Carbon Nanofiber Membranes Loaded with MXene@g-C3N4: Preparation and Photocatalytic Property.

In this study, a Ti3C2 MXene@g-C3N4 composite powder (TM-CN) was prepared by the ultrasonic self-assembly method and then loaded onto a carbon nanofiber membrane by the self-assembly properties of MXene for the treatment of organic pollutants in wastewater. The characterization of the TM-CN and the C-TM-CN was conducted via X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectrometer (FTIR) to ascertain the successful modification. The organic dye degradation experiments demonstrated that introducing an appropriate amount of Ti3C2 MXene resulted in the complete degradation of RhB within 60 min, three times the photocatalytic efficiency of a pure g-C3N4. The C-TM-CN exhibited the stable and outstanding photocatalytic degradation of the RhB solution over a wide range of pH values, indicating the characteristics of the photodegradation of organic pollutants in a wide range of aqueous environments. Furthermore, the results of the cyclic degradation experiments demonstrated that the C-TM-CN composite film maintained a degradation efficiency of over 85% after five cycles, thereby confirming a notable improvement in its cyclic stability. Consequently, the C-TM-CN composite film exhibits excellent photocatalytic performance and is readily recyclable, making it an auspicious eco-friendly material in water environment remediation.

Coaxial microfluidic spinning design produced high strength alginate membranes for antibacterial activity and drug release.

Directional drug delivery and sufficient strength are two conditions that need to be met for wound dressing. In this paper, an oriented fibrous alginate membrane with sufficient strength was constructed via coaxial microfluidic spinning, and zeolitic imidazolate framework-8/ascorbic acid was used to realize drug delivery and antibacterial activity. The effects of the process parameters of the coaxial microfluidic spinning on the mechanical properties of the alginate membrane were discussed. In addition, it was found that the antimicrobial activity mechanism of zeolitic imidazolate framework-8 was attributed to the disruptive effect of reactive oxygen species (ROS) on bacteria, and the quantitative amount of generated ROS were evaluated by detecting •OH and H2O2. Furthermore, a mathematical drug diffusion model was established and showed high consistency with the experimental data (R2 = 0.99). This study provides a new idea for the preparation of dressing materials with high strength and directional drug delivery and also provides some guidance for the development of coaxial microfluidic spin technology to be used in functional materials for drug release.

The microbiome and its association with antibiotic resistance genes in the hadal biosphere at the Yap Trench.

The hadal biosphere, the deepest part of the ocean, is known as the least-explored aquatic environment and hosts taxonomically diverse microbial communities. However, the microbiome and its association with antibiotic resistance genes (ARGs) in the hadal ecosystem remain unknown. Here, we profiled the microbiome diversity and ARG occurrence in seawater and sediments of the Yap Trench (YT) using metagenomic sequencing. Within the prokaryote (bacteria and archaea) lineages, the main components of bacteria were Gammaproteobacteria (77.76 %), Firmicutes (8.36 %), and Alphaproteobacteria (2.25 %), whereas the major components of archaea were Nitrososphaeria (6.51 %), Nanoarchaeia (0.42 %), and Thermoplasmata (0.25 %), respectively. Taxonomy of viral contigs showed that the classified viral communities in YT seawater and sediments were dominated by Podoviridae (45.96 %), Siphoviridae (29.41 %), and Myoviridae (24.63 %). A large majority of viral contigs remained uncharacterized and exhibited endemicity. A total of 48 ARGs encoding resistance to 12 antibiotic classes were identified and their hosts were bacteria and viruses. Novel ARG subtypes mexFYTV-1, mexFYTV-2, mexFYTV-3, vanRYTV-1, vanSYTV-1 (carried by unclassified viruses), and bacAYTB-1 (carried by phylum Firmicutes) were detected in seawater samples. Overall, our findings imply that the hadal environment of the YT is a repository of viral and ARG diversity.

Natural-clay-reinforced hydrogel adsorbent: Rapid adsorption of heavy-metal ions and dyes from textile wastewater.

