Magnetic separation, sunlight-driven photocatalytic activity, and antibacterial studies of Sm-doped Co0.33Mg0.33Ni0.33Fe2O4 nanoparticles.

Magnetic nanoparticles have emerged as a promising tool for wastewater treatment due to their unique properties. In this regard, Co0.33Mg0.33Ni0.33SmxFe2-xO4 (0.00 ≤ x ≤ 0.08) nanoparticles were prepared to examine their magnetic separation efficiency (MSE), photocatalytic, antibacterial, and antibiofilm performances. Pure nanoparticles, having the highest saturation magnetization (Ms = 31.87 emu/g), exhibit the highest MSE, where 95.6% of nanoparticles were separated after 20 min of applying a magnetic field of 150 mT. The catalytic performance of the prepared samples is examined by the photodegradation of rhodamine B (RhB) dye exposed to direct sunlight radiation. Improved photocatalytic activity is exhibited by Co0.33Mg0.33Ni0.33Sm0.04Fe1.96O4 nanoparticles, labeled as Sm0.04, where the rate of the degradation reaction is enhanced by 4.1 times compared to pure nanoparticles. Rising the pH and reaction temperature improves the rate of the photodegradation reaction of RhB. The incorporation of 15 wt% reduced graphene oxide (rGO) with Sm0.04 enhanced the rate of the reaction by 1.7 and 2.4 times compared with pure Sm0.04 sample and rGO, respectively. The antibacterial and antibiofilm activities against Escherichia coli, Leclercia adecarboxylata, Staphylococcus aureus, and Enterococcus faecium are assessed by the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) broth microdilution, the agar well diffusion, the time-kill assays, the biofilm formation, and destruction assays. The bacteria used in these assessments are isolated from wastewater. The nanoparticles exhibit a bacteriostatic activity, with a better effect against the Gram-positive isolates. Co0.33Mg0.33Ni0.33SmxFe2O4 (x = 0.00) nanoparticles have the best effect. The effect is exerted after 2-3 h of incubation. Gram-positive biofilms are more sensitive to nanoparticles.

Selective Functionalization of Carbonyl Closo-Decaborate [2-B10H9CO]- with Building Block Properties via Grignard Reagents.

A green, fast and selective approach for the synthesis of mono-substituted closo-decaborate derivatives [2-B10H9COR]2- has been established via a nucleophilic addition reaction between the carbonyl derivative of closo-decaborate [2-B10H9CO]- and the corresponding Grignard reagent RMgX, where R is the ethyl, iso-propyl, pentyl, allyl, vinyl and propynyl groups. This approach is accomplished under mild conditions with 70-80% yields. The significance of these derivative is their ability to constitute building blocks for polymeric integration via the allyl, vinyl and propynyl substituents. All products were characterized by 11B, 1H and 13C NMR, elemental analysis and mass spectrometry.

Enhanced adsorption performance of magnetic Ni0.5Zn0.5Fe2O4/Zn0.95Co0.05O nanocomposites for the removal of malachite green dye.

This investigation reports the synthesis and characterization of (1-x)Ni0.5Zn0.5Fe2O4/(x)Zn0.95Co0.05O nanocomposites, with 0.0 ≤ × ≤ 0.5. Fourier transform infrared (FTIR) and Raman spectroscopies confirmed the purity of the samples and the presence of bands corresponding to octahedral and tetrahedral iron occupancies for Ni0.5Zn0.5Fe2O4 nanoparticles. A shift in peak positions of these bands was detected upon the addition of Zn0.95Co0.05O nanoparticles. The magnetic properties of the nanocomposites were examined using Mössbauer spectrometry at both room temperature and 77 K. Room temperature analysis showed the existence of both ferromagnetic and superparamagnetic behaviors, while at 77 K, all nanocomposites showed ferromagnetic behavior. The adsorption performance of the nanocomposite on the removal of malachite green (MG) dye solution was investigated by varying the contact time, adsorbent concentration, and reaction temperature. The adsorption reaction followed the second-order kinetics and the sample with x = 0.3 showed the highest adsorption rate. The adsorption rate showed an increase with the increase in the reaction temperature. The adsorption isotherm was determined by applying different adsorption isotherms (Langmuir, Freundlich, and Temkin isotherms), and the results are well-fitted with the Langmuir theoretical model.

Grafting of Anionic Decahydro-Closo-Decaborate Clusters on Keggin and Dawson-Type Polyoxometalates: Syntheses, Studies in Solution, DFT Calculations and Electrochemical Properties.

