Pleurotus spp. Mycelia Enriched in Magnesium and Zinc Salts as a Potential Functional Food

Worldwide, mushrooms belonging to the Pleurotus spp. such as P. citrinopileatus, P. djamor, and P. pulmonarius are highly valued not only for their taste and aroma but also for their health-promoting properties. These species are rich in bioelements, vitamins, and above all, compounds that exhibit immunostimulatory activity. Therefore, in this study, we aimed to determine the effect of the supplementation of culture media using inorganic Mg and Zn salts. This is the first study to establish the bioavailability of the selected elements (Mg and Zn) and anions (Cl⁻, SO₄²⁻) from the enriched biomass by means of the extraction of lyophilized mycelium into artificial digestive juices. The following salts were added to the liquid Oddoux medium: ZnSO₄·7H₂O, ZnCl₂, MgSO₄·7H₂O or MgCl₂·6H₂O. The bioelements, anions and organic compounds in the obtained biomass were determined. The addition of Zn and Mg salts to the media increased the production of biomass by 30% and increased the bioaccumulation of the inorganic salts. Maintaining in vitro cultures under optimized and controlled conditions produced mycelium with a better composition and health properties than otherwise. Such enriched biomass may be classified as potential functional foods, aiding in overcoming deficiencies of elements and organic compounds with biological activity in humans.     

From 1D to 2D Cd(II) and Zn(II) Coordination Networks by Replacing Monocarboxylate with Dicarboxylates in Partnership with Azine Ligands: Synthesis,Crystal Structures,Inclusion, and Emission Properties

Eight mixed-ligand coordination networks, [Cd(2-aba)(NO₃)(4-bphz)_3/2]_n·n(dmf) (1), [Cd(2-aba)₂(4-bphz)]_n·0.75n(dmf) (2), [Cd(seb)(4-bphz)]_n·n(H₂O) (3), [Cd(seb)(4-bpmhz)]_n·n(H₂O) (4), [Cd(hpa)(3-bphz)]_n (5), [Zn(1,3-bdc)(3-bpmhz)]_n·n(MeOH) (6), [Cd(1,3-bdc)(3-bpmhz)]_n ·0.5n(H₂O)·0.5n(EtOH) (7), and [Cd(NO₃)₂(3-bphz)(bpe)]_n·n(3-bphz) (8) were obtained by interplay of cadmium nitrate tetrahydrate or zinc nitrate hexahydrate with 2-aminobenzenecarboxylic acid (H(2-aba)), three dicarboxylic acids, sebacic (decanedioic acid, H₂seb), homophthalic (2-(carboxymethyl)benzoic acid, H₂hpa), isophthalic (1,3-benzenedicarboxylic acid, H₂(1,3-bdc)) acids, bis(4-pyridyl)ethane (bpe) and with four azine ligands, 1,2-bis(pyridin-4-ylmethylene)hydrazine (4-bphz), 1,2-bis(1-(pyridin-4-yl)ethylidene) hydrazine (4-bpmhz), 1,2-bis(pyridin-3-ylmethylene)hydrazine (3-bphz), and 1,2-bis(1-(pyridin-3-yl) ethylidene)hydrazine (3-bpmhz). Compounds 1 and 2 are 1D coordination polymers, while compounds 3–8 are 2D coordination polymers. All compounds were characterized by spectroscopic and X-ray diffraction methods of analysis. The solvent uptakes and stabilities to the guest evacuation were studied and compared for 1D and 2D coordination networks. The de-solvated forms revealed a significant increase of emission in comparison with the as-synthesized crystals.     

