Semi-analytical mean-field model for predicting breathing in metal–organic frameworks

A new semi-analytical mean-field model is proposed to rationalise breathing of MIL-53 type materials. The model is applied on two case studies, the guest-induced breathing of MIL-53(Cr) with CO₂ and CH₄, and the phase transformations for MIL-53(Al) upon xenon adsorption. Experimentally, MIL-53(Cr) breathes upon CO₂ adsorption, which was not observed for CH₄. This result could be ascribed to the stronger interaction of carbon dioxide with the host matrix. For MIL-53(Al) a phase transition from the large pore phase could be enforced to an intermediate phase with volumes of about 1160–1300 Å³, which corresponds well to the phase observed experimentally upon xenon adsorption. Our thermodynamic model correlates nicely with the adsorption pressure model proposed by Coudert et al. Furthermore the model can predict breathing behaviour of other flexible materials, if the user can determine the free energy of the empty host, the interaction energy between a guest molecule and the host matrix and the pore volume accessible to the guest molecules. This will allow to generate the osmotic potential from which the equilibria can be deduced and the anticipated experimentally observed phase may be predicted.     

Theoretical study of conformational disorder and selective adsorption of small organic molecules in the flexible metal-organic framework material MIL-53-Fe

Many of the potential applications for metal-organic framework (MOF) materials require molecular level understanding of their adsorption of small organic molecules, which are not readily accessible from experiment. Through high-level van der Waals corrected, hybrid density functional theory calculations, we elucidate the adsorption configurations of several, representative small organic guest molecules in an archetypal flexible MOF material, MIL-53-Fe. The predicted relative energies between low-energy adsorption configurations of 1,4-benzoquinone in MIL-53-Fe are in very good agreement with the thermal transition temperatures observed experimentally and suggest that thermodynamic factors govern the precise arrangements and loading of guests in the MOF host. Experimentally observed conformational disorder of small organic molecules in MIL-53-Fe is explained by predicted multiple low-energy adsorption configurations that are comparable with the thermal energy of the guests, kT. Finally, we show that the previously observed selective adsorption of pyridine and 2,6-lutidine molecules in water by MIL-53-Fe, can be rationalised through a careful analysis of the host–guest and guest–guest interactions and is controlled by thermodynamic factors.     

Evaluating adsorbed-phase activity coefficient models using a 2D-lattice model

Despite the wide use of the real adsorbed solution theory to predict multicomponent adsorption equilibrium, the models used for the adsorbed phase activity coefficients are usually borrowed from the gas–liquid phase equilibria. In this work, the accuracy of the Wilson and NRTL models for evaluating adsorbed phase activity coefficients is tested using a 2D-lattice model. An accurate model for adsorbed-phase activity coefficients should have no problem in fitting adsorption data obtained using this simple lattice model. The results, however, show that the commonly used Wilson and NRTL models cannot describe the adsorbed phase activity coefficients for slightly non-ideal to strong non-ideal mixtures. Therefore, until new models for adsorbed phase activity coefficients are developed, we should use existing models for liquids with care. In the second part of this work, the use of Monte Carlo simulations on a segregated 2D-lattice model, for predicting adsorption of mixtures is investigated. The segregated model assumes that the competition for adsorption occurs at isolated adsorption sites, and that the molecules from each adsorption site interact with the bulk phase independently. Two binary mixtures in two adsorbent materials were used as case studies for testing the predictions of the segregated 2D-lattice model: the binary system CO₂–N₂ in the hypothetical pure silica zeolite PCOD8200029, with isolated adsorption sites and normal preference for adsorption, and the binary system CO₂–C₃H₈ in pure silica mordenite (MOR), with isolated adsorption sites and inverse site preference. The segregated 2D-lattice model provides accurate predictions for the system CO₂–N₂ in PCOD8200029 but fails in predicting the adsorption behaviour of CO₂–C₃H₈ in pure silica MOR. The predictions of the segregated ideal adsorbed solution theory model are superior to those of the 2D-lattice model.     

