Microcalorimetric studies on the adsorption of DNA by soil colloidal particles

This study applied TAM air isothermal calorimeter to measure the adsorption enthalpies of DNA on eight colloidal fractions from permanent-charge and variable-charge soils. The adsorption of DNA on soil colloids was also examined by equilibrium adsorption analysis. The data evaluated from isotherms fitted by Langmuirean model revealed that the affinity of DNA for variable-charge soil colloids was higher than that for permanent-charge soil colloids. More tightly bound DNA molecules were observed on coarse clays and inorganic clays than on fine clays and organic clays, respectively. The adsorption enthalpies of DNA on permanent-charge soil colloids were higher than those on variable-charge soil colloids. DNA adsorption on organic clays is endothermic, whereas that on inorganic clays is exothermic. Dehydration and electrostatic repulsion were considered to cause the higher adsorption enthalpies of DNA with organic clays, while hydrogen bonding, ligand exchange and electrostatic attraction result in the lower DNA adsorption enthalpies on inorganic clays. The thermodynamic parameters presented in this study have important implication for providing further insight into mechanisms of the adsorption of DNA on soil particles.     

Effects of low-molecular-weight organic ligands and phosphate on DNA adsorption by soil colloids and minerals

Adsorption of DNA on montmorillonite, kaolinite, goethite and soil clays from an Alfisol in the presence of citrate, tartrate and phosphate was studied. A marked decrease in DNA adsorption was observed on montmorillonite and kaolinite with increasing anion concentrations from 0 to 5 mM. However, the amount of DNA adsorbed by montmorillonite and kaolinite was enhanced when ligand concentration was higher than 5 mM. In the system of soil colloids and goethite, with the increase of anion concentrations, a steady decrease was found and the ability of ligands in depressing DNA adsorption followed the sequence: phosphate > citrate > tartrate. Compared to H2O2-treated clays (inorganic clays), a sharp decrease in DNA adsorption was observed on goethite and organo-mineral complexes (organic clays) with increasing ligand concentrations. The results suggest that the influence of anions on DNA adsorption varies with the type and concentration of anion as well as the surface properties of soil components. Introduction of DNA into the system before the addition of ligands had the greatest amount of DNA adsorption on soil colloids and goethite. Organic and inorganic ligands promoted DNA adsorption on montmorillonite and kaolinite when ligands were introduced into the system before the addition of DNA. The results obtained in this study have important implications for the understanding of the persistence and fate of DNA in soil environments especially rhizosphere soil where various organic and inorganic ligands are active.     

Binding and degradation of DNA on montmorillonite coated by hydroxyl aluminum species

Adsorption, desorption and degradation by DNase I of DNA on montmorillonite (M) and different hydroxyaluminum-M complexes (Al(OH)_x-M) containing 2.5, 10.0 and 20.0 mmol coated Al/g clay (AM_2.5, AM₁₀ and AM₂₀) were studied. The adsorption isotherms of DNA on montmorillonite and Al(OH)_x-M complexes conformed to the Langmuir equation. The amount of DNA adsorbed followed the sequence of montmorillonite > AM₂₀ > AM₁₀ > AM_2.5. A marked decrease in the adsorption of DNA on montmorillonite and Al(OH)_x-M complexes was observed with the increase of pH from 4.0 to 9.0. Calcium ion significantly promoted DNA adsorption. The adsorption enthalpy of DNA on montmorillonite was endothermic, whereas that on Al(OH)_x-M complexes was exothermic. The percent desorption of DNA from clays was in the order of montmorillonite > AM_2.5 > AM₁₀ > AM₂₀, suggesting that OH–Al loading on montmorillonite surface increased the binding affinity of DNA. Fourier transform infrared (FTIR) spectra showed that the binding of DNA on AM₁₀ and AM₂₀ changed its conformation from the B-form to the Z-form. The presence of montmorillonite and Al(OH)_x-M complexes provided protection for DNA against degradation by DNase I. The higher level of protection was found with Al(OH)_x-M complexes compared to montmorillonite. The higher stability of DNA in the system of Al(OH)_x-M complexes seemed to be attributed mainly to the conformational change of bound DNA and their greater adsorption capacity for DNase I. The information obtained in this study is of fundamental significance for understanding the behavior of extracellular DNA in soil environments.     

