Metal ions binding onto a lignocellulosic substrate extracted from wheat bran: a NICA-Donnan approach

In this study ion binding to solid organic matter was investigated. We used the NICA-Donnan model to describe the interaction between Cu(II), Pb(II), and Cd(II) ions and a lignocellulosic substrate extracted from wheat bran. Such a material represents a very cheap and flexible substrate, which can be used as a natural filter to remove toxic metal ions from industrial effluents or applied in the decontamination and rehabilitation of abandoned industrial sites. Moreover, such a material also represents a very simple model of natural organic matter derived from lignin and cellulose, for which there is now a lack of thermodynamic data as far as their interaction with toxic metal ions is concerned. Experimental results were obtained in various conditions of pH and ionic strength. In our modeling, we used the acidity constants and the concentration of sites that were determined in a previous work. The parameters deduced from the NICA-Donnan model were also compared to thermodynamic data available for other cases of natural organic matter, mainly humic substances.     

Use of a NICA-Donnan approach for analysis of proton binding to a lignocellulosic substrate extracted from wheat bran

The acid-base properties of a lignocellulosic substrate extracted from wheat bran have been investigated. The lignocellulosic substrate was first studied by use of FTIR, XPS, and solid-state 13C NMR to characterize the surface-active groups. Major contributions arise from the presence of carboxylic and phenolic sites. The former are associated with long-chain fatty acids and the latter are constituent units of lignin. All ionizable sites were quantified by use of the Ca-acetate method and by potentiometric titrations in non-aqueous media. Results were compared with those from conductimetric titrations in water and in the presence of barium ions. Protometric titration curves for the lignocellulosic substrate were obtained at several ionic strengths. Data were also treated with the NICA-Donnan model to determine the intrinsic ionization parameters.     

Effect of moisture content on the interaction between lignocellulosic materials and ozone

The kinetics of ozonolysis for a number of plant materials (aspen and pine sawdust, wheat straw, flax chaff, and sunflower husks) is comparatively studied, and the dependences of the rate of ozone absorption on the water content in lignocellulosic samples are obtained. The kinetic curves of water absorption by different plant materials in a saturated water vapor atmosphere at room temperature are constructed, and the equilibrium values of water content are determined. It is shown that straw is characterized by a higher affinity for water than wood. The range of the moisture contents of lignocellulosic materials that ensures the maximum rate of their reaction with ozone is found. No appreciable effect of the nature of plant material on the rate of ozone absorption was detected, since the process is controlled by the diffusion of ozone in the pores of materials.     

Statistical mechanical approach to competitive binding of metal ions to multi-center receptors

A microscopic site binding model to treat binding of several metal ions to multi-center receptors is proposed. The model introduces the appropriate parameterization in terms of microscopic complexation constants and metal-metal pair interaction energies. The model is solved with statistical mechanical techniques, including direct enumeration or transfer matrices. We obtain microscopic and macroscopic complexation constants, microstate probabilities, and binding isotherms for chain-like receptors, including the long-chain limit. Various examples to illustrate the usefulness of the model are given.     

Ion-exchange equilibrium distribution studies of some metal ions in nitrite media

Ion-exchange equilibrium distribution of some metal ions has been studied in nitrite media, with cation- as well as anion-exchangers. The distribution coefficients (K(D)) show the utility of a new nitrite medium which is a complexing medium for most transition metal ions giving anionic complexes in aqueous solution. Similar studies have been performed in aqueous ethanol. Increase in the concentration of ethanol led to increased complex formation and changed K(D) values.     

A modular approach to porphyrin oligomers using metal ions as connectors

Porphyrins bearing two external coordination sites allowed the stepwise preparation of polymetallic oligomers connected by metal centers.     

Computer calculation of equilibrium concentrations in mixtures of metal ions and complexing species

A method is described for calculating equilibrium concentrations of all species in multi-metal-multi-ligand mixtures from the pH of the solution, the total concentration of each metal and each complexing agent, and the relevant equilibrium constants (pK(a) values and stability constants). No restriction is imposed on types of possible complexes, which can include mixed, hydrolysed, protonated and polynuclear species. Two examples are given. One of these comprises a 10-metal-10-ligand system (195 equilibrium constants). In the second system, mixed complex formation is important. The computer program is given.     

Electrochemical approach to monitoring metal exchange reaction of acetylacetonate complexes with cadmium, copper and zinc ions

Metal exchange reactions of acetylacetonate complexes with Cd(II), Cu(II) and Zn(II) ions were investigated by using cadmium and copper ion selective electrodes. Changes in the electrode potential and pH of the solutions were monitored upon adding the pertinent metal Zn(II) of the acetylacetonate (AA) complexes. In the reverse system in which a stable Cu-AA complex exists in the solution prior to adding a secondary metal ion (Cd(II) or Zn(II)), no Cu(II) was replaced by either ion. In the systems containing Cd(II) and Zn(II) as a complexed form with AA or as free ions, the exchange reactions were not explained by considering the equilibrium stability constants of the Cd-AA and Zn-AA complexes.     