In this study, two natural clay minerals were combined with hydrogels to study the influence of natural adsorbents on the adsorption performance of hydrogels. Here, we separately doped bentonite and vermiculite and discussed their mechanical properties and adsorption properties. It was found that the compressive performance of the hydrogel added with clay increased by 21.6% and the swelling performance decreased or increased to varying degrees. Regarding the adsorption performance of hydrogels, it can be seen from the adsorption Langmuir isotherm model that the adsorption capacity of clay-hydrogels is improved to varying degrees (6.6%-15.8%) compared with non-clay-hydrogels, and clay-hydrogels have different degrees of improvement (6.6%-15.8%). The hydrogel has a removal efficiency of more than 95% for low concentrations of heavy-metal ions and dyes. In addition, the clay-hydrogel has low cost and is easy to prepare, and can be recycled many times. Therefore, the material is of great significance for the treatment of pollutants. PRACTITIONER POINTS: The effect of natural clay on the adsorption performance of hydrogels was studied. Clay can enhance the compression and adsorption properties of hydrogels. The adsorption mechanism and adsorption capacity of clay hydrogels were evaluated.

Expression of LINC00847 in Peripheral Blood Mononuclear Cells of Children with Asthma and Its Prediction between Asthma Exacerbation and Remission.

Objective: Asthma is defined as a heterogeneous disease that is usually characterized by chronic airway inflammation. Long noncoding RNAs play important roles in various biological processes including inflammation. To know more about the relationships between lncRNAs and asthma, we sought to the role of LINC00847 in peripheral blood mononuclear cells (PBMCs) of children with asthma exacerbation or asthma remission. Methods: Microarray analysis was performed on GSE143192 and GSE165934 datasets to screen differentially expressed lncRNAs (DElncRNAs) in human PBMCs between asthma patients and normal controls. LINC00847 was selected from DElncRNAs in human PBMCs between asthma patients and normal controls for further investigation. The expression levels of LINC00847 were quantified in PBMCs collected from 54 children with asthma exacerbation, 54 children with asthma remission, and 54 healthy children by real-time qPCR. The forced expiratory volume in the first second in percent predicted values (FEV1%), ratio of forced expiratory volume in 1 second to forced vital capacity (FEV1/FVC), and peak expiratory flow rate (PEF%) were tested for evaluation of lung function. The concentration of immunoglobulin E (IgE) and eosinophil count was examined. The serum levels of interleukin-4 (IL-4), interferon-γ (IFN-γ), and IL-17A were determined by the ELISA method. Results: The expression level of LINC00847 in PBMCs of asthma exacerbation children was remarkably higher than that in PBMCs of asthma remission children and healthy children (p < 0.001); the expression level of LINC00847 in PBMCs of asthma remission children was notably higher than that in PBMCs of healthy children (p < 0.001). Pearson correlation analysis revealed that the expression levels of LINC00847 in PBMCs of asthma children were negatively correlated with FEV1% (r = -0.489), FEV1/FVC (r = -0.436), PEF% (r = -0.626), and IFN-γ level (r = -0.614) of asthma children, but positively correlated with IgE concentration (r = 0.680), eosinophil count (r = 0.780), IL-4 (r = 0.524), and IL-17A (r = 0.622) levels. When LINC00847 expression was used to distinguish asthma exacerbation from asthma remission, a 0.871 AUC (95% CI: 0.805-0.936) was yielded with sensitivity of 79.63% and specificity of 77.78%. Conclusion: The study demonstrates that increased LINC00847 expression may be associated with the development and progression of asthma, possibly serving as a novel biomarker for predicting asthma exacerbation from asthma remission.

Effect of carboxymethyl chitosan on the storage stability of frozen dough: State of water, protein structures and quality attributes.

Carboxymethyl chitosan (CMCh), an ampholetic chitosan derivative, has found broad applications in the food industry. However, its cryo-protective properties remained less explored compared to other viscous polysaccharides, such as carboxymethyl cellulose, carrageenan etc., which have been widely utilized as frozen food additives. In this study, we investigated the effect of CMCh addition to frozen dough in terms of water state, protein structure, and the textural properties of prepared frozen dumpling wrappers. Results indicated that CMCh restricted the water migration in dough and delayed protein deterioration during frozen storage. Specifically, the content of freezable water in dough was reduced and the water distribution became more uniform as reflected by DCS and LF-NMR analysis. CMCh also stabilized disulfide bond and secondary structures of the protein, leading to inhibition of dough rheology changes. Accordingly, the obtained frozen dumplings wrappers demonstrated decreased cracking rate and water loss, and improved textural properties. Moreover, CMCh with higher degree of carboxymethyl substitution (DS: 1.2, CMCh-B) exhibited better cryo-protective effects compared to CMCh of lower DS (DS: 0.8, CMCh-A). Our study provides novel insights and scientific basis for the development of ampholetic polysaccharides as high-performance food additives.