Changes in microbial community structure and function within particle size fractions of a paddy soil under different long-term fertilization treatments from the Tai Lake region, China

Greenhouse gas (GHG) production and emission from paddy soils impacts global climate change. Soil particle size fractions (PSFs) of different sizes act as soil microhabitats for different kinds of microbial biota with varying conditions of redox reactions and soil organic matter (SOC) substrates. It is crucial to understand the distribution of soil microbial community structure within PSFs and linkage to the GHG production from paddy soils of China. The change of bacterial and methangenic archaeal community and activity relating to CH₄ and CO₂ production with PSFs under different fertilizer applications was studied in this paper. The fertilization trial was initiated in a paddy soil from the Tai Lake region, Jiangsu, China with four treatments of non-fertilized (NF), fertilized with inorganic fertilizers only (CF), inorganic with pig manure (CFM) and inorganic with straw return (CFS), respectively since 1987, and the PSFs (<2 μm, 2–20 μm, 20–200 μm, and 200–2000 μm) were separated by a low energy sonication dispersion procedure from undisturbed samples. Analysis of bacterial community within different size particles was conducted by PCR-DGGE. The results indicated significant variation of bacterial community structure within different PSFs. The methane was predominantly produced in the coarser fractions, while more species and higher diversity of bacteria survived in the size of <2 μm fractions, in which the bacterial community structure was more significantly affected by fertilizer application practices than in the other coarser fractions. Higher bacterial species richness and more diversities in the smallest size fractions was due to the vicinity between microbes, access to carbon resource outside the microaggregates, and smaller pore size as protective agent suitable habitats for microbes rather than high SOC. Whereas, higher CO₂, CH₄ production and methanogenic archaeal community in coarser fractions may be contributed to storage of labile organic carbon in these fractions. It indicated that availability of SOC in PSFs is mainly factor affected survival of methanogenic archaeal community structure, whereas, bacterium community habitation more affected by physical protection of their location in PSFs. Their activity greatly depended on liability of SOC access to PSFs. Fertilizer application caused more change of bacteria community in clay fraction and greatly increased bacterium and methanogen activity in coarser fractions but only a slight effect on methanogenic archaeal community in the particle size fractions.     

Conformation, activity and proteolytic stability of acid phosphatase on clay minerals and soil colloids from an Alfisol

The present study was carried out to investigate the conformation, enzymatic activity and proteolytic stability of acid phosphatase on montmorillonite, kaolinite and soil colloids from an Alfisol by means of circular dichroism (CD) spectroscopy, isothermal titration microcalorimetry (ITC) and biochemical assay, respectively. The results showed that the secondary structure of phosphatase was changed from disordered type to ordered form during adsorption/desorption cycle, organic substance and 2:1-clay mineral in Brown Soil benefited the formation of ordered structure. Enzymatic activity of phosphatase was inhibited while the proteolytic stability was promoted after the interaction with active particles from permanent charge soil. The decrease of enzymatic activity and the increase of proteolytic stability resulted by montmorillonite and organic colloid were both greater than that by kaolinite and inorganic colloid, which was in consistent with the extent of structural change induced by different colloid particles. Thus, one of the most significant factors responsible for the variation of enzymatic activity and proteolytic stability might be the hiding or even damage of active sites and the irrecognition of cleavage sites in enzyme molecules induced by the formation of ordered structure. The information obtained in this study is of crucial significance for the understanding of the behavior and fate of extracellular enzymes in soils with permanent charges.     

Does the nanometre scale topography of titanium influence protein adsorption and cell proliferation?

