 150 years ago and was developed in the late 19th century as a powerful purification tool and as a demonstration of chemical purity. The crystallization of proteins, nucleic acids and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by the manipulation of various parameters that include temperature, ionic strength and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years owing to the advent of practical, easy-to-use screening kits and the application of laboratory robotics. A brief review will be given here of the most popular methods, some guiding principles and an overview of current technologies.

Liquid–liquid diffusion crystallization improves the X-ray diffraction of EndoS, an endo-β-N-acetylglucosaminidase fromStreptococcus pyogeneswith activity on human IgG

Endoglycosidase S (EndoS) is an enzyme secreted by Streptococcus pyogenes that specifically hydrolyzes the β-1,4-di-N-acetylchitobiose core glycan on immunoglobulin G (IgG) antibodies. One of the most common human pathogens and the cause of group A streptococcal infections, S. pyogenes secretes EndoS in order to evade the host immune system by rendering IgG effector mechanisms dysfunctional. On account of its specificity for IgG, EndoS has also been used extensively for chemoenzymatic synthesis of homogeneous IgG glycoprotein preparations and is being developed as a novel therapeutic for a wide range of autoimmune diseases. The structural basis of its enzymatic activity and substrate specificity, however, remains unknown. Here, the purification and crystallization of EndoS are reported. Using traditional hanging-drop and sitting-drop vapor-diffusion crystallization, crystals of EndoS were grown that diffracted to a maximum of 3.5 Å resolution but suffered from severe anisotropy, the data from which could only be reasonably processed to 7.5 Å resolution. When EndoS was crystallized by liquid-liquid diffusion, it was possible to grow crystals with a different space group to those obtained by vapor diffusion. Crystals of wild-type endoglycosidase and glycosynthase constructs of EndoS grown by liquid-liquid diffusion diffracted to 2.6 and 1.9 Å resolution, respectively, with a greatly diminished anisotropy. Despite extensive efforts, the failure to reproduce these liquid-liquid diffusion-grown crystals by vapor diffusion suggests that these crystallization methods each sample a distinct crystallization space.

Bright-yellow to orange-red thermochromic luminescence of an AgI6–ZnII2 heterometallic aggregate

A novel octanuclear Ag(I)(6)-Zn(II)(2) heterometallic aggregate, (NH(4))(2){[Zn(2)(phen)(2)(H(2)O)(4)][Ag(6)(mna)(6)]}·2H(2)O·2CH(3)CH(2)OH (1, H(2)mna = 2-mercaptonicotinic acid, phen = 1,10-phenanthroline), was stepwisely obtained based on a hexanuclear silver(i) metalloligand using a liquid-liquid diffusion method. It is an exceedingly rare example that exhibits interesting temperature dependent photoluminescence behaviors, including gradual changes in energy and intensity upon cooling.

Intercluster Compound between a Tetrakis{triphenylphosphinegold(I)}oxonium Cation and a Keggin Polyoxometalate (POM): Formation during the Course of Carboxylate Elimination of a Monomeric Triphenylphosphinegold(I) Carboxylate in the Presence of POMs

The preparation and structural characterization of a novel intercluster compound, [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PW(12)O(40)](2)·4EtOH (1), constructed between a tetrakis{triphenylphosphinegold(I)}oxonium cation and a saturated α-Keggin polyoxometalate (POM) are described. The tetragold(I) cluster oxonium cation was formed during the course of carboxylate elimination of a monomeric phosphinegold(I) carboxylate complex, i.e., [Au((R,S)-pyrrld)(PPh(3))] [(R,S)-Hpyrrld = (R,S)-2-pyrrolidone-5-carboxylic acid], in the presence of the free acid form of a Keggin POM, H(3)[α-PW(12)O(40)]·7H(2)O. The liquid-liquid diffusion between the upper water/EtOH phase containing the Keggin POM and the lower CH(2)Cl(2) phase containing the monomeric gold(I) complex gave a pure crystalline sample of 1 in good yield (42.1%, 0.242 g scale). Complex 1 was formed by ionic interaction between the tetragold(I) cluster cation and the Keggin POM anion. As a matter of fact, the POM anion in 1 can be exchanged with the BF(4)(-) anion using an anion-exchange resin (Amberlyst A-27) in BF(4)(-) form. By using other Keggin POMs, such as H(4)[α-SiW(12)O(40)]·10H(2)O and H(3)[α-PMo(12)O(40)]·14H(2)O, the same tetragold(I) cluster cation was also formed, i.e., in the forms of [{Au(PPh(3))}(4)(μ(4)-O)](2)[α-SiW(12)O(40)]·2H(2)O (2) and [{Au(PPh(3))}(4)(μ(4)-O)](3)[α-PMo(12)O(40)](2)·3EtOH (3). Compounds 1-3, as dimethyl sulfoxide-soluble, EtOH- and Et(2)O-insoluble dark-yellowish white solids, were characterized by complete elemental analysis, thermogravimetric and differential thermal analyses, Fourier transform IR, X-ray crystallography, and solid-state (CPMAS (31)P and (29)Si) and solution ((31)P{(1)H} and (1)H) NMR spectroscopy. The molecular structures of 1 and 2 were successfully determined. The tetragold(I) cluster cation was composed of four PPh(3)Au(I) units bridged by a central μ(4)-oxygen atom in the geometry of a trigonal pyramid or distorted tetrahedron.

Observation of Diffusion Process of a Water Droplet Immersed in Protein Solution in Microgravity

Pure liquid-liquid diffusion driven by concentration gradients is hard to study in a normal gravity environment since convection and sedimentation also contribute to the mass transfer process. We employ a Mach–Zehnder interferometer to monitor the mass transfer process of a water droplet in EAFP protein solution under micro-gravity condition provided by the Satellite Shi Jian No 8. A series of the evolution charts of mass distribution during the diffusion process of the liquid droplet are presented and the relevant diffusion coefficient is determined.