Low-cost hydrogel adsorbent enhanced by trihydroxy melamine and ß-cyclodextrin for the removal of Pb(II) and Ni(II) in water.

Hydrogels have extensively studied as adsorbents, raw materials for the preparation of adsorbent hydrogels have low strength, while high strength hydrogels have weak adsorption capacity. In this study, PVA hydrogel was crosslinked via trihydroxy melamine and epichlorohydrin, and ß-cyclodextrin with strong adsorption capacity was added to remove the heavy metal ions. Results showed that the addition of trihydroxy melamine with 8%, the compressive strength of the hydrogel was increased by approximately 20%. The Langmuir isotherm model showed that the adsorption capacity of the hydrogel for Pb(II) and Ni(II) reached 505.9 mg/g and 286.7 mg/g, respectively, and the efficiency of removing the low-concentration heavy metal ions in water more than 99%. The hydrogel is low cost, and maintained highly removal efficiency under low pH. The removal efficiency of the hydrogel remained above 90% after five repeated adsorption-desorption experiments. The hydrogels have a potential to be used in wastewater treatment as adsorbents.

Recyclable and degradable nonwoven-based double-network composite hydrogel adsorbent for efficient removal of Pb(II) and Ni(II) from aqueous solution.

This study reports a novel adsorbent structure and shows the satisfactory removal performance of Pb(II) and Ni(II). The fabric structure increases the strength of the hydrogel. The hydrogel plays a major role in the composite structure as a matrix, while the fabric bears the applied load and protects the structure from mechanical damage. The double-network composite hydrogel is reinforced by plasma grafted polylactic acid melt-blown non-woven fabric and polyethylene glycol dimaleate, and its compressive strength reaches 40.6 kPa at 60% strain. The interface substantially improves the compression strength by 42.9%. Through the adsorption isotherm model, the adsorption capacity of the hydrogel for Pb(II) and Ni(II) reaches 233.12 and 165.06 mg/g, respectively, and the removal rate of heavy metal ions in water at low concentrations exceeds 95%, showing the excellent removal rate of heavy metals. Even after the fifth cycle, the removal efficiency barely declines, indicating the feasibility of repeatedly use. Cost analysis reveals that the adsorbent is relatively low cost, solving the problems of difficult recovery, low strength, and easy damage of hydrogel adsorbents, and promoting the industrial application of hydrogels as adsorbents.

NO and ABA Interaction Regulates Tuber Dormancy and Sprouting in Potato.

In plants, nitric oxide synthase (NOS)-like or nitrate reductase (NR) produces nitric oxide (NO), which is involved in releasing seed dormancy. However, its mechanism of effect in potato remains unclear. In this study, spraying 40 µM sodium nitroprusside (SNP), an exogenous NO donor, quickly broke tuber dormancy and efficiently promoted tuber sprouting, whereas 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (c-PTIO), an NO scavenger, repressed the influence of NO on tuber sprouting. Compared with the control (distilled water), SNP treatment led to a rapid increase in NO content after 6 h and a decreased abscisic acid (ABA) content at 12 and 24 h. c-PTIO treatment significantly inhibited increase of NO levels and increased ABA production. In addition, N G -nitro-L-arginine methyl ester, an NOS inhibitor, clearly inhibited the NOS-like activity, whereas tungstate, an NR inhibitor, inhibited the NR activity. Furthermore, NO promoted the expression of a gene involved in ABA catabolism (StCYP707A1, encoding ABA 8'-hydroxylase) and inhibited the expression of a gene involved in ABA biosynthesis (StNCED1, encoding 9-cis-epoxycarotenoid dioxygenase), thereby decreasing the ABA content, disrupting the balance between ABA and gibberellin acid (GA), and ultimately inducing dormancy release and tuber sprouting. The results demonstrated that NOS-like or NR-generated NO controlled potato tuber dormancy release and sprouting via ABA metabolism and signaling in tuber buds.