To investigate the influence of titanium films with nanometre scale topography on protein adsorption and cell growth, three different model titanium films were utilized in the present study. The chemical compositions, surface topographies and wettability were investigated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurement, respectively. The films share the same surface chemistry but exhibit different topographies on a nanometre scale. Thus, they act as model systems for biological studies regarding surface topography effects. The films were obtained by varying the deposition rate and the film thickness, respectively. These films displayed nanometre scale surface roughness (root mean square roughness, R_rms) from 2 to 21 nm over areas of 50 μm × 50 μm, with different grain sizes at their surfaces. Albumin and fibrinogen adsorption on these model titanium films were performed in this study. Bicinchoninic acid assay was employed to determine the amount of adsorbed protein on titanium film surfaces. No statistically significant differences, however, were observed for either albumin or fibrinogen adsorption between the different groups of titanium films. No statistically significant influence of surface roughness on osteoblast proliferation and cell viability was detected in the present study.     

Assessment of the relations between the spectroscopic characteristics of soils and their ability to adsorb organic pollutants

The aim of this research was to study the way the humus content of the soils affects the adsorption of particular organic pollutants. We used five different media during the experiments: two different soils (sandy soil, coherent soil), humic acid extracts extracted from these soils, and a commercially available humic acid product. We studied the adsorbed amount of the given compounds at the particular media, the role of humic materials in the observed adsorption ratios, and whether the co-existence of the different compound changes the adsorption–desorption conditions.The inorganic components of the soils play an important role also in the absorption of the apolar compounds, and as the polarity (or polarizability) of the organic compound increases, the humic materials of the soil, or rather their polar functional groups take the dominant role in the absorption of the pollutant. The absorption and desorption of three apolar compounds were practically not influenced by the presence of other pollutants in the soil, and this phenomenon was also independent from the extracting agent. However, in the case of polar diuron, the presence of other pollutants can result in decrease of mobility.     

高岭石吸附乙烯和苯的Delft分子力学研究

运用Ｄｅｌｆｔ分子力学（ＤＭＭ）程序及其粘土和共轭烯烃力场，计算研究了高岭石对乙烯和苯的吸附作用，探讨了吸附对粘土晶体和有机分子的结构、电荷分布和能量的影响，求得了高岭石吸附乙烯和苯的吸附热等重要物理量．     

Mechanisms of Tebuconazole Adsorption in Profiles of Mineral Soils

The study attempted to identify the soil components and the principal adsorption mechanisms that bind tebuconazole in mineral soils. The K_F values of the Freundlich isotherm determined in 18 soils from six soil profiles in batch experiments after 96 h of shaking ranged from 1.11 to 16.85 μg^1−1/n (mL)^1/n g⁻¹, and the exponent 1/n values from 0.74 to 1.04. The adsorption of tebuconazole was inversely correlated with the soil pH. Both neutral and protonated forms of this organic base were adsorbed mainly on the fraction of humins. The adsorption of the protonated form increased in the presence of hydrogen cations adsorbed in the soil sorption sites. Fourier transform infrared spectroscopy coupled with the molecular modeling studies and partial least squares regression analysis indicated that the tebuconazole molecule is bound in the organic matter through the formation of hydrogen bonds as well as hydrophobic and π–π interactions. Ion exchange was one of the adsorption mechanisms of the protonated form of this fungicide. The created mathematical model, assuming that both forms of tebuconazole are adsorbed on the organic matter and adsorption of the protonated form is affected by the potential acidity, described its adsorption in soils well.     

Atomic absorption spectrophotometric determination of trace copper in waters, aluminium foil and tea samples after preconcentration with 1-nitroso-2-naphthol-3,6-disulfonic acid on Ambersorb 572

An atomic absorption spectrophotometric method for the determination of trace copper after adsorption of its 1-nitroso-2-naphthol-3,6-disulfonic acid chelate on Ambersorb 572 has been developed. This chelate is adsorbed on the adsorbent in the pH range 1–8. The copper chelate is eluted with 5 ml of 0.1 mol l⁻¹ potassium cyanide and determined by flame atomic absorption spectrometry (FAAS). The selectivity of the proposed procedure was also evaluated. Results show that iron(III), zinc(II), manganese(II) and cobalt(II) at the 50 μg l⁻¹ level and sodium(I), potassium(I), magnesium(II), calcium(II) and aluminium(III) at the 1000 μg l⁻¹ level did not interfere. A high enrichment factor, 200, was obtained. The detection limit (3σ) of copper was 0.34 μg l⁻¹. The precision of the method, evaluated by seven replicate analyses of solutions containing 5 μg of copper was satisfactory and the relative standard deviation was 1.7%. The adsorption of copper onto Ambersorb 572 can formally be described by a Langmuir equation with a maximum adsorption capacity of 14.3 mg g⁻¹ and a binding constant of 0.00444 l mg⁻¹. The accuracy of the method is confirmed by analysing tomatoes leaves (NIST 1573a) and lead base alloy (NBS 53e). The results demonstrated good agreement with the certified values. This procedure was applied to the determination of copper in waters (tap, river and thermal waters), aluminium foil and tea samples.     