Mononuclear Transition Metal Cymantrenecarboxylates as Precursors for Spinel-Type Manganites

Novel mononuclear cymantrenecarboxylate complexes of transition metals, [Co(H₂O)₆](CymCO₂)₂·4H₂O (Cym = (η⁵-C₅H₄)Mn(CO)₃) (1), [Ni(H₂O)₆](CymCO₂)₂·4H₂O (2), [Zn(H₂O)₆](CymCO₂)₂·4H₂O (3), [Co(CymCO₂)₂(imz)₂] (imz = imidazole, 4), [Co(CymCO₂)₂(bpy)₂]·2PhMe (bpy = 2,2′-bipyridyl, 5), [Ni(CymCO₂)(bpy)₂(H₂O)][CymCO₂]·0.5MePh·2H₂O (6), [Cu(CymCO₂)₂(imz)₂] (7), and [Cu(CymCO₂)₂(bpy)(H₂O)] (8), were obtained and characterized by single-crystal X-ray analysis. Complexes 1–3 are isostructural. Magnetism of the Co complexes 1, 4, and 5 was studied; it was shown that they exhibit the properties of field-induced single-molecule magnets with magnetization reversal barriers (ΔE/k_B) of 44, 13, and 10 K, respectively. Thermal decomposition of complexes 1–8 was studied by means of DSC and TGA methods. The final products of thermolysis of 1–6 in air, according to powder XRD data, are the pure spinel phases MMn₂O₄; for the cases of copper complexes, the mixtures of CuMn₂O₄ and CuO were found in the products.     

Synthesis,spectroscopic, thermal,crystal structure properties and characterization of new Hofmann-type-like clathrates with 4-aminopyridine and water

In this study, synthesis of two new heteronuclear tetracyanonickelate(II) clathrates based on 4-aminopyridine (4AP) and guest water (H₂O) molecule and investigation of their structural properties were reported. These clathrates were characterized by using vibration spectroscopy, elemental, thermal analysis and single crystal X-ray diffraction (SC-XRD) techniques. Examining the elemental and spectral data of these clathrates, it was observed that the formulas [Zn(II)(4AP)₂Ni(µ-CN)₂(CN)₂]·6H₂O and [Cu(II)(4AP)₄Ni(µ-CN)₂(CN)₂]·H₂O were defined their structures. General information about the structural properties of these clathrates in single crystal form has been obtained by considering the changes in the characteristic peaks of the cyanide group and the 4AP that formed them. The thermal behaviors of these clathrates were obtained by examining the temperature-dependent changes of their masses. The magnetic susceptibilities of these clathrates in single crystal form were measured with a Gouy balance. According to the data obtained using SC-XRD technique, the heterometallic [Zn(II)(4AP)₂Ni(µ-CN)₂(CN)₂]·6H₂O compound has Cmcm and the heterometallic [Cu(II)(4AP)₄Ni(µ-CN)₂(CN)₂]·H₂O compound has crystal structures in the C2 / c space group.     

Synthesis of Hafnium(IV) Polyaminoacetates

The interaction of hafnium(IV) salts (oxide-dichloride, chloride, and bromide) with nitrilotriacetic acid (NTA), diethylenetriamminepentaacetic acid (DTPA), 1,2-diaminocyclohexanetetraacetic acid (CDTA), 1,3-dipropylmino-2-hydroxy N,N,N′,N′-tetraacetic acid (dpta), and N-(2-hydroxyethyl)ethylenediamine triacetic acid (HEDTA) has been studied. The corresponding complexes Na₂[Hf(NTA)₂]·3H₂O (1), Na[HfDTPA]·3H₂O (2), [HfCDTA(H₂O)₂] (3), and Na[Hf₂(dpta)₂]·7.5H₂O·0.5C₂H₅OH (4) have been isolated and characterized and their structures have been determined by single crystal X-ray diffraction. Biological studies of [HfCDTA(H₂O)₂] have shown that in 5% glucose solution this complex has low toxicity and good contrasting ability.     

Ionic Porous Aromatic Framework as a Self-Degraded Template for the Synthesis of a Magnetic γ-Fe2O3/WO3·0.5H2O Hybrid Nanostructure with Enhanced Photocatalytic Property