Preparation and Irreversible Inhibition Mechanism Insight into a Recombinant Kunitz Trypsin Inhibitor from Glycine max L. Seeds.

Soybean Kunitz trypsin inhibitor (SKTI), extracted from soybean (Glycine max L.) seeds, possesses insect resistance and anti-tumor properties. But its specific mechanisms of action are not yet known. This article reports an efficient method to produce recombinant SKTI (rSKTI) in Escherichia coli, reveals some biochemical properties of rSKTI, and discusses the inhibition mechanism of SKTI. The rSKTI was expressed as inclusion body in E. coli BL21 (DE3). After refolding, the active rSKTI was obtained and was further purified with anion-exchange chromatography (DEAE-FF) efficiently. There were similar biochemical properties between SKTI and rSKTI. The optimum pH and the optimum temperature were pH 8.0 and 35 °C, respectively, being stable during pH 7.0-11.0 and below 37 °C. The activity against trypsin was inhibited by Co2+, Mn2+, Fe3+, Al3+, and epoxy chloropropane. Inhibition kinetic assay of SKTI against trypsin as Lineweaver-Burk plots analysis both showed an unchanged Km and a decreased Vmax with N-benzoyl-L-arginine ethyl ester (BAEE) as substrate. Molecular modeling showed Arg63 of SKTI (active residue of SKTI) that interacts with four residues of trypsin, including three catalytic site (His57, Asp102, and Ser195) and one binding site (Asp189), forming five interactions. These provide reference for understanding the inhibition mechanism of such kind of Kunitz trypsin inhibitors.

Fabrication of cefotaxime sodium-functionalized gold nanoclusters for the detection of copper ions in Chinese herbal medicines.

Antibiotic-based gold nanoclusters (AuNCs) are a good sensing platform for specific recognition; however, the related studies are few. Herein, a simple and facile strategy was proposed for the fabrication of bright blue fluorescent AuNCs through the degradation product (DCTX) of cefotaxime sodium that induced the reduction of HAuCl4. Various analytical techniques were applied to characterize the prepared AuNCs@DCTX. AuNCs@DCTX exhibited a strong emission peak centered at 420 nm and a quantum yield of 11.8%. Furthermore, an aggregation-induced fluorescence quenching mode endowed the AuNCs@DCTX probe with good specificity and sensitivity for Cu2+ detection. The proposed probe had a linear range of 0.01-40 µM, a precision with a relative standard deviation of 1.2% (n = 8), and a detection limit of 8 nM (signal/noise = 3). Interestingly, the probe could be reused through switching the "off" and "on" states by the addition of Cu2+ and EDTA. The practicality of the sensing platform was investigated for the determination of Cu2+ in four Chinese herbal medicines (CHMs), and the results were in accordance with those obtained by the FAAS method. This study has provided an alternate way for the fabrication of thiolate-protected AuNCs for sensing applications.

Mono and co-immobilization of imidazolium ionic liquids on silica: effects of the substituted groups on the adsorption behavior of 2,4-dinitrophenol.

Ionic liquid modified silicas with high adsorption capacity for phenols prompt us to deeply explore the contribution of interactions between the adsorbent and adsorbate, with a particular focus on hydrophobicity, π-π, electrostatic and acid-base interactions. Herein, by introducing a series of typical substituent groups including N,N-dimethylaminopropyl (A), benzyl (B), dodecyl (D) and naphthylmethyl (N) in an imidazole ring (Im), three mono-immobilized and two co-immobilized imidazolium ionic liquid modified silicas, namely SilprAImCl, SilprBImCl, SilprNImCl, SilprDBImCl and SilprDAImCl, werre synthesized for removal and recovery of 2,4-dinitrophenol (2,4-DNP) from aqueous solutions. Adsorption kinetics, isotherms, thermodynamic analysis and desorption experiments have been carried out. The experimental results reveal that the substituent groups such as N,N-dimethylaminopropyl, benzyl and naphthylmethyl on the imidazole ring can significantly enhance the adsorption of 2,4-DNP via the acid-base interaction or π-π interaction and the adsorption capacity of 2,4-DNP follows the order: SilprNImCl > SilprAImCl > SilprBImCl. Furthermore, SilprDBImCl exhibits the largest adsorption capacity and SilprDAImCl has the lowest among the five adsorbents. These interesting finds indicate that the combination of hydrophobicity and π-π interactions lead to enhanced adsorption performance towards 2,4-DNP, while the combination of the hydrophobicity and acid-base interactions can restrain greatly adsorption of 2,4-DNP from aqueous medium. Adsorption mechanisms of 2,4-DNP on the five adsorbents have been clarified. These results will provide a deeper insight for efficient removal of phenols from water environments.