Differences in the adsorption and diffusion behaviour of water and non-polar gases in nanoporous carbon: role of cooperative effects of pore confinement and hydrogen bonding

We investigate the effect of pore confinement and molecular geometry on the adsorption and self-diffusion of H₂O, CO₂, Ar, CH₄, C₃H₆, SF₆ and C₅H₁₂, in a realistic model of nanoporous silicon carbide derived carbon (SiC-DC), constructed using hybrid reverse Monte Carlo simulation. Adsorption isotherms, adsorbate–adsorbate and adsorbate–adsorbent contributions to the isosteric heat of adsorption are determined to study the effect of pore confinement, microporosity and molecular geometry on adsorption of these gases. We describe the cooperative effect of pore confinement and hydrogen bonding on the formation of water clusters and anomalous adsorption behaviour of water compared with non-polar gases. We find that, in contrast to literature results based on the slit-pore model, pore-filling does not occur below the saturation pressure in hydrophobic amorphous carbon materials such as SiC-DC and activated carbon fibre. We also compare self-diffusivities and activation energy barriers of water and non-polar gases in the microporous structure of SiC-DC to identify underlying correlations with molecular properties. We demonstrate that the self-diffusivity of water deviates considerably from the correlation between diffusivity and molecular kinetic diameter observed for non-polar gases. This is attributed to the reduced diffusivity of water, and its relatively large energy barrier at high loadings despite its small kinetic diameter, which is due to the blocking effect of water clusters at pore entries.     

Enhanced bioelectrochemical performance caused by porous metal-organic framework MIL-53(Fe) as the catalyst in microbial fuel cells

To enhance the oxygen reduction reaction (ORR) activity and power generation capacity of a microbial fuel cell (MFC), MIL-53(Fe) (Fe-based Materials of Institute Lavoisier) as the electrochemical catalyst was synthesized using the hydrothermal method. The catalytic structure and morphology of all materials were comprehensively characterized by Fourier Transform infrared spectrometer (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). The results show that there were many nanopores on MIL-53(Fe), which improved the electrocatalytic activity. The MIL-53(Fe)-modified air cathode MFC had a voltage output of approximately 0.37 V and maintained that output for one week. The maximum power density was 397 ± 6.3 mW/m². MIL-53(Fe) was an excellent electrochemical catalyst, significantly enhancing the catalytic oxygen reduction ability and promoting the power output of the MFC. This study provides a method to apply MIL-53(Fe) materials in microbial fuel cells.     

Theoretical Studies on α-Helix—DNA Interactions

Abstract

The ¹H NMR relaxation effects produced by paramagnetic Cr(III) complexes on nucleoside 5′-mono- and -triphosphates in D₂O solution at Ph′=3 were measured. The paramagnetic probes were [Cr(III)(H₂O) ₆]³⁺, [Cr(III)(H₂O)₃ (HATP)], [Cr(III)(H₂O)₃(HCTP)] and [Cr(III) (H₂O)₃(UTP)^?, while the matrix nucleotides (0.1 M) were H₂AMP, HIMP^?, and H₂ATP^2-. For the aromatic base protons, the ratios of the transverse to longitudinal paramagnetic relaxation rates (R_2p/R_1p) for the [Cr(III)(H₂O)₆]³⁺/H₂ATP^2-, [Cr(III)(H₂O)₃(HATP)]/H₂ATP^2-, [Cr(III)(H₂O)₃(HCTP)]/H₂ATP² and [Cr(III)(H₂O)₃(UTP)]^?/H₂ATP² systems were below 2.33 so the dipolar term predominates. For a given nucleotide, R_1p for the purine H(8) signal was larger than for the H(2) signal with the [Cr(III)(H₂O)₆]³⁺ probe, while R_1p for the H(2) signal was larger with all the other Cr(III) probes. Molecular mechanics computations on the [Cr(III)(H₂O)₄(HPP)(α,β)], [Cr(III)(NH₃)₄(HPP)(α,β)], [Co(III)(NH₃)₃(H₂PPP)(α,βγ)] and [Co(III)(NH₃)₄(HPP)(α,β)] complexes gave calculated energy-minimized geometries in good agreement with those reported in crystal structures. The molecular mechanics force constants found were then used to calculate the geometry of the inner sphere [Cr(III)(H₂O)₆]³⁺ and [Cr(III)(H₂O)₃(HATP)(α,βγ)] complexes as well as the structures of the outer sphere [Cr(III) (H₂O)₆]³⁺-(H₂AMP) and [Cr(III)(H₂O)₆]-(HIMP)^? species. The gas-phase structure of the [Cr(III)(H₂O)₃(HATP)(α,βγ)] complex shows the existence of a hydrogen bond interaction between a water ligand and the adenine N(7) (O…N = 2.82 Å). The structure is also stabilized by intramolecular hydrogen bonds involving the -O(2′)H group and the adenine N(3) (O…N = 2.80 Å) as well as phosphate oxygen atoms and a water molecule (O…O = 2.47 Å). The metal center has an almost regular octahedral coordination geometry.