Construction of 3D Layer-Pillared Homoligand Coordination Polymers from a 2D Layered Precursor

Herein, we present a new method for preparing homoligand 3D coordination polymers. First, a layered metal-organic framework Zn3(BDC)3(H2O)2 x 4DMF 1 (BDC is terephthalate, DMF is N,N-dimethylformamide) was fabricated from a H2BDC by liquid-liquid diffusion. Second, the layered product, 1, was used as a precursor to solvothermally react with further H2BDC at 140-180 degrees C, resulting in two products of BDC insertion into the layered structure. These are [Zn3(p-BDC)4] x 2HPIP, 2 (HPIP is partly protonated piperazine), and [Zn3(p-BDC)3(H2BDC)] x (C6H15NO) x H2O x 3DMF, 3 (C6H15NO is triethylamine N-oxide). Single-crystal X-ray diffraction shows that 2 possesses a layer-pillared structure of mu4-BDC, with 1D channels, while 3 has a layer-pillared structure of mu2-BDC, with 2D channels. N2-sorption experiments show 3 has a relatively high BET surface area of 750 m(2)/g. It is proposed that 2 follows the crystal growth mechanism of Ostwald ripening, whereas the crystal structure of 3 might be formed by an insertion mechanism.

Measurement of Diffusion Coefficients of Dimethyl Formamide and Dimethyl Acetamide in Segmented Poly (urethane-urea)

セグメント化ポリウレタンウレア(SPUU)の乾式紡糸工程には溶剤としてDMFまたはDMAcが使われている.乾式紡糸工程のシミュレーションでは拡散係数が基礎データとして必要不可欠である.しかしSPUU中へのDMFの拡散係数に関しては大沢らの報告以外には見当たらない.その上,この拡散係数は液体中への液体の相互拡散に限られているため,糸条がノズル付近の液体状態から巻き取り付近の固体状態に変化する乾式紡糸の全工程にわたって適用することはできないと考えられる.そのため本研究では石英スプリングを用いた実験装置を新たに製作し,収着実験よりSPUUフィルム中へのDMF(またはDMAc)の拡散係数を新たに求める.そして実験データから,拡散係数と温度の関係をアレニウス式で表現する.この論文では,実験で求めたDMFとDMAcの拡散係数の温度依存性の比較と,モアレパターン法とフィルム法で求めた拡散係数の比較検討する.フィルム法で求めた拡散係数はモアレパターン法で求めた拡散係数の10分の1ぐらいである.そしてフィルム法で求めたDMFとDMAcの拡散係数はほぼ同じである.

The liquid–liquid diffusive extraction of hydrocarbons from a North Sea oil using a microfluidic format

Extraction of a GC-amenable hydrocarbon fraction from oil by liquid-liquid diffusion across a laminar interface can be performed in a microfluidic format. Analysis of figures of merit, determined using standard analytical techniques, show this method to be an effective new tool for rapidly processing small quantities of oil and petroleum for GC analysis. Methods based upon similar microsystems devices could find widespread use in a variety of fields, including those associated with organic geochemistry and oil exploration and production, where the manipulation of petroleum constituents (greater than C14) is necessary for analytical purposes.

Apocrustacyanin C(1) crystals grown in space and on earth using vapour-diffusion geometry: protein structure refinements and electron-density map comparisons.

Models of apocrustacyanin C(1) were refined against X-ray data recorded on Bending Magnet 14 at the ESRF to resolutions of 1.85 and 2 A from a space-grown and an earth-grown crystal, respectively, both using vapour-diffusion crystal-growth geometry. The space crystals were grown in the APCF on the NASA Space Shuttle. The microgravity crystal growth showed a cyclic nature attributed to Marangoni convection, thus reducing the benefits of the microgravity environment, as reported previously [Chayen et al. (1996), Q. Rev. Biophys. 29, 227-278]. A subsequent mosaicity evaluation, also reported previously, showed only a partial improvement in the space-grown crystals over the earth-grown crystals [Snell et al. (1997), Acta Cryst. D53, 231-239], contrary to the case for lysozyme crystals grown in space with liquid-liquid diffusion, i.e. without any major motion during growth [Snell et al. (1995), Acta Cryst. D52, 1099-1102]. In this paper, apocrustacyanin C(1) electron-density maps from the two refined models are now compared. It is concluded that the electron-density maps of the protein and the bound waters are found to be better overall for the structures of apocrustacyanin C(1) studied from the space-grown crystal compared with those from the earth-grown crystal, even though both crystals were grown using vapour-diffusion crystal-growth geometry. The improved residues are on the surface of the protein, with two involved in or nearby crystal lattice-forming interactions, thus linking an improved crystal-growth mechanism to the molecular level. The structural comparison procedures developed should themselves be valuable for evaluating crystal-growth procedures in the future.

Crystallization and X-ray diffraction data analysis of leukotriene A4 hydrolase from Saccharomyces cerevisiae.

The Saccharomyces cerevisiae leukotriene A4 (LTA4) hydrolase (scLTA4 hydrolase) has been crystallized in order to study the two activities of LTA4 hydrolase in an evolutionary perspective. Single well diffracting crystals are obtained after switching from the hanging-drop method to liquid-liquid diffusion in capillaries using PEG 8000 as precipitant. These crystals belong to space group P2(1)2(1)2(1), with unit-cell parameters a = 70.8, b = 98.1, c = 99.2 A. Intensity data to 2.3 A resolution were collected from a native scLTA4 hydrolase crystal using synchrotron radiation. A molecular-replacement solution was obtained using the human LTA4 hydrolase structure and the program BEAST.