Thermo-FTIR spectroscopic study of the siderophore ferrioxamine B: spectral analysis and stereochemical implications of iron chelation, pH, and temperature

FTIR spectra of the microbial siderophore, ferrioxamine B, and its nonchelated form (iron free; desferrioxamine B) were studied to facilitate in-depth investigation on the undisrupted structure of the siderophore and its interactions with the environment. Effects of iron chelation as well as those of various levels of pH and temperature on the stereochemical structure of the free ligand and the ferric complex were examined. The presence of a number of functional groups in these compounds and the mutual interaction between them resulted in significant shifts and overlapping of their characteristic absorption bands. Thermal and pH treatments combined with a comprehensive use of curve-fitting analysis facilitated bands resolution. Absorption bands of all functional groups were identified. The results imply that the compact and rigid structure of the ferric complex (ferrioxamine B) is sustained by intense and specific intramolecular hydrogen bonds. Dehydration was the main process observed at low temperature (25-60 degrees C). At 105 degrees C the free ligand form (desferrioxamine B) had already begun to decompose, whereas ferrioxamine B exhibited stability. The thermal destruction became acute at the 170 degrees C treatment for both molecules. The secondary amide groups and the hydroxamate groups, which comprise the binding site for the Fe atom in the complex, were found to be the most sensitive to the thermal degradation. Significant pH effects were observed only for desferrioxamine B samples at pH 9, accompanied by partial decomposition, similar to that observed at 105 degrees C. Deprotonation of desferrioxamine B was found to begin with the deprotonation of the NH(3+) group. Characteristics of the rigid conformational structure of the ferric complex and the state of the NH(3+) group, both assumed to play an important role in the recognition and uptake of the siderophore by membranal receptors, were elaborated by means of FTIR and are discussed in detail.     

Influence of polysaccharide structure on dextran adsorption by montmorillonite

Two dextrans of similar molecular weight (?2 × 10⁶) but containing different structural linkages (B-215F: 95% α-1→ 6 and 5% α-1→ 3 and Polytran: 75% β-1→ 3 and 25% β-1→ 6) were adsorbed on Na-montmorillonite. Adsorption isotherms showed strong, H-2-type (high-affinity. Langmuir mono-layer adsorption) clay-dextran interactions for both polymers. Maximum adsorption of the Polytran dextran (60 $\text{mg}\text{100mg}$ clay) was 33 per cent greater than that of the B-512F dextran (44.5 $\text{mg}\text{100mg}$ clay) for comparative equilibrium systems. Stable clay-Polytran complexes containing up to 47% dextran were prepared. Excess Na₂SO₄ (0.1 m) did not affect the quantity of dextran adsorption by montmorillonite at the 15% dextran concentration. Acid hydrolysis and modified Pregl method-C analyses did not quantitatively recover adsorbed dextran from complexes containing more than 13 mg of dextran adsorbed per 100 mg of clay. Loss on ignition determinations were in good agreement with the difference measurements of dextran adsorption, suggesting that part of the C was expelled as something other than CO₂ in the ignition determinations. The maximum adsorption segment for Polytran was much smaller than the individual molecule. In contrast, the maximum adsorption segment for the B-512F dextran appeared to be the same magnitude as the individual polymer molecule. Adsorption segment length was regarded as a manifestation of the relative proportions of primary and secondary alcohol groups of the molecules.     