The structures of the two outer-sphere species reveal that the phosphate group interacts strongly with the hexa-aquochromium probe. In both complexes, the nucleotides have a similar “anti” conformation around the N(9)-C(l′) glycosidic bond. However, a very important difference characterizes the two structures. For the (HIMP)^? complex, strong hydrogen bond interactions exist between one and two water ligands and the inosine N(7) and O(6) atoms, respectively (O…O = 2.63 Å O…N = 2.72, 2.70 Å). For the H₂AMP complex, the [Cr(III) (H₂O)c]³⁺ cation does not interact with N(7) since it is far from the purine system. Hydrogen bonds occur between water ligands and phosphate oxygens. The Cr-H(8) and Cr-H(2) distances revealed by the energy-minimized geometries for the two outer sphere species were used to calculate the R_1p values for the H(8) and H(2) signals for comparison with the observed R_1p values: 0.92(c), 1.04(ob) (H(8)) and 0.06(c), 0.35(ob) (H(2)) for H₂AMP; and 3.76(c), 4.53(ob) (H(8)) and 0.16(c), 0.77(ob) s^?1 (H(2)) for HIMP^?. These results suggest that the dynamic relaxation effects can be only partially understood with molecular mechanics computations, although the success of the geometry calculations suggests that future efforts in the development of computational methods are justified.     

Evaluation of urinary biomarkers of oxidative/nitrosative stress in adolescents and adults with Down syndrome

Urinary biomarkers of oxidative stress have been little studied in adults with Down syndrome (DS), usually no more than two biomarkers have been measured in the population studied and controversial results are reported in literature. Thus, we aimed to assess a set of oxidative and nitrosative stress biomarkers in urine samples of adolescents and adults with DS, with and without hypothyroidism, which comprise: 8-hydroxy-2′-deoxyguanosine (8-OHdG), isoprostane 15-F_2t-IsoP, thiobarbituric acid-reacting substances (TBARS), advanced glycation end products (AGEs), dityrosine (diTyr), hydrogen peroxide (H₂O₂) and nitrite/nitrate (NOx). Fluorimetric and spectrophotometric assays were performed in DS (n = 78), some of them taking levothyroxine for hypothyroidism (n = 24), and in their healthy age-matched controls (n = 65). We found that levels of AGEs, diTyr, H₂O₂ and NOx are increased in DS patients in any or in all age groups, whereas Cr levels were lower in DS than in controls in all age groups. Besides, correlations with age in DS were positive for diTyr and negative for Cr, TBARS, 15-F_2t-IsoP and NOx. We also found lower levels of Cr from 15 to 19 years, higher levels of TBARS and AGEs from 20 to 40 years and higher levels of diTyr from 15 to 40 years in DS patients receiving levothyroxine than in DS without hypothyroidism diagnosed. We conclude that AGEs, diTyr, H₂O₂ and NOx could be used as oxidative stress biomarkers in DS in contrast to 8-OHdG, 15-F_2t-IsoP and TBARS, at least with the methods used. However, renal impairment could occur in DS and Cr adjustment may bias the results, particularly in hypothyroid patients.     