Investigation of 1-Dodecylimidazolium Modified Filter Papers as a Thin-Film Microextraction Phase for the Preconcentration of Bisphenol A from Plant Oil Samples.

Based on the tunability of ionic liquids (ILs) according to the specific requirement of an application, 1-dodecylimidazolium chloride with amphiphilic structures was chemically fabricated on the surface of filter papers (DIL-FPs) for the first time. After synthesis, DIL-FPs was characterized by scanning electronic microscopy, energy dispersive X-ray spectroscopy and Fourier-transform infrared spectroscopy. DIL-FPs was used as a novel thin-film microextraction (TFME) phase for the preconcentration of amphiphilic bisphenol A from plant oil samples. The related extraction variables were studied in a spiked sunflower seed oil. Under the optimal conditions, the linear range was 5.0 - 1000 µg L-1 with a correlation coefficient of 0.9976. The limit of detection (S/N = 3) and the enrichment factor of the proposed method were 2.7 µg L-1 and 118, respectively. The intra-day precision and inter-day precision for six repeated determinations were 2.3 and 4.9%, respectively. These plant oil samples used in this work were free of bisphenol A contaminations. The recovery study carried out in different plant oil samples and mean recoveries ranged from 77.16 to 97.10%. The developed DIL-FPs extraction film phase followed by HPLC-UV provides a potential pretreatment strategy for the analysis of weak organic acid compounds in plant oil samples.

Comparison and evaluation of five types of imidazole-modified silica adsorbents for the removal of 2,4-dinitrophenol from water samples with the methyl group at different positions of imidazolium ring.

The objective of this work was to improve the understanding the influence of the methyl group at different positions of imidazolium ring on the adsorption behaviors of imidazole-modified silica adsorbents. Five adsorbents named as SilprImCl, SilprM1ImCl, SilprM2ImCl, SilprM4ImCl and SilprM1M2ImCl were synthesized using imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole and 1,2-dimethylimidazole, respectively. These adsorbents were characterized by scanning electron microscope, infrared spectra, thermogravimetric analysis, elemental analysis and BET analysis. Firstly, phenol, 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP) and 2,4-dinitrophenol (2,4-DNP) were used as adsorbates to investigate the selectivity of SilprImCl and its adsorption capacities followed the order of 2,4-DNP≫4-NP>2-NP≫3-NP>phenol. Therefore, 2,4-DNP was used to investigate the adsorption behaviors of the five adsorbents. It was inferred that the adsorbents are of primary anion-exchange and electrostatic nature. The electrostatic nature was affected significantly by the methyl group at different positions of imidazolium ring. The adsorbed amounts of 2,4-DNP decreased in the order of: SilprM1M2ImCl≈SilprM1ImCl>SilprM4ImCl>SilprM2ImCl>SilprImCl. The adsorption-elution experiments indicated that 2,4-DNP can be removed from aqueous solutions by a SilprM4ImCl packed column and the recovery of 91.6% was obtained. The adsorbent could be regenerated and reused ten times at least by simple washings with HCl and water in turn.

Recovery of nickel from aqueous samples with water-soluble carboxyl methyl cellulose-acetone system.