Electronic spectra of gas phase ions. An equilibrium perturbation approach

A method is proposed by which the electronic absorption of an ion may be obtained by perturbation of a chemical equilibrium established in an ion cyclotron resonance spectrometer.     

Hybrid process for the conversion of lignocellulosic materials

Because of the recalcitrant nature of lignocellulosic materials, it is important to pretreat the biomass in order to obtain a suitable material for the bioconversion. In this study, two different types of pretreatments were performed. The first experiment used a 2-gal Parr reactor operated at 140, 150,160, and 170‡C with sulfuric acid concentrations varying from 0.5 to 2%. A second pretreatment was performed with a two-stage low-temperature process. The first-stage pretreatment was performed at 100 or 120‡C with sulfuric acid concentrations of 0.5, 2, and 5% followed by a secondstage pretreatment at 120‡C with 2% acid concentration. The best residues for enzymatic hydrolysis and simultaneous saccharification and fermentations (SSF) came from the higher temperature pretreatment with the Parr reactor. However, a large portion of the xylose fraction was degraded to furfural and glucose was degraded to HMF. On the contrary, the two-stage low temperature pretreatment resulted in a very low percentage of xylose degradation, and no glucose degradation. The residues from this two-stage pretreatment performed satisfactorily toward the production of ethanol by SSFs. This study discusses the results obtained from these experiments.     

Classification of metal ions according to their complexing properties: a data-driven approach

Factor, cluster and self-organizing map analyses were performed for the stability constants of complexes of 24 metal ions and hydrogen with 3960 ligands (15606 values of log K₁). Five factors reproduce 89% of data variability. Both direct clusterization and clusterization on the basis of factor analysis established the existence of six different classes of similar cations. The similarity series for metal ions and relative similarity of several ions are discussed and the Kohonen two-dimensional map, which visually represents the similarity, is presented.     

Potentiometric study of complexation between taurine and metal ions

The protolytic and complexation properties of taurine are studied by a potentiometric method. The dissociation constants of 2-aminoethanesulfonic acid functional groups and the stability constants of taurine complexes with copper(II), cobalt(II), nickel(II), zinc(II), manganese(II), cadmium(II), silver(I), magnesium(II), calcium(II), strontium(II), and barium(II) ions are calculated.     

Interactions between metal ions and carbohydrates. Spectroscopic characterization and the topology coordination behavior of erythritol with trivalent lanthanide ions

The coordination of carbohydrate to metal ions is important because it may be involved in many biochemical processes. The synthesis and characterization of several novel lanthanide-erythritol complexes (TbCl(3)·1.5C(4)H(10)O(4)·H(2)O (TbE(I)), Pr(NO(3))(3)·C(4)H(10)O(4)·2H(2)O (PrEN), Ce(NO(3))(3)·C(4)H(10)O(4)·2H(2)O (CeEN), Y(NO(3))(3)·C(4)H(10)O(4)·C(2)H(5)OH (YEN), Gd(NO(3))(3)·C(4)H(10)O(4)·C(2)H(5)OH (GdEN)) and Tb(NO(3))(3)·C(4)H(10)O(4)·C(2)H(5)OH (TbEN) are reported. The structures of these complexes in the solid state have been determined by X-ray diffraction. Erythritol is used as two bidentate ligands or as three hydroxyl group donor in these complexes. FTIR spectra indicate that two kinds of structures, with water and without water involved in the coordination sphere, were observed for lanthanide nitrate-erythritol complexes. FIR and THz spectra show the formation of metal ion-erythritol complexes. Luminescence spectra of Tb-erythritol complexes have the characteristics of the Tb ion.     

利用吉布斯吸附等温式探索求解电解质溶液活度的新方法

以吉布斯吸附等温式积分式为基础,数学推证表面势的表达式,并应用表面势的数学表达式探求了一种测算电解质溶液活度系数的新方法.选取KIM计算电解质溶液溶质的活度系数公式为新方法的活度系数经验关系式的具体表达形式,利用实验直接测得的不同浓度下的表面张力数据,采用最优化拟合的方法,求算出活度系数经验关系式中的待定系数,从而可以求得不同浓度下的电解质溶液中的溶质的活度系数和活度.计算结果与KIM文献值对比,活度系数曲线在不同的坐标尺度下有很好的一致性,这使得通过测定电解质溶液表面张力测算其活度成为可能.     