An ionic porous aromatic framework is developed as a self-degraded template to synthesize the magnetic heterostructure of γ-Fe₂O₃/WO₃·0.5H₂O. The Fe₃O₄ polyhedron was obtained with the two-phase method first and then reacted with sodium tungstate to form the γ-Fe₂O₃/WO₃·0.5H₂O hybrid nanostructure. Under the induction effect of the ionic porous network, the Fe₃O₄ phase transformed to the γ-Fe₂O₃ state and complexed with WO₃·0.5H₂O to form the n-n heterostructure with the n-type WO₃·0.5H₂O on the surface of n-type γ-Fe₂O₃. Based on a UV-Visible analysis, the magnetic photocatalyst was shown to have a suitable band gap for the catalytic degradation of organic pollutants. Under irradiation, the resulting γ-Fe₂O₃/WO₃·0.5H₂O sample exhibited a removal efficiency of 95% for RhB in 100 min. The charge transfer mechanism was also studied. After the degradation process, the dispersed powder can be easily separated from the suspension by applying an external magnetic field. The catalytic activity displayed no significant decrease after five recycles. The results present new insights for preparing a hybrid nanostructure photocatalyst and its potential application in harmful pollutant degradation.     

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs,and other topologies

The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with Cu^I and/or Cu^II cations that show a remarkable range of framework topologies and structures. Complex [Cu^I ₄Cu^II _1.5(L1)₃(CN)₆]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu₃(L2)₄(H₂O)₃]·6(OTf)·n(DMSO) 2 and [Cu₂(L3)₂Br₂(H₂O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4³.12³)(4².12²) topology or a coordination chain. Complex [Cu₂(L1)₂(OTf)₂(NMP)₂(H₂O)₂]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.6².8)(6².8)(4.6².8²) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF₄·2(CH₃CN)·H₂O 5 features a 2D network of 6³ topology while the Cu^II analogue [Cu₂(L1)₂(NMP)(H₂O)]·4BF₄·12NMP·1.5H₂O 6 has an interpenetrating (10,3)-b type structure and complex [Cu₂(L2)₂Br₃(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.8² topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C₆₀ through soaking the crystals in a toluene solution.     

Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid

Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the π electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO)–Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)₂·2H₂O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(μ-Pip)₂(4-Acpy)]₂ (1); a mixture of one dimer and two monomers [Zn(µ-Pip)(Pip)(Isn)₂]₂·2[Zn(Pip)₂(HPip)(Isn)]·2MeOH (2); and two dimers [Cd(μ-Pip)(Pip)(4-Acpy)₂]₂ (3) and [Cd(μ-Pip)(Pip)(Isn)₂]₂·MeOH (4). They exhibit bridged (1, µ₂-η¹:η¹), bridged, chelated and monodentated (2, µ₂-η¹:η¹, µ₁-η¹:η¹ and µ₁-η¹), or simultaneously bridged and chelated (3 and 4, µ₂-η²:η¹) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations.     

Entwässerung von ZnSO4·7H2O durch organische Lösungsmittel und unter Hochvakuum

Zusammenfassung In der vorliegenden Arbeit wurde der Entwässerungsprozeß von ZnSO₄·7 H₂O mit organischen Lösungsmitteln bei Raum-temperatur sowie unter Hochvakuum bei 20, 60, 100 und 140°C untersucht und die Strukturveränderungen mit Hilfe von IR-Spektren und Röntgenpulverdiagrammen diskutiert. Mit C₂H₅OH (99,2%) oder Aceton führt die Entwässerung in 30 Minuten zu ZnSO₄·6 H₂O und nach mehreren Stunden zu einer Mischung von ZnSO₄·6 H₂O und ZnSO₄·H₂O. Mit Xylol beobachtet man diesen Prozeß nicht. Unter Hochvakuum gelangt man bei 20°C in 46 Stdn. und bei 60°C in 16 Stdn. zu ZnSO₄·H₂O, bei 140°C im Verlaufe von 24 Stdn. bis zu wasserfreiem ZnSO₄.

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Desiccation of ZnSO₄·7 H₂Owith organic solvents and under high vacuum

In this paper the desiccation process of ZnSO₄·7 H₂O with organic solvents at room temperature and under high vacuum at 20, 60, 100, and 140°C was investigated. The structural changes were discussed by means of IR-spectra and X-ray powder diagrams. With C₂H₅OH (99.2%) or acetone the desiccation leads within 30 minutes to ZnSO₄·6 H₂O and after several hours to a mixture of ZnSO₄·6 H₂O and ZnSO₄·H₂O. With xylene this process in praxi does not exist. Under high vacuum one reaches ZnSO₄·H₂O at 20°C within 46 hours and at 60°C within 16 hours. ZnSO₄ is free of water at 140°C within 24 hours.