烷基十八胺在离子交换树脂上的吸附及影响研究

研究发现，各种离子交换树脂对烷基十八胺均有较强的吸附作用，阳树脂吸附作用最强，可以近似100％吸附，吸附烷基十八胺后的树脂强度降低，沉降速度改变。常用的无机复苏液无法将吸附的十八胺洗脱出来。     

Calorimetric comparison of the interactions between salivary proteins and Streptococcus mutans with and without antigen I/II

Antigen I/II can be found on streptococcal cell surfaces and is involved in their interaction with salivary proteins. In this paper, we determine the adsorption enthalpies of salivary proteins to Streptococcus mutans LT11 and S. mutans IB03987 with and without antigen I/II, respectively, using isothermal titration calorimetry. In addition, protein adsorption to the cell surfaces was determined spectrophotometrically. S. mutans LT11 with antigen I/II, yielded a much higher, exothermic adsorption enthalpy at pH 6.8 (ranging from −2073 × 10⁻⁹ to −31707 × 10⁻⁹ μJ per bacterium) when mixed with saliva than did S. mutans IB03987 (−165 × 10⁻⁹ to −1107 × 10⁻⁹ μJ per bacterium) at all bacterial concentrations studied (5 × 10⁹, 5 × 10⁸, and 5 × 10⁷ ml⁻¹), largest effects per bacterium being observed for the lowest concentration. However, the enthalpy of salivary protein adsorption to S. mutans LT11 became smaller at pH 5.8. Adsorption isotherms for the S. mutans LT11 showed considerable protein adsorption at pH 6.8 (1.2–2.1 mg/m²), that decreased only slightly at pH 5.8 (1.1–1.6 mg/m²), with the largest amount adsorbed at the lowest bacterial concentration. This suggests that the protein(s) in the saliva with the strongest affinity for antigen I/II is (are) readily depleted from saliva. In conclusion, antigen I/II surface proteins on S. mutans play a determinant role in adsorption of salivary proteins through the creation of enthalpically favorable adsorption sites.     

Adsorption of Pseudomonas putida on clay minerals and iron oxide

Adsorption of Pseudomonas putida on minerals including montmorillonite, kaolinite and goethite was studied. The adsorption isotherms of P. putida on the examined minerals conformed to the Langmuir equation. The amount of P. putida adsorbed followed the order: goethite > kaolinite > montmorillonite. A greater extent of P. putida adsorption on minerals was observed in the range of temperature from 15 to 35 °C. The adsorption of P. putida on minerals decreased with the increase of pH from 3.0 to 10.0. Magnesium ion was more efficient than sodium ion in promoting P. putida adsorption on minerals. The results suggest that electrostatic interactions play a vital role in P. putida adsorption by soil colloidal factions. The information obtained in this study is of fundamental significance for the understanding of the survival and transport of bacteria in soil systems.     

Preconcentration and decomposition of perfluorinated carboxylic acids on an activated charcoal cartridge with sodium biphenyl reagent and its determination at microg L(-1) level on the basis of flow injection-fluorimetric detection of fluoride ion