The effect of metal ions with different valences on the retardation of soil-bentonite barrier materials and its mechanism

In this paper, with K＋, Ca2＋ and Fe3＋ as the objects of study, retardation of soil-bentonite （SB） barrier materials for metal ions with different valences is investigated, and the adsorption mechanism, migration patterns and permeation behavior are explored so as to provide a theoretical basis for their application. The results show that the adsorption process for metal ions with different valences by SB barrier materials is fast, and the higher the valence, the greater the adsorption capacity. The fitting of the adsorption process conforms to pseudo-second-order adsorption kinetics and Langmuir-Freundlich adsorption equation, which explains that chemical adsorption is the dominating state and that the SB surface has certain heterogeneity. The permeability coefficient of K＋, Ca2＋ and Fe3＋ in SB each has a maximum and the higher the valence, the sooner the maximum appears. Also the higher the valence, the more obvious the effect on SB retardation performance; and the sooner the ion breaks through the barrier wall completely, that is, the wall＇s retardation performance for higher valent ions may decline.     

Fragmentation of electrospray-produced oligodeoxynucleotide ions adducted to metal ions

In this article, we describe the unique fragmentations of oligodeoxynucleotides (ODNs) whose phosphate groups are completely depleted of protons and replaced with metal ions. The production of the ubiquitous [a(n) - base] ions still occurs, but no longer by transfer of an acidic phosphate proton to an adjoining 3' base. Nor is the extent of the reaction determined by the proton affinity of that base. Rather, the reaction now occurs via a cleavage 3' to both pyrimidines and purines; cleavage 3' to pyrimidine is more favorable than that 3' to purine. We also demonstrate that an ODN is more stable in the gas phase when its phosphate groups are bound to metal ions than when its phosphate groups are attached to hydrogens. This study also provides further evidence for the ODN fragmentation mechanism that involves H transfer to a nucleobase. To establish the structural utility of this new fragmentation, we applied it to distinguishing small ODNs containing a photomodified cis,syn-cyclobutane pyrimidine dimer from the parent ODNs, a system that cannot be distinguished by collisional activation of precursor species that do not contain metal ions.     

Adsorption of graphene oxide/chitosan porous materials for metal ions

Porous graphene oxide/chitosan（PGOC） materials were prepared by a unidirectional freeze-drying method.Their porous structure,mechanical property and adsorption for metal ions were investigated.The results show that the incorporation of graphene oxide（GO） significantly increased the compressive strength of the PGOC materials.The saturated adsorption capacity of Pb²⁺ increased about 31%,up to 99 mg/g when 5 wt%GO was incorporated These biodegradable,nontoxic,efficient PGOC materials will be a potential adsorbent for metal ions in aqueous solution.     

Adsorption of several metal ions onto a model soil sample: equilibrium and EPR studies

Soils play an important role in the control of metallic cations in the environment. Therefore, knowledge of the adsorption properties of soil is crucial in understanding and solving pollution problems. Adsorption isotherms provide a macroscopic view of the retention phenomena. The aim of this paper is to study iron, manganese, and chromium adsorption onto a soil sample as a function of the reaction time, pH, and metal concentration. The adsorption isotherms allow the determination of the affinity order of metals for the surface of the soil sample as such: Fe(3+)>Cr(3+)>Mn(2+). The equilibrium data fit well with the Langmuir and Freundlich models and confirm the affinity order of the soil sample for these metals. These adsorption data are combined with EPR spectroscopy to obtain structural information about the surface complexes formed. Iron is held in inner-sphere complexes. Manganese is simultaneously held in outer- and inner-sphere complexes. Due to poor resolution, chromium was not detected by EPR and thus it is impossible to infer coordination sphere and coordination number. Iron and manganese are in an octahedral environment.     

Interaction of bivalent transition metal ions with iminodiacetato-(pentaammine/tetraammine)cobalt(III) ions. A kinetic and equilibrium study

Summary The kinetics of reversible complexation of Ni^II and Co^II with iminodiacetato(pentaammine)cobalt(III), [(NH₃)₅-Co(idaH₂)]³⁺ and Ni^II with iminodiacetato(tetraammine)-cobalt(III), [(NH₃)₄Co(idaH)]²⁺, have been investigated by the stopped-flow technique at 25 °C, pH = 5.7–6.9 and I = 0.3 mol dm ^–3. The reaction paths (NH₃)₅Co(idaH)²⁺+M²⁺(NH₃)₅Co(ida)M³⁺+H⁺ (NH₃)₅Co(ida)⁺+M²⁺(NH₃)₅Co(ida)M³⁺ (NH₃)₄Co(ida)⁺+Ni²⁺(NH₃)₄Co(ida)Ni³⁺ have been identified (idaH = N⁺H₂(CH₂CO₂)₂H, ida = NH(CH₂COO)^2–]. The rate parameters for the formation and dissociation of the binuclear species are reported. The data are essentially consistent with an I _d mechanism. The dissociation rate constants of the binuclear species indicate that Ni²⁺ and Co²⁺ are chelated by the coordinated iminodiacetate moiety.