Computational exploration of the gas adsorption on the iron tetracarboxylate metal-organic framework MIL-102

Density functional theory calculations have been combined with forcefield-based grand canonical Monte Carlo simulations to explore the adsorption of CO₂, N₂, CH₄ and H₂ on the small one-dimensional channel MIL-102, a naphthalene tetracarboxylate-based metal-organic framework (MOF) built up from a connection of trimers of trivalent iron. A detailed analysis is provided on the preferential arrangement of the confined adsorbates as well as the energetics of the host/guest interactions. The co-adsorption properties of this solid for the elimination of CO₂ from hydrogen, natural and flue gases are then revealed. The so-predicted performances are further compared with those reported so far for a diverse series of MOFs.     

Review of methodologies for extracting plant-available and amorphous Si from soils and aquatic sediments

There is a variety of methodologies used in the aquatic sciences and soil sciences for extracting different forms of Si from sediments and soils. However, a comparison of the published extraction techniques is lacking. Here we review the methodologies used to extract different Si fractions from soils and sediments. Methods were classified in those to assess plant-available Si and those to extract Si from amorphous silica and allophane. Plant-available Si is supposed to comprise silicic acid in soil solution and adsorbed to soil particles. Extraction techniques for plant-available Si include extractions with water, CaCl₂, acetate, acetic acid, phosphate, H₂SO₃, H₂SO₄, and citrate. The extractants show different capabilites to desorb silicic acid, with H₂SO₃, H₂SO₄ and citrate having the greater extraction potential. The most common extractants to dissolve amorphous silica from soils and aquatic sediments are NaOH and Na₂CO₃, but both also dissolve crystalline silicates to varying degrees. In soils moreover Tiron is used to dissolve amorphous silica, while oxalate is used to dissolve allophanes and imogolite-type materials. Most techniques analyzing for biogenic silica in aquatic environments use a correction method to identify mineral derived Si. By contrast, in the soil sciences no correction methods are used although pedologists are well aware of the overestimation of amorphous silica by the NaOH extraction, which is most commonly used to extract silica from soils. It is recommended that soil scientists begin to use the techniques developed in the aquatic sciences, since it seems impossible to extract amorphous Si from soils completely without dissolving some of the crystalline silicates.     

Hydrogen-rich pure water prevents superoxide formation in brain slices of vitamin C-depleted SMP30/GNL knockout mice

Hydrogen is an established anti-oxidant that prevents acute oxidative stress. To clarify the mechanism of hydrogen’s effect in the brain, we administered hydrogen-rich pure water (H₂) to senescence marker protein-30 (SMP30)/gluconolactonase (GNL) knockout (KO) mice, which cannot synthesize vitamin C (VC), also a well-known anti-oxidant. These KO mice were divided into three groups; recipients of H₂, VC, or pure water (H₂O), administered for 33 days. VC levels in H₂ and H₂O groups were <6% of those in the VC group. Subsequently, superoxide formation during hypoxia-reoxygenation treatment of brain slices from these groups was estimated by a real-time biography imaging system, which models living brain tissues, with Lucigenin used as chemiluminescence probe for superoxide. A significant 27.2% less superoxide formed in the H₂ group subjected to ischemia-reperfusion than in the H₂O group. Thus hydrogen-rich pure water acts as an anti-oxidant in the brain slices and prevents superoxide formation.     