蒙脱石纳米复合物的制备及其吸附作用研究

对天然蒙脱石(M)矿物进行钠化改型和柱撑复合,制备了蒙脱石纳米复合物(MN),并对其进行表征,同时研究其对黄曲霉毒素的吸附作用。结果表明：与M相比,MN的层间距和比表面积明显增大,d₍₀₀₁₎值增加到1.96 nm,比表面积达到149.68m²/g,而且孔体积增加,孔直径缩小,微孔比例提高。吸附试验表明：复合改性后,MN对黄曲霉毒素的吸附容量和吸附速率均明显优于M。这些结果提示MN可望成为性能优越的黄曲霉毒素吸附剂。     

Fractionation of humic acids upon adsorption on montmorillonite and palygorskite

The adsorption of three humic acid (HA) preparations by clays—montmorillonite (Wyoming, USA) and palygorskite (Kolomenskoe district, Moscow oblast)—has been studied. The HA preparations were isolated from samples of the humus-accumulative horizons of a leached chernozem (Voronezh) and a chestnut soil (Volgograd), and a commercial preparation of sodium humate (Aldrich) was also used. The solid-state ¹³C NMR spectroscopy and IR spectroscopy revealed the selective adsorption of structural HA fragments (alkyls, O-alkyls (carbohydrates), and acetal groups) on these minerals. As a result, the aromaticity of the organic matter (OM) in the organic-mineral complexes (OMCs) and the degree of its humification have been found to be lower compared to the original HA preparations. The fractionation of HAs is controlled by the properties of the mineral surfaces. The predominant enrichment of OMCs with alkyls has been observed for montmorillonite, as well as an enrichment with O-alkyls (carbohydrates) for palygorskite. A decrease in the C : N ratio has been noted in the elemental composition of the OM in complexes, which reflected its more aromatic nature and (or) predominant sorption of N-containing structural components of HA molecules. The adsorption of HA preparations by montmorillonite predominantly occurs on the external surface of mineral particles, and the interaction of nonpolar alkyl groups of HAs with this mineral belongs to weak (van der Waals, hydrophobic) interactions. The adsorption of HA preparations by palygorskite is at least partly of chemical nature: Si-OH groups of minerals are involved in the adsorption process. The formation of strong bonds between the OM and palygorskite explains the long-term (over 300 million years) retention of fossil fulvate-type OM in its complex with palygorskite, which we revealed previously.     

Molecular simulations to estimate thermodynamics for adsorption of polar organic solutes to montmorillonite

Ideally, one could use molecular mechanics or quantum mechanics to predict the magnitude of organic solute adsorption from water to soil minerals. Reproduction and/or prediction of mineral and interfacial structures remains challenging, but calculation of meaningful energy relations through computational chemistry techniques is even more difficult than structural calculations. This paper attempts to define the necessary and relevant components for an overall scheme that allows translation of computed interaction enthalpies to experimental adsorption enthalpies and vice versa. While the scheme could be applied to quantum calculations, we test it for the possibility of using empirical molecular mechanics to estimate relative energies for the adsorption of non‐ionic organic solutes in clay mineral‐water‐solute systems. We used molecular dynamics’ simulations to estimate relative clay–organic interaction enthalpies for a series of nitro‐aromatic solutes and hydrated, K‐saturated montmorillonite, for comparison with experimental adsorption isotherm data for the same clay‐nitroaromatic systems. The trend of computed interaction enthalpies (e.g. −234 ± 17 kJ mol⁻¹ for trinitrobenzene and −154 ± 16 kJ mol⁻¹ for p‐nitrobenzene) agreed modestly well with the trend of adsorption maxima from the experiments. Furthermore, we developed several variants on a thermodynamic cycle framework for comparing computed interaction energies with experimentally determined adsorption enthalpies. The algorithms, which include estimates for enthalpy changes both in bulk solution and in the clay interlayer, show promise: for p‐dinitrobenzene and for 1,3,5‐trinitrobenzene, the overall predicted adsorption enthalpies (e.g. −13 ± 22 and −67 ± 23 kJ mol⁻¹, respectively) were in modest agreement with experiments (−18 ± 1 and −28 ± 4 kJ mol⁻¹, respectively). We discuss shortcomings of the methods, in hopes of encouraging better estimates for the various energy terms, improvement of the algorithms, and more valid comparisons between quantum mechanical or molecular mechanical interaction energies and experimental enthalpies.     