A simple and efficient method, which involves carboxyl methyl cellulose (CMC) and acetone, was developed for recovery of trace nickel from aqueous solutions. This method was based on the fact that Ni2+ could react with CMC and form water-soluble complexes, which would solidify in excess acetone. After centrifugation, the solid mass consisting of the nickel complex and free CMC was easily dissolved with water and the nickel was determined by flame atomic absorption spectrometry (FAAS). Several factors influencing the recovery of nickel were thoroughly investigated and the optimized conditions were as follows: 5.00 mL water sample, 0.50 mL 0.5% CMC, 1.00 mL of 3.0 mg mL(-1) KNO3 and 20 mL acetone. Under the optimized conditions, the loading capacity of CMC for nickel was 20.6 mg Ni/g polymer. The linear range was 0.025-3.0 microg mL(-1), the limit of detection was 0.019 microg mL(-1) and the pre-concentration factor was 4. Ni(II) can be well recovered in this CMC-acetone system from binary ions mixtures containing Zn(II), Ba(II), Ca(II), Mo(VI), Co(II), Cd(II), Mg(II), Mn(II) and Cr(III). The developed method had been applied to the recovery of trace nickel in water samples with satisfactory results. A possible mechanism for the nickel precipitate was proposed. The efficient, convenient and affordable method provides an alternative method for the recovery of nickel from environmental waters.

Sulfonated microporous organic-inorganic hybrids as strong Bronsted acids.

It has been discovered that the use of excess zirconium in reactions with 4,4'-biphenyl and 4,4'-terphenylbis(phosphonic acid) in DMSO or DMSO-ethanol mixtures produces microporous inorganic-organic hybrids. Surface areas of 400 m(2)/g and pore sizes in the range of 10-20 A in diameter are routinely obtained. These materials are readily sulfonated with SO(3) under pressure to yield strong Bronsted acids. The acid strength, measured by (13)C NMR shifts of acetone and cyclopentanone in contact with the sulfonates, indicates an acidity close to that of 100% H(2)SO(4). Condensation and cracking reactions were obtained for both ketones under mild conditions. A working hypothesis is presented to account for the high surface area and microporosity. The combination of high surface areas and pore dimensions that are between those of zeolites and mesoporous silicas commends these materials for applications in separations, ion exchange, and catalysis.

New lead inorganic-organic hybrid microporous and layered materials: synthesis, properties, and crystal structures.

Two new lead(II) phosphonates, namely, Pb2[PMIDA]*1.5H2O (1) (H4PMIDA = H2O3PCH2N(CH2CO2H)2) and Pb(H2L) (2) (H4L = CH3N(CH2PO3H2)2), have been synthesized by hydrothermal reactions at 150 degrees C. Complex 1 crystallized in tetragonal P42/n with cell dimensions of a = 17.317(7) and c = 7.507(5) A and Z = 8. In complex 1, Pb(1) is 6-coordinated by chelation in a tetradentate fashion by a PMIDA ligand (3 O, 1 N) and two phosphonate oxygen atoms from neighboring Pb(PMIDA) units in a severely distorted octahedral geometry, whereas Pb(2) is 6-coordinated by 4 carboxylate and 2 phosphonate oxygen atoms also with a severely distorted octahedral environment. These two different types of Pb(II) ions are interconnected through bridging carboxylate and phosphonate groups, resulting in a 3D network with micropores, whose cavity is filled by lattice water molecules interlinked via hydrogen bonds. Each PMIDA ligand bridges with 8 Pb(II) ions (3 Pb(1) and 5 Pb(2)). Complex 2 is orthorhombic, P2(1)2(1)2(1), with a = 7.382(5), b = 7.440(6), and c = 30.75(2) A and Z = 8. The structure of 2 features a 2D double lead(II) phosphonate layer along the ab plane. Each lead(II) ion is 5-coordinated by five phosphonate oxygen atoms from four ligands in a distorted trigonal bipyramid geometry. These double layers are further interconnected via hydrogen bonds between the protonated and uncoordinated phosphonate oxygens along the c-axis.

Synthesis, characterization, and crystal structures of two new divalent metal complexes of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6: a hydrogen-bonded 1D array and a 3D network with a large channel.