Functional dual hydrophilic dendrimer‐modified metal‐organic framework for the selective enrichment of N‐glycopeptides

Analysis of protein glycosylation remains a significant challenge due to the low abundance of glycoproteins or N‐glycopeptides. Here we have synthesized an amino‐functionalized metal‐organic framework (MOF) MIL‐101(Cr)‐NH₂ whose surface is grafted with a hydrophilic dendrimer poly(amidoamine) (PAMAM) for N‐glycopeptide enrichment based on the hydrophilic interactions. The selected substrate MOF MIL‐101(Cr) owns high surface area which provides nice support for peptide adsorption. In addition, the MOF displayed a good hydrophilic property after being modified with amino groups. Most importantly, the grafted hydrophilic dendrimer PAMAM was firstly applied in the postsynthetic modification of MOFs. And this functionalization route using macromolecular dendrimer opens a new perspective in MOFs design. Owing to its long dendritic chains and abundant amino groups, our material displayed dual hydrophilic property. In the enrichment of standard glycoprotein HRP digestion, the functional MOF material was shown to have low detection limit (1 fmol/μL) and good selectivity when the concentration of nonglycopeptides was 100 fold higher than the target N‐glycopeptides. All the results proved that MIL‐101(Cr)‐NH₂@PAMAM has great potential in the glycoproteome analysis.     

小鼠白细胞介素4基因的化学合成、克隆与表达

利用381A型DNA合成仪,分29个寡聚核苷酸片段化学合成了小鼠IL-4全基因,共442bp。以pUC12质粒作为载体,将所有合成片段分前后两组进行磷酸化、退火、连接和克隆,经过菌落原位杂交、酶切鉴定和质粒DNA序列分析,分别得到了含有小鼠IL-4前后两半基因片段的两种重组质粒,回收前半基因片段,插入到含有后半基因重组质粒的EcoRI和PstI酶切位点之间,成功地得到了含有小鼠IL-4全基因的重组质粒pFR101。将全合成基因插入到质粒pSM53中,得表达质粒pFR105,转化大肠杆菌TAP106,根据IL-4对CTLL细胞的作用,肯定了TAP106(pFR105)细菌中有小鼠IL-4活性蛋白的表达。     

ESR Spin Trapping Detection of Hydroxyl Radicals in the Reactions of Cr(V) Complexes with Hydrogen Peroxide

Electron spin resonance (ESR) measurments provide direct evidence for the involvement of Cr(V) in the reduction of Cr(VI) by NAD(P)H. Addition of hydrogen peroxide (H₂O₂) to NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) signal and generates hydroxyl (OH) radicals (as detected via spin trapping), suggesting that Cr(V) reacts with H₂O₂ to generate the OH radicals. Reaction between H₂O₂ and a Cr(V)-glutathione complex. and between H₂O₂ and several Cr(V)-cdrboxylato complexes also produces OH radicals. These results suggest that Cr(V) complexes catalyze the generation of OH radicals from H₂O₂, and that OH radicals might play a significant role in the mechanism of Cr(VI) cytotoxicity.     

Hybrid mesoporous silicates: A distinct aspect to synthesis and application for decontamination of phenols

Water pollution due to organic compounds is of great concern and efforts are being made to develop efficient adsorbents for remediation of toxic pollutants. The development of new functionalized materials with increased performance is growing to meet the regulatory standards in response to public concerns for environment. In this study, an attempt has been made to investigate the influence of synthesis parameters like the reaction temperature, the surfactant-to-silica ratio and reaction time on the structural and textural properties of novel ordered mesoporous silica hybrids. In order to understand the effect of different synthesis parameters, all the prepared materials were systematically characterized by various analytical, spectroscopic and imaging techniques such as XRD, BET, TG etc. It was deduced from these studies that the synthesis temperature influence greatly the structural order whereas both the P104/Na₂SiO₃ molar ratio and reaction time found to influence textural properties significantly. However, under optimized experimental condition, we could achieve the functionalized silica hybrids that offers successful incorporation of -Amino, -Glucidoxy, -Methacrylate, -Vinyl and -Phenyl moieties indicated by FTIR peaks at 793 cm^?1, 2870 cm^?1, 796 cm^?1, 1630 cm^?1 and 954 cm^?1. XRD studies reveal orthorhombic and tetragonal symmetry for the hybrids and these materials were found to be thermally stable due to incorporation of organic moiety in silica matrix. Functionalized silica hybrids then applied as adsorbents demonstrated efficient and comparable removal of 4-aminophenol and p-nitrophenol in 20 min facilitated through organic moiety. Detailed modeling of the sorption using equilibrium and kinetic isotherms has been carried out to get an insight into the transport process. The adsorption isotherms of phenol derivatives are well-fitted with the Langmuir, Freundlich and Temkin Isotherms and the adsorption kinetics follows the pseudo second order model. The modeling confirms that the uptake is a chemisorption process.     