On the mechanism of specific phosphate adsorption by hydroxylated mineral surfaces: A review

Abstract

The mechanism of specific phosphate adsorption by hydroxy‐lated mineral surfaces comprises two aspects: the phosphate‐hydroxyl surface reaction and the configuration of the adsorbed phosphate ion. Evidence pointing to ligand exchange as the mechanism of the phosphate‐surface hydroxyl reaction include kinetics of adsorption and desorption; hydroxyl ion release; infrared spectroscopy, and stereochemical calculations. Data pertaining to the coordination of adsorbed phosphate on hydroxy‐lated mineral surfaces have not been conclusive overall. Isotopic exchange experiments and studies of desorption kinetics do not provide definitive information on surface coordination. Measurements of hydroxyl ion release and crystallographic calculations provide support for the existence of both monodentate and bidentate surface complexes of phosphate ions. Infrared spectroscopic investigations suggest a binuclear complex on dried, phosphated goethite. However, these studies cannot be extrapolated automatically to soil minerals, since the addition of water favors formation of a monodentate surface complex. Further research is needed to establish the configuration of adsorbed phosphate ions.     

A study of phosphate adsorption by four Bangladesh soils

The adsorption curves for four soils were divided into segments I, II and III. Segment I ($\text{< 2}\text{μg P/ml equil. concn.}$) and segment II (2–150 μg P/ml equil. concentr.) conformed to the Langmuir equation similar to that of pure materials like gibbsite, pseudoboehmite and kaolinite, whereas segment III $\text{(> 75–150 μ}\text{g P/ml equil. concn.}\text{)}$ conformed to the Freundlich equation and was unlike the previous finding of linear relationship for pure materials.     

Leaching of nitrate in calcareous soils as influenced by its adsorption on calcium carbonate

Adsorption of the nitrate ion on calcium carbonate and its leaching in calcareous soils were examined by equilibrium and elution techniques. Nitrate ions adsorbed on the surface of CaCO₃ fitted the Langmuir model well at an equilibrium concentration of 40 ppm NO₃⁻. Sulphate ions reduced adsorption of nitrate. Data for elution of surface-applied nitrate from laboratory soil columns, when plotted in the form of elution curves and semi-log plots, indicated interactions of nitrate with the soils. The elution curves had long trailing portions due to desorption of nitrate. The length of the trailing portion of a curve was determined by the amount of nitrate adsorbed which in turn seems to depend upon the total surface area of CaCO₃. Sulphate ions when present in the displacing fluid seem to desorb nitrate ions from the surface of the CaCO₃, whereas chloride ions have little or no effect.     

Comparison of the adsorption of maize root mucilage and polygalacturonic acid on montmorillonite homoionic to divalent lead and cadmium

Summary Root mucilage material (RM) was isolated from maize plants grown in the field, and its affinity to montmorillonite (M) homoionic to Pb²⁺ and Cd²⁺ was compared with that of a commercial polygalacturonic acid (PGA). Adsorption isotherms of the commercial and natural materials on the two clay systems were compared in unbuffered systems at pH 3 and pH 6. Adsorption of PGA occurred only at pH 3, and was higher on M-Pb than on M-Cd. In contrast, the adsorption of RM was higher on M-Cd than on M-Pb. Total amounts of RM adsorbed at pH 3 were about 3 times lower on M-Cd and 20 times lower on M-Pb than the respective amounts of PGA adsorbed at the same pH. Polygalacturonic acid had a high content of relatively well dissociated (pKa = 3.5) carboxylic groups, and adsorbed on the clay surface at pH values lower than its pKa. At pH 6, the dissociation of the acid groups favoured its solubility, and the metal cations were then probably displaced by ion exchange. The lower affinity of RM to the clay materials was related to its average molecular weight, which was lower than that of PGA, and to its water solubility, which was higher than that of PGA. The low pH dependence of the adsorption of RM was related to its lower carboxylic acidity and higher content in hydroxyl and amino groups.     