Reaction of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6 (H(4)L) with copper(II) acetate in 1:1 ethanol/water mixed solvents afforded a new crystal-engineered supramolecular metal phosphonate, Cu(H(2)L) (complex 1). By reaction of the same ligand with cadmium(II) nitrate in a 2:1 (M/L) ratio in methanol, a cadmium(II) complex with a 3D network structure was isolated, Cd(2.75)(L)(H(2)O)(7) x 1.5NO(3) x 7H(2)O x MeOH (complex 2). The copper(II) complex crystallized in the monoclinic space group P2(1)/c, with a =10.125(4), b = 14.103(6), and c = 14.537(6) A, beta = 91.049(8) degrees, V = 2075.4(16) A(3), and Z = 2. The Cu(II) ions in complex 1 are 6-coordinated by two phosphonate oxygen atoms, two nitrogen, and two oxygen atoms from the crown ether ring. Their coordination geometry can be described as Jahn-Teller-distorted octahedral, with elongated Cu-O(crown) distances (2.634(4) and 2.671(4) A for Cu(1) and Cu(2), respectively). The other two crown oxygen atoms remain uncoordinated. Neighboring two Cu(H(2)L) units are further interlinked via a pair of strong hydrogen bonds between uncoordinated phosphonate oxygen atoms, resulting in a one-dimensional supramolecular array along the a axis. The cadmium(II) complex is tetragonal, P4(2)/n (No. 86) with a = 20.8150(9) and c = 18.5846(12) A, V = 8052.0(7) A(3), and Z = 8. Among four cadmium(II) atoms in an asymmetric unit, one is 8-coordinated by four chelating phosphonate groups, the second one is 8-coordinated by 6 coordination atoms from a crown ring and two oxygen atoms from two phosphonate groups, the third Cd(II) atom is octahedrally coordinated by three aqua ligands and three phosphonate oxygen atoms from three phosphonate groups, and the fourth one is 6-coordinated by four aqua ligands and two oxygen atoms from two phosphonate groups in a distorted octahedral geometry. These cadmium atoms are interconnected by bridging phosphonate tetrahedra in such a way as to form large channels along the c direction, in which the lattice water molecules, methanol solvent, and nitrate anions reside. The effect of extent of deprotonation of phosphonic acids on the type of complex formed is also discussed.

Synthesis, characterization, and crystal structures of two divalent metal diphosphonates with a layered and a 3D network structure.

Reactions of N-methyliminobis(methylenephosphonic acid), CH(3)N(CH(2)PO(3)H(2))(2) (H(4)L), with divalent metal acetates under different conditions result in metal diphosphonates with different structures. Mn(H(3)L)(2).2H(2)O (complex 1) with a layer structure was prepared by a layering technique. It is triclinic, P1 macro with a = 9.224(3) A, b = 9.780(3) A, c = 10.554(3) A, alpha = 82.009(6) degrees, beta = 74.356(6) degrees, gamma = 89.853(6) degrees, Z = 2. The Mn(II) ion is octahedrally coordinated by six phosphonate oxygen atoms from four ligands, two of them in a bidentate and two in a unidentate fashion. Each MnO(6) octahedron is further linked to four neighboring MnO(6) octahedra through four bridging phosphonate groups, resulting in a two-dimensional metal phosphonate (002) layer. These layers are held together by strong hydrogen bonds between uncoordinated phosphonate oxygen atoms. The zinc complex Zn(3)(HL)(2) (complex 2) was synthesized by hydrothermal reactions (4 days, 438 K, autogenous pressure). It is monoclinic, P2(1)/n with a = 7.7788(9) A, b = 17.025(2) A, c = 13.041(2) A, beta = 94.597(2) degrees, Z = 4. The structure of complex 2 features a 3D network built from ZnO(4) tetrahedra linked together by bridging phosphonate groups. Each zinc cation is tetrahedrally coordinated by four phosphonate oxygen atoms from four ligands, each of which connects with six zinc atoms, resulting in voids of various sizes. Magnetic measurements for the manganese complex shows an antiferromagnetic interaction at low temperature. The effect of the extent of deprotonation of phosphonic acids on the type of complex formed is discussed.

In Situ NMR Investigations of Heterogeneous Catalysis with Samples Prepared under Standard Reaction Conditions.

Only 170 milliseconds are required to cool the catalyst bed by 150 K in the catalytic reactor shown on the right. Thus, NMR spectroscopic investigations can be carried out on products that are formed after very short contact times and under real catalysis conditions.