Trivalent chromium pretreatment alleviates the toxicity of oxidative damage in wheat plants exposed to hexavalent chromium

Treating plants with abiotic or biotic factors can lead to the establishment of a unique primed state of defense. Primed plants display enhanced defense reactions upon further challenge with environmental stressors. Here, we report that trivalent chromium (Cr(III)) pretreatment can alleviate hexavalent chromium (Cr(VI)) toxicity in 2-week-old wheat plants. The data indicate that Cr(III)-pretreated wheat displayed longer survival times and less heavy metal toxicity symptoms under Cr(VI) exposure than the control. To investigate the possible mechanism from an antioxidant defense perspective, we determined the H₂O₂ and lipid peroxide content (TBARS), the activities of antioxidant enzymes (SOD, CAT, APX and GR) and the antioxidant metabolite content (ascorbate and glutathione content, AsA/DHA and GSH/GSSG ratios) in pretreated wheat roots. The results showed that 0.5 μM Cr(III) pretreatment can alleviate oxidative damage, such as H₂O₂ and TBARS accumulation, in root tissues compared to the control during the first 3 days of Cr(VI) exposure. Furthermore, we determined that this pretreatment can significantly increase the antioxidant enzyme activities and total ascorbate and glutathione contents compared to the control treatment. In addition, redox homeostasis declined slightly in pretreated wheat compared to the control in the presence of Cr(VI). We discuss a possible mechanism for Cr(III)-mediated protection of wheat.     

Hydrogen peroxide spraying alleviates drought stress in soybean plants

To ascertain the effect of exogenously applied hydrogen peroxide (H₂O₂) on drought stress, we examined whether the spraying of soybean leaves with H₂O₂ would alleviate the symptoms of drought stress. Pre-treatment by spraying leaves with H₂O₂ delayed foliar wilting caused by drought stress compared to leaves sprayed with distilled water (DW). Additionally, the relative water content of drought-stressed leaves pre-treated with H₂O₂ was higher than that of leaves pre-treated with DW. Therefore, we analyzed the effect of H₂O₂ spraying on photosynthetic parameters and on the biosynthesis of oligosaccharides related to water retention in leaves during drought stress. Under conditions of drought stress, the net photosynthetic rate and stomatal conductance of leaves pre-treated with H₂O₂ were higher than those of leaves pre-treated with DW. In contrast to DW spraying, H₂O₂ spraying immediately caused an increase in the mRNA levels of d-myo-inositol 3-phosphate synthase 2 (GmMIPS2) and galactinol synthase (GolS), which encode key enzymes for the biosynthesis of oligosaccharides known to help plants tolerate drought stress. In addition, the levels of myo-inositol and galactinol were higher in H₂O₂-treated leaves than in DW-treated leaves. These results indicated that H₂O₂ spraying enabled the soybean plant to avoid drought stress through the maintenance of leaf water content, and that this water retention was caused by the promotion of oligosaccharide biosynthesis rather than by rapid stomatal closure.     

Hydrogen sulfide alleviates chromium stress on cauliflower by restricting its uptake and enhancing antioxidative system

The present study evaluated the physiological and biochemical mechanisms through which exogenous sodium hydrosulfide (H₂S donor) mitigates chromium (Cr) stress in cauliflower. The different levels of Cr included 0, 10, 100 and 200 µM. Results reported that Cr exposure reduced growth and biomass, chlorophyll (Chl) contents, gas exchange parameters and enzymatic antioxidants. Chromium stress enhanced the production of electrolyte leakage (EL), hydrogen peroxide (H₂O₂) and malondialdehyde (MDA) contents and increased Cr content in the roots, stem, leaf and flowers. Exogenous H₂S improved the physiological and biochemical attributes of Cr-stressed cauliflower. Hydrogen sulfide decreased Cr content in different parts of Cr-stressed plants, whereas it increased the Chl contents and gas exchange attributes. H₂S reduced the EL, H₂O₂ and MDA concentrations, enhancing the antioxidant enzymes activities in Cr-stressed roots and leaves compared to the Cr treatments alone. Collectively, our results provide an insight into the protective role of H₂S in Cr-stressed cauliflower and suggest H₂S as a potential candidate in reducing Cr toxicity in cauliflower and other crops.     