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Mit 4 Abbildungen     

Two Unexpected Temperature-Induced Supermolecular Isomers from Multi-Topic Carboxylic Acid: Hydrogen Bonding Layer or Helix Tube

Under ambient conditions or 160 °C, two supramolecular isomers, namely [(H₄PTTA)(H₂O)₂(DMF)] and [(H₄PTTA)(H₂O)₃]··Guest (1-L and 1-H, H₄PTTA = N-phenyl-N′-phenyl bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide tetra-carboxylic acid, Guest = DMF and H₂O), were obtained through the reaction of H₄PTTA in a mixture of H₂O and dimethylformamide. The single crystal structures reveal the temperature-dependent supramolecular isomerism derived from the torsion of semi-rigid of H₄PTTA. The 1-L prepared at room temperature is a hydrogen bond based achiral layer, while the hydrothermal synthesized 1-H is isomer resulted in an H-bond-based chiral tubes-packed supramolecular framework.     

Structure and Population of Complex Ionic Species in FeCl2 Aqueous Solution by X-ray Absorption Spectroscopy

Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl₂). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl₂ solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl₂ aqueous solution at different concentrations (1–4 molL⁻¹) and temperatures (25–80 °C). We found that at low temperature and low FeCl₂ concentration, the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl₂(H₂O)₄]⁰. The observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. The transition from the single charged Fe[Cl(H₂O)₅]⁺ to the neutral Fe[Cl₂(H₂O)₄]⁰ causes a significant drop in the solution conductivity, which well correlates with the existing conductivity models.     

Structure Controlling Factors of Oxido-Bridged Dinuclear Iron(III) Complexes

Oxido bridges commonly form between iron(III) ions, but their bond angles and symmetry vary with the circumstances. A large number of oxido-bridged dinuclear iron(III) complexes have been structurally characterized. Some of them belong to the C₂ point group, possessing bent Fe–O–Fe bonds, while some others belong to the C_i symmetry, possessing the linear Fe–O–Fe bonds. The question in this study is what determines the structures and symmetry of oxido-bridged dinuclear iron(III) complexes. In order to gain further insights, three oxido-bridged dinuclear iron(III) complexes were newly prepared with 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) ligands: [Fe₂OCl₂(bpy)₄][PF₆]₂ (1), [Fe₂O(NO₃)₂(bpy)₄][PF₆]₂·0.6MeCN·0.2(2-PrOH) (2), and [Fe₂OCl₂(phen)₄][PF₆]₂·MeCN·0.5H₂O (3). The crystal structures of 1, 2, and 3 were determined by the single-crystal X-ray diffraction method, and all of them were found to have the bent Fe–O–Fe bonds. Judging from the crystal structure, some intramolecular interligand hydrogen bonds were found to play an important role in fixing the structures. Additional density functional theory (DFT) calculations were conducted, also for a related oxido-bridged dinuclear iron(III) complex with a linear Fe–O–Fe bond. We conclude that the Fe–O–Fe bridge tends to bend like a water molecule, but is often stretched by interligand steric repulsion, and that the structures are mainly controlled by the intramolecular interligand interactions.     

Cross-linking nanostructured spherical capsules as building units by crystal engineering: related chemistry

