Inorganic-metalorganic hybrids based on copper(II)-monosubstituted Keggin polyanions and dinuclear copper(II)-oxalate complexes. Synthesis, X-ray structural characterization, and magnetic properties

Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-bipyridine-oxalate complexes in the corresponding alkaline acetate buffer led to the formation of hybrid metal organic-inorganic compounds K(2)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)].14H(2)O (1), K(14)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}](2)[SiW(11)O(39)Cu(H(2)O)].55H(2)O (2), (NH(4))(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (3), and Rb(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (4). Their structures have been established by single-crystal X-ray diffraction. The main structural feature of these compounds is the presence of copper(II)-monosubstituted alpha-Keggin polyoxoanions as inorganic building blocks, on which the mu-oxalatodicopper metalorganic blocks are supported. Compound 1contains the discrete hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)](2)(-), whereas the polymeric hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}(2)](n)(4)(n)(-) gives a monodimensional character to compounds 2-4. Magnetic and EPR results are discussed with respect to the crystal structure of the compounds. DFT calculations on both the [Cu(2)(bpy)(2)(H(2)O)(4)(mu-ox)](2+) cationic complex and the metalorganic blocks have been performed in order to determine the optimized geometry and the magnetic coupling constants, respectively.     

The first immobilization of pyridine-bis(oxazoline) chiral ligands

[formula: see text] A chiral pyridine-bis(oxazoline) ligand, functionalized with a vinyl group in the pyridine ring, can be polymerized with styrene and divinylbenzene to obtain supported chiral ligands. As proof of the usefulness of this supported ligands, the corresponding ruthenium complexes are catalysts for the cyclopropanation reaction of styrene with ethyl diazoacetate with up to 85% ee.     

Associative and segregative phase separations of poly(N-tert-butylacrylamide)/poly(acrylic acid) mixtures. Effect of solvent

Poly(N-tert-butylacrylamide) (PNtBAm) and poly(acrylic acid) (PAA) form interpolymer complexes in 1- and 2-propanol, blend in ethanol, whereas a segregative phase separation is observed when using methanol as solvent as shown by Fourier transform infrared (FTIR) spectrometry and elemental analysis studies. The composition of PNtBAm/PAA complexes has been determined. Thermal studies demonstrated that all complexes show unique glass transition temperatures, higher than those of the polymer components. Complexation of PAA with PNtBAm results in an improvement of its thermal stability. Solvent effects and specific interactions in the system PNtBAm/PAA have been studied by FTIR, revealing that differences in the polymer–solvent interactions are a decisive factor governing complex formation in solution.     

The finite <Emphasis Type="Italic">p</Emphasis>-groups with <Emphasis Type="Italic">p</Emphasis> conjugacy classes of non-normal subgroups

Let ν(G) be the number of conjugacy classes of non-normal subgroups of a finite group G. The finite groups for which ν(G) ≤ 2 were determined by Dedekind and by Schmidt in the early times of group theory. On the other hand, if G is a finite p-group, La Haye and Rhemtulla have proved that either ν(G) ≤ 1 or ν(G) ≥ p. In this note, we determine all finite p-groups satisfying ν(G) = p for p > 2.     

New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species

A series of nine [Sb₇W₃₆O₁₃₃Ln₃M₂(OAc)(H₂O)₈]^17? heterometallic anions ( Ln₃M₂ ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW₉O₃₃} capping unit formed by a planar {MW₆O₂₄} fragment to which three {WO₂} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW₆O₂₄} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln₃M₂ anions possess chirality owing to a {Sb₄O₄} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce₃Co₂ derivative.     