油料作物秸秆生物炭对水体中铅离子的吸附特性与机制

为探索利用废弃生物质资源制备生物炭去除水体中Pb~(2+)污染的可行性,以农业废弃物胡麻秸秆和油菜秸秆为原材料,采用限氧裂解法在700℃条件下制备油菜秸秆(rape straw)生物炭和胡麻秸秆(flax straw)生物炭,通过2种生物炭对Pb~(2+)的批量吸附试验,利用4种吸附动力学模型(拟一级动力学、拟二级动力学、Elovich模型和颗粒内扩散模型)和4种等温吸附模型(Langmuir、Freundlich、Temkin和D-R模型)研究了胡麻和油菜秸秆生物炭对Pb~(2+)的吸附行为。同时,通过(brunauer emmett teller,BET)比表面积和孔径分析、扫描电子显微镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)等手段对生物炭的结构和性质进行了表征,初步探讨了2种生物炭对Pb~(2+)的吸附机制。结果表明,胡麻和油菜秸秆生物炭分别在4 h和10 h达到吸附平衡,理论最大吸附量分别达到220.07和307.59 mg/g;2种生物炭对Pb~(2+)的吸附符合拟二级动力学模型,吸附等温线符合Langmuir等温吸附模型,表明其吸附过程为单分子层吸附;2种生物炭对Pb~(2+)的吸附作用为物理-化学复合过程,吸附机制主要包括静电作用、离子/配体交换、阳离子–π作用。研究结果可为油料作物秸秆的资源化利用和生物炭对水中重金属污染防治提供理论依据。     

香蕉皮改性材料对废水中二价Cd离子的吸附特性与机理

为探究农业生物质制备绿色吸附材料处理含Cd~(2+)废水方法,以香蕉皮为原料,制备改性吸附材料。采用单因素试验,优化了改性工艺条件。通过静态吸附试验,结合等温模型和吸附动力学模型探讨了其对Cd~(2+)吸附过程。利用比表面及孔径分析(brunner-emmet-teller)、扫描电镜(scanning electron microscope)、能谱仪(energy disperse spectroscopy)、元素分析仪、傅里叶变换红外光谱(Fourier transform infrared spectroscopy)等手段对改性前后材料的表面形态和结构进行表征,并分析了改性和吸附过程的机理。结果表明:改性较佳工艺条件为Na OH浓度为0.25 mol/L,改性时间为30 min。在此条件下香蕉皮改性后,对水中Cd~(2+)的理论饱和吸附量由37.61 mg/g提高到87.15 mg/g,平衡时间由60 min缩短到45 min。吸附符合Langmuir等温模型(R~2=0.998)和准二级动力学模型(R2=0.999)。改性后的香蕉皮对水中Cd~(2+)的吸附以离子交换吸附为主。研究结果可为木质纤维素生物质改性制备绿色吸附材料处理含重金属废水提供理论依据。     

Use of chrome azurol S reagents to evaluate siderophore production by rhizosphere bacteria

Summary Siderophores produced by rhizosphere bacteria may enhance plant growth by increasing the availability of Fe near the root or by inhibiting the colonization of roots by plant pathogens or other harmful bacteria. To examine the populations of siderophore-producing bacteria colonizing the roots of two grass species that differed in their susceptibility to Fe deficiency, we inoculated serial dilutions of root samples onto chrome azurol S (CAS) agar and several other selective and non-selective culture meida. CAS agar effectively differentiated bacteria that were capable of excreting large amounts of siderophore, but the composition of the medium limited its usefulness for ecological studies. A large proportion (71–79%) of the bacterial population that grew on a non-selective medium (tryptic soy agar) failed to grow on CAS agar, and several isolates that showed no sign of siderophore production on CAS agar produced siderophore in liquid culture. Similar populations of siderophore-producing bacteria were observed on roots of St. Augustine grass, which frequently exhibits Fe chlorosis, and bermuda grass, which does not. Roots of both grasses were colonized by bacteria that produced siderophore in vitro at concentrations ranging from 100 to 230 M. The CAS assay solution was also used to compare siderophore production by Pseudomonas fluorescens Q6, an isolate from bermuda grass, and by P. putida B 10, a plant growth-promoting pseudomonad. P. fluorescens Q6 produced 2.4 times more siderophore in vitro than P. putida B 10.     