Perfluorinated surfactants of heptafluorobutylate and pentadecafluorooctanoate ions were adsorbed on an activated charcoal cartridge and decomposed with sodium biphenyl (SBP) reagent to form inorganic fluoride ion. The fluoride ion thus formed was determined by flow injection analysis (FIA) using quercetin-Zr complex as a fluorimetric reagent, where λ_ex and λ_em were 422 and 491 nm, respectively. The limit of detection for fluoride ion by the FIA system was developed to 1.1 × 10⁻⁶ M (signal to noise ratio of three), when 50% (v/v) tetrahydrofuran (THF) was used as a dissolving solvent for quercetin. The perfluorinated surfactants in the sample solution were quantitatively adsorbed on the cartridge containing 100 mg of activated charcoal and were decomposed with 0.5 mL of sodium biphenyl reagent after drying thoroughly by flowing through dry nitrogen gas. The fluoride ion formed was recovered with 3 mL of purified water as an eluent, and it was determined by the fluorimetric flow injection system. The blank fluorescence signal accompanied during the adsorption/decomposition on the cartridge was reduced by washing the activated charcoal with acetone. The blank signal was also observed from dimethoxyethane, which was used in sodium biphenyl reagent. When 600 mL sample solution was used and 200 times enrichment was applied, the heptafluorobutylate and pentadecafluorooctanoate ions at the concentrations of 2.1 μg L⁻¹ were quantitatively recovered as fluoride ion, and the limit of detections for the perfluorinated surfactants were 0.3 and 0.3 μg L⁻¹ for the two perfluorinated surfactants, respectively (3 sigma of the blank signal).     

Adsorption and desorption of lysozyme on nano-sized magnetic particles and its conformational changes

Adsorption and desorption of lysozyme on nano-sized magnetic particles and its conformational change were studied in this work. Adsorption of lysozyme on nano-sized magnetic particles (Fe₃O₄) was carried out at different pH. Maximum adsorption of lysozyme (4.65 mg/m²) occurred at its isoelectric point (pI=11.1). Differential scanning calorimetry (DSC) results show that the lysozyme adsorbed on magnetic particles did not show any thermal transition over the range 20–100 °C. High desorption of lysozyme from magnetic particles was achieved using NaH₂PO₄ (pH 4.0) (90%) and NaSCN (pH 6.0) (97%) as desorbents. The conformational change of the lysozyme desorbed by NaH₂PO₄ was small, while the lysozyme desorbed by NaSCN underwent a significant conformational change as measured by the intrinsic fluorescence. Eighty-eight and 82% activity was retained in the desorbed enzyme for desorption by NaH₂PO₄ and NaSCN, respectively.     

Experiment and theory of low-pressure nitrogen adsorption in organic layers supported or grafted on inorganic adsorbents: toward a tool to characterize surfaces of hybrid organic/inorganic systems

We report experimental nitrogen adsorption isotherms of organics-coated silicas, which exhibit a low-pressure desorption branch that does not meet the adsorption branch upon emptying of the pores. To address the physical origin of such a hysteresis loop, we propose an equilibrium thermodynamic model that enables one to explain this phenomenon. The present model assumes that, upon adsorption, a small amount of nitrogen molecules penetrate within the organic layer and reach adsorption sites that are located on the inorganic surface, between the grafted or adsorbed organic molecules. The number of accessible adsorption sites thus varies with the increasing gas pressure, and then we assume that it stays constant upon desorption. Comparison with experimental data shows that our model captures the features of nitrogen adsorption on such hybrid organic/inorganic materials. In particular, in addition to predicting the shape of the adsorption isotherm, the model is able to estimate, with a reasonable number of adjustable parameters, the height of the low-pressure hysteresis loop and to assess in a qualitative fashion the local density of the organic chains at the surface of the material.     

Adsorption of trimethylamine on zirconium silicate and polyethylene powder surfaces

Sorptive interactions of volatile organic compounds (VOCs) with indoor surfaces play a major role in inhalation exposure to these species. Using ZrSiO₄ and polyethylene (PE) to model mineral surfaces and carpeting, respectively, the adsorption behavior of gaseous trimethylamine (TMA) was examined under conditions of 80% relative humidity (RH) in N₂ and in the presence of 1000 ppm CO₂ or NH₃. TMA adsorption and desorption behavior were studied using attenuated total reflection infrared (ATR-IR) and X-ray photoelectron (XPS) spectroscopies. Spectral data revealed that TMA adsorbed on both surfaces in a protonated state. Stronger adsorption was observed to occur on ZrSiO₄. XPS scans indicate that the “dry” ZrSiO₄ surface maintains OH groups available for bonding, supporting earlier research showing that partition coefficients increase as RH decreases.     