Herein we report the synthesis of a new class of compounds associating Keggin and Dawson-type Polyoxometalates (POMs) with a derivative of the anionic decahydro-closo-decaborate cluster [B10H10]2- through aminopropylsilyl ligand (APTES) acting as both a linker and a spacer between the two negatively charged species. Three new adducts were isolated and fully characterized by various NMR techniques and MALDI-TOF mass spectrometry, notably revealing the isolation of an unprecedented monofunctionalized SiW10 derivative stabilized through intramolecular H-H dihydrogen contacts. DFT as well as electrochemical studies allowed studying the electronic effect of grafting the decaborate cluster on the POM moiety and its consequences on the hydrogen evolution reaction (HER) properties.

Unprecedented coupling reaction between two anionic species of a closo-decahydrodecaborate cluster and an Anderson-type polyoxometalate.

A novel decahydrodecaborate-functionalized Anderson type polyoxometalate has been synthesized and characterized in solution by ESI-MS, various NMR techniques and electrochemical methods. DFT studies provide strong support to understand the properties of this hybrid system.

ß-Cyclodextrin-Mediated Enantioselective Photochemical Electrocyclization of 1,3-Dihydro-2H-azepin-2-one.

The photochemical electrocyclization reaction of the title compound in the presence of ß-cyclodextrin was examined in different conditions. No enantioselectivity was observed in solution, but solid-state reactions of a 1:1 complex as a suspension or a thin film, followed by reduction, provided (1R,5R)-2-azabicyclo[3.2.0]heptan-3-one in isolated yields up to 79% and with ee values up to 45%.

Conformational Effects through Hydrogen Bonding in a Constrained γ-Peptide Template: From Intraresidue Seven-Membered Rings to a Gel-Forming Sheet Structure.

A series of three short oligomers (di-, tri-, and tetramers) of cis-2-(aminomethyl)cyclobutane carboxylic acid, a γ-amino acid featuring a cyclobutane ring constraint, were prepared, and their conformational behavior was examined spectroscopically and by molecular modeling. In dilute solutions, these peptides showed a number of low-energy conformers, including ribbonlike structures pleated around a rarely observed series of intramolecular seven-membered hydrogen bonds. In more concentrated solutions, these interactions defer to an organized supramolecular assembly, leading to thermoreversible organogel formation notably for the tripeptide, which produced fibrillar xerogels. In the solid state, the dipeptide adopted a fully extended conformation featuring a one-dimensional network of intermolecularly H-bonded molecules stacked in an antiparallel sheet alignment. This work provides unique insight into the interplay between inter- and intramolecular H-bonded conformer topologies for the same peptide template.

Magnetic Anisotropy in Pentacoordinate NiII and CoII Complexes: Unraveling Electronic and Geometrical Contributions.

The magnetic properties of the pentacoordinate [MII (Me4 cyclam)N3 ]+ (Me4 cyclam=tetramethylcyclam; N3 =azido; M=Ni, Co) complexes were investigated. Magnetization and EPR studies indicate that they have an easy plane of magnetization with axial anisotropy parameters D close to 22 and greater than 30 cm-1 for the Ni and Co complexes, respectively. Ab initio calculations reproduced the experimental values of the zero-field splitting parameters and allowed the orientation of the anisotropy tensor axes with respect to the molecular frame to be determined. For M=Ni, the principal anisotropy axis lies along the Ni-Nazido direction perpendicular to the Ni(Me4 cyclam) mean plane, whereas for M=Co it lies in the Co(Me4 cyclam) mean plane and thus perpendicular to the Co-Nazido direction. These orientations match one of the possible solutions experimentally provided by single-crystal cantilever torque magnetometry. To rationalize the geometry and its impact on the orientation of the anisotropy tensor axis, calculations were carried out on model complexes [NiII (NCH)5 ]2+ and [CoII (NCH)5 ]2+ by varying the geometry between square pyramidal and trigonal bipyramidal. The geometry of the complexes was found to be the result of a compromise between the electronic configuration of the metal ion and the structure-orienting effect of the Me4 cyclam macrocycle. Moreover, the orientation of the anisotropy axes is mainly dependent on the geometry of the complexes.

Two Compartmentalized Inner Receptors for the Tetramethylammonium Guest within a Keplerate-Type Capsule.

