Isomorphous replacement of M(II) ions in M(II)-Gd(III) dimers (M(II) = Cu(II), Mn(II), Ni(II), Co(II), Zn(II)): magnetic studies of the products

Complexes [M(II)Gd(III){pyCO(OEt)pyC(OH)(OEt)py}?](ClO?)?·EtOH [M(II) = Cu(II) (1), Mn(II) (2), Ni(II) (3), Co(II) (4) and Zn(II) (5)] crystallize in the monoclinic Cc space group and contain one hexacoordinate M(II) ion and one enneacoordinate Gd(III) ion, bridged by three {pyCO(OEt)pyC(OH)(OEt)py}? ligands. Magnetic susceptibility measurements indicate a ferromagnetic interaction for 1 and antiferromagnetic interactions for 2-4. Using the ? = -J?(Gd(III))?(M(II)) spin Hamiltonian formalism, fits to the magnetic susceptibility data yielded J values of +0.32 cm?1 for 1, -1.7 cm?1 for 2, and -0.22 cm?1 for 3. In complex 4, the orbital contributions of Co(II) precluded the determination of the magnetic coupling. The complex follows the Curie-Weiss law with θ = -2.07 K (-1.44 cm?1).     

Rational Screening of High-Voltage Electrolytes and Additives for Use in LiNi0.5Mn1.5O4-Based Li-Ion Batteries

In the present work, we focus onthe experimental screening of selected electrolytes, which have been reported earlier in different works, as a good choice for high-voltage Li-ion batteries. Twenty-four solutions were studied by means of their high-voltage stability in lithium half-cells with idle electrode (C+PVDF) and the LiNi_0.5Mn_1.5O₄-based composite as a positive electrode. Some of the solutions were based on the standard 1 M LiPF₆ in EC:DMC:DEC = 1:1:1 with/without additives, such as fluoroethylene carbonate, lithium bis(oxalate) borate and lithium difluoro(oxalate)borate. More concentrated solutions of LiPF₆ in EC:DMC:DEC = 1:1:1 were also studied. In addition, the solutions of LiBF₄ and LiPF₆ in various solvents, such as sulfolane, adiponitrile and tris(trimethylsilyl) phosphate, atdifferent concentrations were investigated. A complex study, including cyclic voltammetry, galvanostatic cycling, impedance spectroscopy and ex situ PXRD and EDX, was applied for the first time to such a wide range of electrolytesto provide an objective assessment of the stability of the systems under study. We observed a better anodic stability, including a slower capacity fading during the cycling and lower charge transfer resistance, for the concentrated electrolytes and sulfolane-based solutions. Among the studied electrolytes, the concentrated LiPF₆ in EC:DEC:DMC = 1:1:1 performed the best, since it provided both low SEI resistance and stability of the LiNi_0.5Mn_1.5O₄ cathode material.     

Isocratic liquid chromatographic determination of three paraben preservatives in hygiene wipes using a reversed phase core-shell narrow-bore column

The first HPLC method for the separation of three paraben preservatives (methyl-, ethyl- and propyl parabens) using a core-shell analytical column is reported in this study. The separation was completed in less than 8 min at a low flow rate of 0.4 mL min⁻¹ and an isocratic mobile phase containing 20% acetonitrile as organic modifier. The backpressure was < 200 bar in all cases, enabling the usage of conventional HPLC equipment. The proposed analytical procedure was validated for linearity (0.5–20 μg L⁻¹), limits of detection (15–43 μg L⁻¹) and quantification (50–142 μg L⁻¹), selectivity, within day (1.3–1.5%) and day-to-day (3.4–4.6%) precision and accuracy. The proposed method has been applied to the determination of the selected paraben preservatives in commercially available hygiene wipes. The mean percent recoveries were found to be in the range of 98.0–98.4%.      

A cationic cysteine-hydrazide as an enrichment tool for the mass spectrometric characterization of bacterial free oligosaccharides