Novel hydrophobic ligand-containing hydrogel membrane matrix: preparation and application to gamma-globulins adsorption

In this study, phenylalanine as a hydrophobic ligand was covalently attached to the co-monomer methacrylochloride. Then, poly(2-hydroxyethylmethacrylate-co-methacrylamidophenyalanine) [poly(HEMA–MAPA)] membranes were prepared by UV-initiated photopolymerization of HEMA and methacrylamidophenyalanine. The γ-globulins adsorption onto these affinity membranes from aqueous solutions containing different amounts of γ-globulins at different pH was investigated in a batch system. The γ-globulins adsorption capacity of the membranes was increased as the ligand density on the membrane surface increase. The non-specific adsorption of the γ-globulins on the pHEMA membranes was negligible. The adsorption phenomena appeared to follow a typical Langmuir isotherm. The maximum adsorption capacity (q_m) of the poly(HEMA–MAPA4) membrane for γ-globulins was 2.37 mg g⁻¹ dry membrane. The equilibrium constant (k_d) value was found to be 1.61×10⁻¹ mg ml⁻¹. More than 87% (up to 100%) of the adsorbed γ-globulins were desorbed in 120 min in the desorption medium containing 50% ethylene glycol in 1.0 M NaCl.     

Nitrofuran antibiotic residues in pork: The FoodBRAND retail survey

Use of nitrofuran drugs in food-producing animals has been prohibited within the EU because they may represent a public health risk. Monitoring compliance with the ban has focused on the detection of protein-bound nitrofuran metabolites which, in contrast to the parent compounds, are stable and persist in animal tissues. As part of the “FoodBRAND” project, an extensive survey of pork was undertaken across 15 European countries. Samples (n = 1500) purchased at retail outlets were analysed for the nitrofuran metabolites AOZ, AMOZ, AHD and SEM using LC–MS/MS determination of nitrobenzaldehyde derivatives. Limits of quantification for the method were 0.1 μg/kg (AOZ, AMOZ), 0.2 μg/kg (SEM) and 0.5 μg/kg (AHD). Of the 1500 samples tested, measurable residues of nitrofuran metabolites were confirmed in 12 samples (0.8% incidence overall) of which 10 samples were purchased in Portugal (AOZ, 0.3 μg/kg; AMOZ, 0.2–0.6 μg/kg) and one sample each in Italy (AMOZ, 1.0 μg/kg) and Greece (AOZ, 3.0 μg/kg).     

Interaction between tetracycline and smectite in aqueous solution

The fate and transport of commonly used antibiotics in soil and groundwater have attracted renewed studies due to increased sensitivities of analytical instruments and thus frequent detections of these compounds even in treated wastewater. Smectite, an important soil component, has large surface area and high cation exchange capacity, while tetracycline (TC) can exist in different forms and charges under different pH conditions. Thus, the interaction between smectite and TC in aqueous systems is of great importance. This research focused on elucidating the mechanisms of TC uptake by smectite, in terms of TC adsorption, cation desorption, and pH changes associated with TC adsorption by smectite and intercalation in smectite. TC adsorption onto smectite was a relatively fast process even though most of the adsorption sites were in the interlayer position involved in intercalation as confirmed by the expansion of d₀₀₁ spacing. The TC adsorption capacity was equivalent to 0.74–1.11 times the cation exchange capacity for three of the four smectite minerals studied. Accompanying TC adsorption was simultaneous adsorption of H⁺, resulting in protonation of TC on the dimethylamine group. At higher TC input concentrations further adsorption of H⁺ resulted in the ratio of H⁺ adsorbed to TC adsorbed greater than one, suggesting that additionally adsorbed H⁺ could serve as counterions to partially offset the negative charges on the tricarbonyl or phenolic diketone functional groups. The positive correlations between cations desorbed and TC adsorbed, as well as TC adsorbed and H⁺ adsorbed, provided a first time evidence to confirm cation exchange as the main mechanism of TC uptake, even under neutral pH conditions.