The host-guest interactions between the spherical porous Keplerate anion, [Mo132O372(CH3CO2)30(H2O)72](42-) (abbreviated {Mo132}) and the tetramethylammonium cation have been investigated extensively by one- and two-dimensional (EXSY, ROESY, and DOSY) and variable-temperature NMR. Evidence of two inner receptor sites specific for a NMe4(+) guest appears consistent with a quite striking compartmentalization phenomenon. ROESY NMR analyses showed that both sites exhibit a close spatial proximity with the hanging inner acetate groups, while a quantitative EXSY study revealed that these two sites are differentiated by their exchange rates. These NMR data support the hypothesis that these two inner sites could be delimited by the hanging inner acetate groups forming triangular (S1) or pentagonal (S2) hydrophobic pockets on the inner side of the capsule wall. Furthermore, the stability constants associated with the trapping process of the NMe4(+) guest on both the S1 and S2 sites have been determined, showing that the stability constant of the S1 sites decreases significantly as the concentration of the capsule increases gradually, while that of the S2 sites remains nearly unaffected. Such an observation has been interpreted as a result of the plugging process of the {Mo9O9} pores by the counterions NH4(+), which causes unfavorable electrostatic interactions for the NMe4(+) coordination on the proximal S1 site. Finally, the thermodynamic parameters of the NMe4(+) transfer from the solvated situation to the interior of the capsule were estimated from variable-temperature NMR experiments that provide the split of the global process into two successive events corresponding to the plugging and transfer across the inorganic shell.

Hydrophobic effect as a driving force for host-guest chemistry of a multi-receptor Keplerate-type capsule.

The effectiveness of the interactions between various alkylammonium cations and the well-defined spherical Keplerate-type {Mo132} capsule has been tracked by (1)H DOSY NMR methodology, revealing a strong dependence on the self-diffusion coefficient of the cationic guests balanced between the solvated and the plugging situations. Analysis of the data is fully consistent with a two-site exchange regime involving the 20 independent {Mo9O9} receptors of the capsule. Furthermore, quantitative analysis allowed us to determine the stability constants associated with the plugging process of the pores. Surprisingly, the affinity of the capsule for a series of cationic guests increases continuously with its apolar character, as shown by the significant change of the stability constant from 370 to 6500 for NH4(+) and NEt4(+), respectively. Such observations, supported by the thermodynamic parameters, evidence that the major factor dictating selectivity in the trapping process is the so-called "hydrophobic effect". Computational studies, using molecular dynamics simulations, have been carried out in conjunction with the experiments. Analysis of the radial distribution functions g(r) reveals that NH4(+) and NMe4(+) ions behave differently in the vicinity of the capsule. The NH4(+) ions do not exhibit well-defined distributions when in close vicinity. In contrast, the NMe4(+) ions displayed sharp distributions related to different scenarios, such as firmly trapped or labile guest facing the {Mo9O9} pores. Together, these experimental and theoretical insights should aid in the exploitation of these giant polyoxometalates in solution for various applications.

Synthesis, characterization, and tuning of the liquid crystal properties of ionic materials based on the cyclic polyoxothiometalate [{Mo4O4S4(H2O)3(OH)2}2(P8W48O184)](36-).

A series of compounds resulting from the ionic association of a nanoscopic inorganic cluster of formula [K2NaxLiy{Mo4O4S4(OH)2(H2O)3}2(HzP8W48O184)]((34-x-y-z)-), 1, with several organic cations such as dimethyldioctadecylammonium DODA(+), trimethylhexadecylammonium TMAC16(+), alkylmethylimidazoliums mimCn(+) (n = 12-20) and alkyl-dimethylimidazoliums dmimCn(+) (n = 12 and 16) was prepared and characterized in the solid state by FT-IR, EDX, Elemental analysis, TGA and solid state NMR. The solid state NMR experiments performed on (1)H, (13)C and (31)P nuclei evidenced the interactions between the cations and 1 as well as the organization of the alkyl chains of the cations within the solid. Polarized optical microscopy, DSC and SA-XRD experiments implicated mesomorphic phases for DODA(+) and mimCn(+) salts of 1. The crystallographic parameters were determined and demonstrated that the inter-lamellar spacing could be controlled upon changing the length of the alkyl chain, a very interesting result if we consider the huge size of the inorganic cluster 1 and the simple nature of the cations.

New triethoxysilylated 10-vertex closo-decaborate clusters. Synthesis and controlled immobilization into mesoporous silica.

Novel silylated hydroborate clusters comprising the closo-decaborate cage were prepared and characterized by (1)H, (13)C, (11)B, (29)Si NMR and mass spectroscopy ESI. The synthesis of such silylated clusters was achieved using reactive derivatives of [B10H10](2-), [1-B10H9N2](-) and [2-B10H9CO](-). These silylated decaborate clusters constitute a new class of precursors that can be covalently anchored onto various silica supports without any prior surface modification. As a proof of concept, the synthesized precursors were successfully anchored on mesoporous silica, SBA-15 type, in different percentages, where the mesoporous material retained its structure. All materials modified with closo-decaborate were characterized by (11)B and (29)Si solid state NMR, XRD, TEM and nitrogen sorption.