The failure of using equilibrium adsorption of fosthiazate onto montmorillonite clay particles to predict their cotransport in porous media as revealed by batch and column studies

Journal of Soils and Sediments - Adsorption of fosthiazate onto montmorillonite clay particles (MPs) and cotransport of fosthiazate and MPs in sand and soil porous media were investigated for the...     

正压式气流排种器排种效果试验

为了探讨正压式气流排种器的排种均匀性,论文对具有代表性的苜蓿种子、披碱草种子和玉米种子进行了排种试验。结果表明,该排种器排种均匀性和通用性较好,对豆科牧草种子（苜蓿）、禾本科牧草种子（披碱草）和大田作物种子（玉米）均可较均匀的排种,且都达到了行业标准要求。风速和喂入速度对种子的各行排量一致性变异系数和总排量稳定性变异系数V 有显著影响,相关系数都高达0.97左右。最后,通过优化试验方案,得出各种种子的最佳工作条件：披碱草种子,喂入速度为470～500 g/min,风速为27～30 m/s;苜蓿种子,喂入速度为505～525 g/min,对应的风速为30～33 m/s;玉米种子,喂入速度为5200～5500 g/min,风速为32～35 m/s。     

Heavy metal sorption on soil minerals affected by the siderophore desferrioxamine B: the role of Fe(III) (hydr)oxides and dissolved Fe(III)

Phytoextraction of heavy metals from polluted soils has often been found to be limited by the bioavailability of the pollutants. Inorganic or organic ligands are occasionally used as complexing agents to enhance the mobility of the heavy metals. However, the opposite effect is also possible. We studied the influence of the hydroxamate siderophore desferrioxamine B (DFOB) on the sorption of Cu, Zn and Cd to clay minerals, with the emphasis on the role of dissolved Fe(III) and Fe(III) minerals. Depending on the surface charge of the minerals and on pH, sorption of heavy metals can be either enhanced or diminished. We show here that this effect of DFOB disappears if dissolved Fe(III) is added to suspensions of clay minerals in excess to DFOB. We found that the solid Fe(III) phases ferrihydrite and goethite did not impede the effect of DFOB on the sorption of heavy metal, however. Between pH 4 and 10, DFOB completely prevented Cu sorption on ferrihydrite. A strong mobilizing effect was also observed for Zn, but not for Cd. In presence of goethite, concentrations of dissolved Cu, Zn and Cd were enhanced only above approximately pH 5, 7 and 8, respectively. Below these pH values the binding of these metals to goethite was even stronger with than without DFOB. In the absence of heavy metals, DFOB‐promoted dissolution of ferrihydrite was much faster than that of goethite due to the larger surface area of ferrihydrite. In the alkaline pH range, where sorption of DFOB on the surfaces of the iron oxides was greater, dissolution of both minerals was reduced.     

生物炭Mg/Al-LDHs复合材料对磷的吸附特性及机理

为有效控制水体富营养化和实现农业废弃物资源化利用,以生物炭作为类水滑石(Layered Double Hydroxide,LDHs)的载体,采用共沉淀法制备出生物炭镁铝水滑石复合材料(Mg/Al-LDHs@BC),并研究其对水中磷酸盐的吸附特性.采用X射线衍射、扫描电子显微镜、Zeta电位仪、傅立叶红外光谱仪和X射线光...