The compound [Mo₇₂Fe₃₀O₂₅₂(CH₃COO)₁₀{Mo₂O₇(H₂O)}{H₂Mo₂O₈(H₂O)}₃ (H₂O)₉₁]·ca. 140 H₂O 3≡3a·ca. 140 H₂O, an important educt for an unusual solid state reaction, can now be obtained easily by reacting (NH₄)₄₂[{Mo^V₂O₄(CH₃COO)}₃₀{(Mo)Mo₅O₂₁(H₂O)₆}₁₂]·10 CH₃COONH₄·ca. 300 H₂O 1 with FeCl₃·6 H₂O in water. Interestingly, the freshly precipitated crystals of 3 contain discrete spherical clusters of the type {Mo^VI₇₂Fe^III₃₀} with as yet unprecedented 30×5 unpaired electrons (S=150/2 at room temperature). Upon drying 3, its cluster units 3a get covalently linked to form layers in a step by step solid state reaction, according to the scheme described below, resulting finally in the crystalline reaction product [H₄Mo₇₂Fe₃₀O₂₅₄(CH₃COO)₁₀{Mo₂O₇(H₂O)}{H₂Mo₂O₈(H₂O)}₃(H₂O)₈₇]·ca. 80 H₂O 44a·ca. 80 H₂O. The linking process at the Fe sites follows the well known inorganic condensation process leading to Fe^III polycations in aqueous solution according to the scheme Fe(OH₂)+(H₂O)Fe Fe(OH)+(H₂O)Fe Fe–O–Fe and thus is based on a type of crystal engineering with nanostructured spherical building blocks. This process does not allow chaotic characteristics in contrast to the mentioned polycation formation. Careful investigation leads to the identification of an intermediate 5 containing clusters 5a — with the same cluster composition as 3a and 4a — in the closest possible non-covalent contact. The related materials are of tremendous interest for magnetochemistry (nano-magneto-technology).

     

Characterisation and coagulation performance of polysilicate-ferric-zinc

A new type of coagulant, polysilicate-ferric-zinc (PSFZn) with different Fe/Zn molar ratios, was synthesised using water glass (industrial grade, w(SiO₂) = 21 mass %, ρ = 1.34 × 10³ kg m^?3, modulus = 3.2), FeSO₄ · 7H₂O, ZnSO₄, and NaClO₃ by way of co-polymerisation in the same (Fe + Zn)/Si molar ratio based on polysilicate-ferric (PSF). The effect of the Fe/Zn molar ratios on the morphology and structure was systematically investigated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) analysis. Three samples, namely PSFZn4, PSFZn1, and PSFZn0.25, represented Fe/Zn molar ratios of 4, 1, and 0.25, respectively, and were selected for a comparative study while a constant (Fe + Zn)/Si molar ratio equal to 1 was maintained. Accordingly, PSFZn was found to be a complex compound rather than a simple mixture of raw materials. With the decrease in Fe/Zn, a great change occurred in the surface morphology, from a tetrahedral cluster structure to a lamellar structure. The Fe—O and Fe—O—Si bonds were gradually replaced by Zn—O and Zn—O—Si. However, the crystalline peaks were more obvious with the increase in the number of zinc ions; hence the new polymer would be formed from iron, zinc, and polysilicate. In addition, the coagulation performance of PSFZn was investigated using a surface water sample. PSFZn4 exhibited a better coagulation performance than the other PSFZn coagulants. Additionally, the trends in changes in pH with different coagulation times after adding PSFZn were studied relative to PSF and FS. The replacement of zinc ions with iron ions could effectively counter the rapid decrease in pH. The effect of settling time on the coagulation efficiency was also investigated. PSFZn4 exhibited a better settlement performance than PSF and poly aluminium chloride (PAC). Hence, the partial substitution of zinc salt with iron salt not only addresses the inadequacies of iron salt but also improves the coagulation efficiency of zinc salt in water treatment.     

Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities

The self-assembly of 2,6-diformyl-4-methylphenol (DFMP) and 1-amino-2-propanol (AP)/2-amino-1,3-propanediol (APD) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H₃L and H₅L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu₄(HL²⁻)₂(N₃)₄]·4CH₃OH·56H₂O (1) and [Cu₄(L³⁻)₂(OH)₂(H₂O)₂] (2), dinuclear [Cu₂(H₃L1²⁻)(N₃)(H₂O)(NO₃)] (3), polynuclear {[Cu₂(H₃L1²⁻)(H₂O)(BF₄)(N₃)]·H₂O}_n (4), heptanuclear [Cu₇(H₃L1²⁻)₂(O)₂(C₆H₅CO₂)₆]·6CH₃OH·44H₂O (5), and decanuclear [Cu₁₀(H₃L1²⁻)₄(O)₂(OH)₂(C₆H₅CO₂)₄] (C₆H₅CO₂)₂·20H₂O (6). X-ray studies have revealed that the basic building block in 1, 3, and 4 is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL²⁻ or H₃L1²⁻, and one μ-1,1-azido (N₃⁻) ion and in 2, 5, and 6 by μ-phenoxide oxygen of L³⁻ or H₃L1²⁻ and μ-O²⁻ or μ₃-O²⁻ ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (1 and 6), 2D-sheets (3), and 3D-structures (4). In 5, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In 1, 3, and 5, Cu(II) ions in [Cu₂] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm⁻¹.     