Tetrahydroxy-p-benzoquinone as a source of polydentate O-donor ligands. Synthesis, crystal structure, and magnetic properties of the [Cu(bpy)(dhmal)]2 dimer and the two-dimensional [{SiW12O40}{Cu2(bpy)2(H2O)(ox)}2].16H2O inorganic-metalorganic hybrid

The use of tetrahydroxy-p-benzoquinone as a slow source of dihydroxymalonato and oxalato ligands led to the isolation under open-air mild reaction conditions of five different compounds, two of them prepared for the first time: [Cu(bpy)(dhmal)]2 (1) and [{SiW12O40}{Cu2(bpy)2(H2O)(ox)}2].16H2O (5) (bpy, 2,2'-bipyridine; dhmal, dihydroxymalonate; ox, oxalate). A possible mechanism for the oxidation of the benzoquinone to give the croconate dianion, which undergoes further ring-opening oxidation to decompose into dihydroxymalonate and oxalate, is proposed. All compounds have been characterized by elemental analysis, thermogravimetry, infrared spectroscopy, and powder X-ray diffraction. Single-crystal X-ray diffraction, electron paramagnetic resonance, and magnetic susceptibility measurements have been performed for compounds 1 and 5. A complete band assignment of the experimental FT-IR spectra is given through comparison with the ones calculated using density functional theory (DFT). The neutral dimer 1 constitutes the first structurally characterized example of a transition metal-dhmal complex, and it contains two copper atoms bridged by two dihydroxymalonato ligands acting in a mu2-kappa3O,O',O":kappa1O coordination fashion, so that an equatorial-axial Cu2(mu2-O)2 rhomboid core is formed. On the other hand, the inorganic-metalorganic hybrid compound 5 shows a two-dimensional arrangement of Keggin polyanions linked by one of the Cu atoms of the oxalate cationic dimers to give layers parallel to the (10) plane, the remaining ox-Cu-bpy fragments acting as interlamellar separators. In both cases, magnetic and EPR results are discussed with respect to the crystal structure of the compounds and, for compound 1, also with respect to DFT calculations of the exchange coupling constant.     

Pressurized hot ethanol extraction of carotenoids from carrot by-products

Carotenoids are known for their antioxidant activity and health promoting effects. One of the richest sources of carotenoids are carrots. However, about 25% of the annual production is regarded as by-products due to strict market policies. The aim of this study was to extract carotenoids from those by-products. Conventional carotenoid extraction methods require the use of organic solvents, which are costly, environmentally hazardous, and require expensive disposal procedures. Pressurized liquid extraction (PLE) utilizes conventional solvents at elevated temperatures and pressure, and it requires less solvent and shorter extraction times. The extraction solvent of choice in this study was ethanol, which is a solvent generally recognized as safe (GRAS). The extraction procedure was optimized by varying the extraction time (2-10 min) and the temperature (60-180 °C). β-Carotene was used as an indicator for carotenoids content in the carrots. The results showed that time and temperatures of extraction have significant effect on the yield of carotenoids. Increasing the flush volume during extraction did not improve the extractability of carotenoids, indicating that the extrication method was mainly desorption/diffusion controlled. Use of a dispersing agent that absorbs the moisture content was important for the efficiency of extraction. Analysing the content of β-carotene at the different length of extraction cycles showed that about 80% was recovered after around 20 min of extraction.     

A review of bacterial cellulose: sustainable production from agricultural waste and applications in various fields

Bacterial cellulose (BC) is a polymer with interesting conformation and properties. BC can be obtained in different shapes and is easily modified by chemical and physical means, so its applications in the production of new materials and nanocomposites for different purposes have been in the focus of many research projects. However, one of the major challenges to address in bacterium-derived polymer technology is to find suitable carbon sources as substrates that are cheap and do not compete with food production for achieving large scale industrial applications. Agricultural wastes are defined as the residues from the growing and processing of raw agricultural products such as crops, fruits, vegetables and dairy products. Their composition can vary depending on the type of agricultural activity and harvesting conditions, but these residues are suitable for the production of BC. The aim of this review is to give insight into the production of BC using agro-wastes and an overview of the most interesting and novel applications of this biopolymer in different areas i.e. environmental applications, optoelectronic and conductive devices, food ingredients and packaging, biomedicine, and 3D printing technology.

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