Biogas upgrading using single-walled carbon nanotubes by molecular simulation

Abstract

Biogas from anaerobic digestion of biological wastes is a renewable energy resource that mainly contains CH₄, CO₂, trace amounts of H₂S and a fraction of H₂O vapour. In order to transfer biogas into biomethane to meet the standards for use as vehicle fuel or for injection in the natural gas grid, removing H₂S from biogas in advance is necessary. In addition, biogas is usually saturated with water vapour. It is significant to study the effect of the presence of H₂O on the biogas separation performance. Adsorption of H₂S/CO₂/CH₄ and H₂O/CO₂/CH₄ ternary mixtures using single-walled carbon nanotubes (SWCNT) were investigated via the Grand Canonical Monte Carlo (GCMC) method. We studied the effects of carbon nanotube diameter, –COOH modification, temperature and pressure on H₂S adsorption. The results indicate that the presence of hydrophilic –COOH groups does affect the separation of H₂S/CO₂/CH₄ mixtures. Temperature swing adsorption is more suitable than pressure swing adsorption for the separation of H₂S/CO₂/CH₄ mixtures. The effect of water vapour on the separation of CO₂/CH₄ was also investigated. The result shows that the presence of H₂O has little effect on the selectivity of CO₂/CH₄ in pristine CNT, but the selectivity of CO₂/CH₄ with the presence of H₂O is markedly enhanced after modification in –COOH modified SWCNT with specific modification degree. It is expected that this work could provide some useful information for biogas upgrading.     

Heterogeneity and incorporation of chromium isotopes in recent marine molluscs (Mytilus)

The mollusc genus Mytilus is abundant in various modern marine environments and is an important substrate for palaeo‐proxy work. The redox‐sensitive chromium (Cr) isotope system is emerging as a proxy for changes in the oxidation state of the Earth's atmosphere and oceans. However, potential isotopic offsets between ambient sea water and modern biogenic carbonates have yet to be constrained. We measured Cr concentrations ([Cr]) and isotope variations (δ⁵³Cr) in recent mollusc shells (Mytilus) from open and restricted marine environments and compared these to ambient sea water δ⁵³Cr values. We found a large range in mollusc [Cr] (12–309 ppb) and δ⁵³Cr values (?0.30 to +1.25‰) and in the offset between δ⁵³Cr values of mollusc shells and ambient sea water (, ?0.17 to ?0.91‰). Step digestions of cultivated Mytilus edulis specimens indicate that Cr is mainly concentrated in organic components of the shell (periostracum: 407 ppb, n = 2), whereas the mollusc carbonate minerals contain ≤3 ppb Cr. Analyses of individual Cr‐hosting phases (i.e., carbonate minerals and organic matrix) did not reveal significant differences in δ⁵³Cr values, and thus, we suggest that Cr isotope fractionation may likely take place prior to rather than during biomineralisation of Mytilus shells. Heterogeneity of δ⁵³Cr values in mollusc shells depends on sea water chemistry (e.g., salinity, food availability, faeces). The main control for δ⁵³Cr values incorporated into shells, however, is likely vital effects (in particular shell valve closure time) since Cr can be partially or quantitatively reduced in sea water trapped between closed shell valves. The δ⁵³Cr values recorded in Mytilus shells may thus be de‐coupled from the redox conditions of ambient sea water, introducing additional heterogeneity that needs to be better constrained before using δ⁵³Cr values in mollusc shells for palaeo‐reconstructions.