反应修饰剂ZnSO_4和预处理对苯选择加氢制环己烯Ru-Zn催化剂性能的影响

共沉淀法制备了Ru-Zn催化剂,考察了反应修饰剂ZnSO_4和预处理对苯选择加氢制环己烯Ru-Zn催化剂性能的影响。结果表明,反应修饰剂ZnSO_4可以与Ru-Zn催化剂中助剂Zn O反应生成(Zn(OH)2)3(ZnSO_4)(H_2O)盐。随反应修饰剂ZnSO_4浓度增加,(Zn(OH)2)3(ZnSO_4)(H_2O)盐量逐渐增加,Ru-Zn催化剂活性逐渐降低,环己烯选择性逐渐升高。因为(Zn(OH)2)3(ZnSO_4)(H_2O)盐中的Zn2+可以使Ru变为有利环己烯生成的缺电子的Ruδ+物种,而且还可以占据不适宜环己烯生成的强Ru活性位。但当反应修饰剂ZnSO_4浓度高于0.41 mol·L-1后,继续增加ZnSO_4浓度,由于Zn2+水解浆液酸性太强,可以溶解部分(Zn(OH)2)3(ZnSO_4)(H_2O)盐,RuZn催化剂活性升高,环己烯选择性降低。环己烯选择性略微降低,是由于ZnSO_4溶液中大量的Zn2+可以与生成的环己烯形成配合物,稳定生成的环己烯,抑制环己烯再吸附到催化剂表面并加氢生成环己烷。在ZnSO_4最佳浓度0.61 mol·L-1下对Ru-Zn催化剂预处理15 h,Ru-Zn催化剂中助剂Zn O可以与ZnSO_4完全反应生成(Zn(OH)2)3(ZnSO_4)(H_2O)盐,在该催化剂上25 min苯转化68.2%时环己烯选择性和收率分别为80.2%和54.7%。而且该催化剂具有良好的稳定性和重复使用性能。     

Self-Assembly by Tridentate or Bidentate Ligand: Synthesis and Vapor Adsorption Properties of Cu(II), Zn(II), Hg(II) and Cd(II) Complexes Derived from a Bis(pyridylhydrazone) Compound

Four complexes, [Cu₄L₂(OCH₃)₂(CH₃OH)₂]·2H₂O (1), [Zn₂L₂Cl₄]·2H₂O·2CH₃OH (2), [Hg₂L₂Br₄]·4CH₃OH (3), and {[CdL₂Cl₂]·4H₂O·4CH₃OH}_n (4), have been synthesized and characterized from a bis(pyridylhydrazone) ligand (L) with copper(II), zinc(II), mercury(II) or cadmium(II), respectively. Complex 1 exists as a centrosymmetric tetranuclear dimer with L as deprotonated tridentate ligand. Complexes 2 and 3 exist as centrosymmetric metallamacrocycles with L as bidentate ligand. Complex 4 exists as a 1D looped-chain coordination polymer. The thermal stabilities and vapor adsorption properties of the four complexes were investigated as well.     

