Highly-controlled grafting of mono and dicationic 4,4'-bipyridine derivatives on SBA-15 for potential application as adsorbent of CuCl(2) from ethanol solution

Ultra-large-pore FDU-12 (ULP-FDU-12) silica with face-centered cubic structure (Fm3m type) of spherical mesopores was synthesized using Pluronic F127 triblock copolymer (EO(106)PO(70)EO(106)) and ethylbenzene as a new micelle expander at initial temperature of 14 °C. Ethylbenzene was identified on the basis of its reported extent of solubilization in poly(ethylene oxide)-poly(propylene oxide)-type surfactant micelles, which was similar to that of xylene, the latter having been shown earlier to afford ULP-FDU-12. The unit-cell parameter of as-synthesized ULP-FDU-12 was 55 nm, which is similar to the highest value reported when xylenes (mixture of isomers) were used and larger than that achieved with trimethylbenzene. The unit-cell parameter of calcined ULP-FDU-12 reached 52 nm. For the obtained materials, the nominal pore cage diameter calculated from nitrogen adsorption reached 32 nm, whereas the actual pore cage diameter calculated using the geometrical relation was 36 nm. The pore entrance size was below 5 nm before the acid treatment, but was greatly enlarged as a result of the treatment. The sample prepared without hydrothermal treatment was converted to ordered closed-pore silica at as low as 400-450 °C. Our study confirms the ability to select micelle expanders on the basis of data on solubilization of compounds in micelle solutions.     

Expedient one-pot organometallics-free synthesis of tris(2-pyridyl)phosphine from 2-bromopyridine and elemental phosphorus

2-Bromopyridine reacts with elemental phosphorus (red or white) in a superbasic KOH/DMSO(H₂O) suspension at 100 °C (for red phosphorus) and 75 °C (for white phosphorus) over 3 h to afford tris(2-pyridyl)phosphine in a 62% yield (from red phosphorus) and a 50% yield (from white phosphorus). Under microwave assistance, the reaction with red phosphorus takes just 20 min to produce tris(2-pyridyl)phosphine in 53% yield. A hitherto unknown complex, [Pd(PPy₃)₂Cl₂]·CH₂Cl₂, synthesized from tris(2-pyridyl)phosphine and PdCl₂, has the cis-configuration; this is unusual for bis(phosphino)palladium dichloride complexes.     

Capillary cavity flow past a circular cylinder

Cavity flow past a circular cylinder is considered accounting for the surface tension on the cavity boundary. The fluid is assumed to be inviscid and incompressible, and the flow is assumed to be irrotational. The solution is based on two derived governing expressions, which are the complex velocity and the derivative of the complex potential defined in an auxiliary parameter region. An integral equation in the velocity magnitude along the free surface is derived from the dynamic boundary condition. The Brillouin–Villat criterion is employed to determine the location of the point of flow separation. The cases of zero surface tension and zero cavitation number are obtained as limiting cases of the solution. Numerical results concerning the effects of surface tension and cavitation development on the cavity detachment, the drag force and the geometry of the free boundaries are presented over a wide range of the Weber and the cavitation numbers.     

Exploration of the Crystal Structure and Thermal and Spectroscopic Properties of Monoclinic Praseodymium Sulfate Pr2(SO4)3

Praseodymium sulfate was obtained by the precipitation method and the crystal structure was determined by Rietveld analysis. Pr₂(SO₄)₃ is crystallized in the monoclinic structure, space group C2/c, with cell parameters a = 21.6052 (4), b = 6.7237 (1) and c = 6.9777 (1) Å, β = 107.9148 (7)°, Z = 4, V = 964.48 (3) ų (T = 150 °C). The thermal expansion of Pr₂(SO₄)₃ is strongly anisotropic. As was obtained by XRD measurements, all cell parameters are increased on heating. However, due to a strong increase of the monoclinic angle β, there is a direction of negative thermal expansion. In the argon atmosphere, Pr₂(SO₄)₃ is stable in the temperature range of T = 30–870 °C. The kinetics of the thermal decomposition process of praseodymium sulfate octahydrate Pr₂(SO₄)₃·8H₂O was studied as well. The vibrational properties of Pr₂(SO₄)₃ were examined by Raman and Fourier-transform infrared absorption spectroscopy methods. The band gap structure of Pr₂(SO₄)₃ was evaluated by ab initio calculations, and it was found that the valence band top is dominated by the p electrons of oxygen ions, while the conduction band bottom is formed by the d electrons of Pr³⁺ ions. The exact position of ZPL is determined via PL and PLE spectra at 77 K to be at 481 nm, and that enabled a correct assignment of luminescent bands. The maximum luminescent band in Pr₂(SO₄)₃ belongs to the ³P₀ → ³F₂ transition at 640 nm.     