In Campylobacterales and related ε-proteobacteria with N-linked glycosylation (NLG) pathways, free oligosaccharides (fOS) are released into the periplasmic space from lipid-linked precursors by the bacterial oligosaccharyltransferase (PglB). This hydrolysis results in the same molecular structure as the oligosaccharide that is transferred to a protein to be glycosylated. This allowed for the general elucidation of the fOS-branched structures and monosaccharides from a number of species using standard enrichment and mass spectrometry methods. To aid characterization of fOS, hydrazide chemistry has often been used for chemical modification of the reducing part of oligosaccharides resulting in better selectivity and sensitivity in mass spectrometry; however, the removal of the unreacted reagents used for the modification often causes the loss of the sample. Here, we develop a more robust method for fOS purification and characterize glycostructures using complementary tandem mass spectrometry (MS/MS) analysis. A cationic cysteine hydrazide derivative was synthesized to selectively isolate fOS from periplasmic fractions of bacteria. The cysteine hydrazide nicotinamide (Cyhn) probe possesses both thiol and cationic moieties. The former enables reversible conjugation to a thiol-activated solid support, while the latter improves the ionization signal during MS analysis. This enrichment was validated on the well-studied Campylobacter jejuni by identifying fOS from the periplasmic extracts. Using complementary MS/MS analysis, we approximated data of a known structure of the fOS from Campylobacter concisus. This versatile enrichment technique allows for the exploration of a diversity of protein glycosylation pathways.     

Experimental Evidence for the Incorporation of Two Metals at Equivalent Lattice Positions in Mixed-Metal Metal–Organic Frameworks

Metal–organic frameworks containing multiple metals distributed over crystallographically equivalent framework positions (mixed-metal MOFs) represent an interesting class of materials, since the close vicinity of isolated metal centers often gives rise to synergistic effects. However, appropriate characterization techniques for detailed investigations of these mixed-metal metal–organic framework materials, particularly addressing the distribution of metals within the lattice, are rarely available. The synthesis of mixed-metal FeCuBTC materials in direct syntheses proved to be difficult and only a thorough characterization using various techniques, like powder X-ray diffraction, X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy, unambiguously evidenced the formation of a mixed-metal FeCuBTC material with HKUST-1 structure, which contained bimetallic Fe−Cu paddlewheels as well as monometallic Cu−Cu and Fe−Fe units under optimized synthesis conditions. The in-depth characterization showed that other synthetic procedures led to impurities, which contained the majority of the applied iron and were impossible or difficult to identify using solely standard characterization techniques. Therefore, this study shows the necessity to characterize mixed-metal MOFs extensively to unambiguously prove the incorporation of both metals at the desired positions. The controlled positioning of metal centers in mixed-metal metal–organic framework materials and the thorough characterization thereof is particularly important to derive structure–property or structure–activity correlations.     

Relaxation of microparticles exposed to hydrodynamic forces in microfluidic conduits

The behavior of microparticles exposed to gravitational and lift forces and to the velocity gradient in flow velocity profile formed in microfluidic conduits is studied from the viewpoint of the transient period (the relaxation) between the moment at which a particle starts to be transported by the hydrodynamic flow and the time at which it reaches an equilibrium position, characterized by a balance of all active forces. The theoretical model allowing the calculation of the relaxation time is proposed. The numerical calculus based on the proposed model is compared with the experimental data obtained under different experimental conditions, namely, for different lengths of microfluidic channels, different average linear velocities of the carrier liquid, and different sizes and densities of the particles used in the study. The results are important for the optimization of microfluidic separation units such as microthermal field-flow fractionation channels in which the separation or manipulation of the microparticles of various origin, synthetic, natural, biological, etc., is performed under similar experimental conditions but by applying an additional thermodynamic force.

Mono- and diprotonation of the superbasic bisguanidine 1,2-Bis(N,N,N',N'-tetramethylguanidino)benzene (btmgb) and Pt II and Pt IV complexes of chelating bisguanidines and guanidinates

New Pt complexes of chelating bisguanidines and guanidinate ligands were synthesized and characterized. 1,2-Bis(N,N,N',N'-tetramethylguanidino)benzene (btmgb) was used as a neutral chelating bisguanidine ligand, and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate (hpp(-)) as a guanidinate ligand. The salts [btmgbH](+)[HOB(C(6)F(5))(3)](-) and [btmgbH(2)]Cl(2) and the complexes [(btmgb)PtCl(2)], [(btmgb)PtCl(dmso)](+)[PtCl(3)(dmso)](-), and [(btmgb)PtCl(dmso)](+)[Cl(-)] were synthesized and characterized. In the [btmgbH](+) cation the proton is bound to only one N atom. In the other complexes, both imine N atoms are coordinated to the Pt(II), thus adopting a eta(2)-coordinational mode. The hpp(-) anion, which usually prefers a bridging binding mode in dinuclear complexes, is eta(2)-coordinated in the Pt(IV) complex [(eta(2)-hpp)(hppH)PtCl(2){N(H)C(O)CH(3)}], which is formed (in low yield) by reaction between cis-[(hppH)(2)PtCl(2)] and H(2)O(2) in CH(3)CN.