Slow Relaxation of the Magnetization in Anilato-Based Dy(III) 2D Lattices

The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) with two different anilato-type ligands (dianions of the 3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone: C₆O₄X₂²⁻, with X = H and Cl) in dimethyl sulfoxide (dmso). The two compounds prepared, formulated as: [Dy₂(C₆O₄H₂)₃(dmso)₂(H₂O)₂]·2dmso·18H₂O (1) and [Dy₂(C₆O₄Cl₂)₃(dmso)₄]·2dmso·2H₂O (2) show distorted hexagonal honeycomb layers with the solvent molecules (dmso and H₂O) located in the interlayer space and in the hexagonal channels that run perpendicular to the layers. The magnetic measurements of compounds 1, 2 and [Dy₂(C₆O₄(CN)Cl)₃(dmso)₆] (3), a recently reported related compound, show that the three compounds present slow relaxation of the magnetization. In compound 1 the SIM behaviour does not need the application of a DC field whereas 2 and 3 are field-induced SIM (FI-SIM) since they show slow relaxation of the magnetization when a DC field is applied. We discuss the differences observed in the crystal structures and magnetic properties based on the X group of the anilato ligands (H, Cl and Cl/CN) in 1–3 and in the recently reported derivative [Dy₂(C₆O₄Br₂)₃(dmso)₄]·2dmso·2H₂O (4) with X = Br, that is also a FI-SIM.     

新法合成手性磷酸锌钠

对合成手性磷酸锌钠(NaZnPO₄·H₂O) (CZP)的新方法进行了研究,用Na₃PO₄·12H₂Oand ZnSO₄·7H₂O作为起始原料,聚乙二醇-400（PEG-400）为表面活性剂,通过一步低热固相反应得到了手性磷酸锌钠。用TG/DTG,XRD, TEM 及 SEM表征了产物。实验结果表明,Na₃PO₄·12H₂O与ZnSO₄·7H₂O的配比采用不同的p/Zn比（0.9～1.15）,在60 ℃下陈化不同的时间(2.0～8.0 h) 所得到的NaZnPO₄·H₂O,除了结晶度稍为不同之外,晶体的手性结构是一样的。对照实验的结果显示陈化温度及阴离子调控着NaZnPO₄·H₂O的对映体形态。即,若以ZnSO₄·7H₂O或Zn(NO₃)₂·6H₂O为锌源,当反应混合物在60 ^oC陈化时,生成产物的结构是空间群为 P6₁22 的第一种手性结构,当反应混合物在室温陈化时,生成产物的结构则是空间群为 P6₅22 的第二种手性结构。     

ZnO Nanoparticles of Rubia cordifolia Extract Formulation Developed and Optimized with QbD Application,Considering Ex Vivo Skin Permeation,Antimicrobial and Antioxidant Properties

The objective of the current research is to develop ZnO-Manjistha extract (ZnO-MJE) nanoparticles (NPs) and to investigate their transdermal delivery as well as antimicrobial and antioxidant activity. The optimized formulation was further evaluated based on different parameters. The ZnO-MJE-NPs were prepared by mixing 10 mM ZnSO₄·7H₂O and 0.8% w/v NaOH in distilled water. To the above, a solution of 10 mL MJE (10 mg) in 50 mL of zinc sulfate was added. Box–Behnken design (Design-Expert software 12.0.1.0) was used for the optimization of ZnO-MJE-NP formulations. The ZnO-MJE-NPs were evaluated for their physicochemical characterization, in vitro release activity, ex vivo permeation across rat skin, antimicrobial activity using sterilized agar media, and antioxidant activity by the DPPH free radical method. The optimized ZnO-MJE-NP formulation (F13) showed a particle size of 257.1 ± 0.76 nm, PDI value of 0.289 ± 0.003, and entrapment efficiency of 79 ± 0.33%. Drug release kinetic models showed that the formulation followed the Korsmeyer–Peppas model with a drug release of 34.50 ± 2.56 at pH 7.4 in 24 h. In ex vivo studies ZnO-MJE-NPs-opt permeation was 63.26%. The antibacterial activity was found to be enhanced in ZnO-MJE-NPs-opt and antioxidant activity was found to be highest (93.14 ± 4.05%) at 100 µg/mL concentrations. The ZnO-MJE-NPs-opt formulation showed prolonged release of the MJE and intensified permeation. Moreover, the formulation was found to show significantly (p < 0.05) better antimicrobial and antioxidant activity as compared to conventional suspension formulations.