Amine-Reactive BODIPY Dye: Spectral Properties and Application for Protein Labeling

A boron-dipyrromethene (BODIPY) derivative reactive towards amino groups of proteins (NHS-Ph-BODIPY) was synthesized. Spectroscopic and photophysical properties of amine-reactive NHS-Ph-BODIPY and its non-reactive precursor (COOH-Ph-BODIPY) in a number of organic solvents were investigated. Both fluorescent dyes were characterized by green absorption (521–532 nm) and fluorescence (538–552 nm) and medium molar absorption coefficients (46,500–118,500 M⁻¹·cm⁻¹) and fluorescence quantum yields (0.32 – 0.73). Solvent polarizability and dipolarity were found to play a crucial role in solvent effects on COOH-Ph-BODIPY and NHS-Ph-BODIPY absorption and emission bands maxima. Quantum-chemical calculations were used to show why solvent polarizability and dipolarity are important as well as to understand how the nature of the substituent affects spectroscopic properties of the fluorescent dyes. NHS-Ph-BODIPY was used for fluorescent labeling of a number of proteins. Conjugation of NHS-Ph-BODIPY with bovine serum albumin (BSA) resulted in bathochromic shifts of absorption and emission bands and noticeable fluorescence quenching (about 1.5 times). It was demonstrated that the sensitivity of BSA detection with NHS-Ph-BODIPY was up to eight times higher than with Coomassie brilliant blue while the sensitivity of PII-like protein PotN (PotN) detection with NHS-Ph-BODIPY and Coomassie brilliant blue was almost the same. On the basis of the molecular docking results, the most probable binding sites of NHS-Ph-BODIPY in BSA and PotN and the corresponding binding free energies were estimated.     

An Efficient Method of Birch Ethanol Lignin Sulfation with a Sulfaic Acid-Urea Mixture

For the first time, the process of birch ethanol lignin sulfation with a sulfamic acid-urea mixture in a 1,4-dioxane medium was optimized experimentally and numerically. The high yield of the sulfated ethanol lignin (more than 96%) and containing 7.1 and 7.9 wt % of sulfur was produced at process temperatures of 80 and 90 °C for 3 h. The sample with the highest sulfur content (8.1 wt %) was obtained at a temperature of 100 °C for 2 h. The structure and molecular weight distribution of the sulfated birch ethanol lignin was established by FTIR, 2D ¹H and ¹³C NMR spectroscopy, and gel permeation chromatography. The introduction of sulfate groups into the lignin structure was confirmed by FTIR by the appearance of absorption bands characteristic of the vibrations of sulfate group bonds. According to 2D NMR spectroscopy data, both the alcohol and phenolic hydroxyl groups of the ethanol lignin were subjected to sulfation. The sulfated birch ethanol lignin with a weight average molecular weight of 7.6 kDa and a polydispersity index of 1.81 was obtained under the optimum process conditions. Differences in the structure of the phenylpropane units of birch ethanol lignin (syringyl-type predominates) and abies ethanol lignin (guaiacyl-type predominates) was manifested in the fact that the sulfation of the former proceeds more completely at moderate temperatures than the latter. In contrast to sulfated abies ethanol lignin, the sulfated birch ethanol lignin had a bimodal and wider molecular weight distribution, as well as less thermal stability. The introduction of sulfate groups into ethanol lignin reduced its thermal stability.     

New pecJ-n (n = 1, 2) Basis Sets for High-Quality Calculations of Indirect Nuclear Spin–Spin Coupling Constants Involving 31P and 29Si: The Advanced PEC Method

In this paper, we presented new J-oriented basis sets, pecJ-n (n = 1, 2), for phosphorus and silicon, purposed for the high-quality correlated calculations of the NMR spin–spin coupling constants involving these nuclei. The pecJ-n basis sets were generated using the modified version of the property-energy consistent (PEC) method, which was introduced in our earlier paper. The modifications applied to the original PEC procedure increased the overall accuracy and robustness of the generated basis sets in relation to the diversity of electronic systems. Our new basis sets were successfully tested on a great number of spin–spin coupling constants, involving phosphorus or/and silicon, calculated within the SOPPA(CCSD) method. In general, it was found that our new pecJ-1 and pecJ-2 basis sets are very efficient, providing the overall accuracy that can be characterized by MAEs of about 3.80 and 1.98 Hz, respectively, against the benchmark data obtained with a large dyall.aae4z⁺ basis set of quadruple-ζ quality.     

Koszul duality for extension algebras of standard modules

We define and investigate a class of Koszul quasi-hereditary algebras for which there is a natural equivalence between the bounded derived category of graded modules and the bounded derived category of graded modules over (a proper version of) the extension algebra of standard modules. Examples of such algebras include, in particular, the multiplicity free blocks of the BGG category O, and some quasi-hereditary algebras with Cartan decomposition in the sense of König.     

Analytic description of enhanced backscattering and negative polarization from a cloud of dipoles

We develop a second-order model of the light scattered by a cloud of randomly positioned dipoles and consider the interference of reciprocal rays that lead to enhanced backscatter and negative polarization. For large pathlength separations, we derive analytic expressions for the individual polarization intensities.