Synthesis of FDU-1 silica with narrow pore size distribution and tailorable pore entrance size in the presence of sodium chloride

Ordered silicas with large (9-15 nm), uniform, cagelike mesopores were synthesized under acidic aqueous conditions from tetraethyl orthosilicate in the presence of sodium chloride using poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer B50-6600 (EO39BO47EO39, Dow Chemicals) as a supramolecular template. Except for the use of NaCl in our case, the synthesis mixture composition was the same as that originally reported by Zhao et al. for the synthesis of FDU-1 silica, which was later shown to exhibit a cubic close-packed (Fm3m) structure with stacking faults related to the occurrence of hexagonal close-packed stacking sequences. The copolymer-templated silicas were formed at room temperature and in most cases were subjected to the hydrothermal treatment at 373 or 393 K. The calcined materials were characterized using small-angle X-ray scattering (SAXS) and nitrogen and argon adsorption at 77 K. SAXS patterns were generally similar to those reported for FDU-1 silica, indicating the cubic close-packed (Fm3m) structure, but the presence of stacking faults characteristic of a hexagonal close-packed structure cannot be precluded. The addition of the salt was found to significantly narrow the pore size distributions and to improve the uniformity of entrances to the cagelike mesopores, whereas the pore diameter, specific surface area, and pore volume were similar (in most cases slightly lower) to those for FDU-1 silicas obtained in the absence of NaCl. The materials synthesized in the presence of NaCl also appeared to have better resolved SAXS patterns. The feasibility of tailoring the pore cage diameter (from approximately 9.5 to 14.5 nm) and pore entrance diameter (from below 4 to approximately 8 nm) simply by adjusting the hydrothermal treatment temperature and time was demonstrated, indicating that these simple and convenient ways of structural design of cagelike mesopores are operative in the case of syntheses in the presence of inorganic salts.     

MA-XRF study of 15th–17th century icons from the collection of the National Museum in Krakow,Poland

In 2015, the National Museum in Krakow, Poland, started a grant from the National Programme for the Development of Humanities, its goal to investigate an important collection of old Orthodox painting, including more than 50 15th to 17th century icons originating from the territory of the historical Orthodox Diocese of Przemyśl within the borders of the Polish Kingdom. The aim of researching the iconography, provenance, and technology of the artworks was to describe their specific features and destination, in detail, and to characterise their artistic milieu. Many different techniques were used during research, such as X-ray fluorescence (XRF), X-ray diffraction, reflectography, radiography, ultraviolet–visible imaging, Fourier-transform infrared spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy of prepared paint layer cross sections, and dendro-chronological analysis. This paper focuses on highlighting the advantages and disadvantages of the spatially resolved macro-XRF scanning (MA-XRF) technique. Most interesting results concluded from elemental distribution maps obtained through the use of Bruker, M6 Jetstream MA-XRF scanner include the following: characterisation of the type of gold and silver foil used in the icons; determination of main pigments, including the use of lead tin yellow unusual in iconography; and the noting of an interesting distribution of blue pigments as well as the presence of orpiment. Surprisingly, a considerable amount of zinc with azurite addition was observed in brown layers. The results obtained primarily highlight all the typical features of local Carpathian icon craft.     

Determination of the rate constant of oxygen quenching of the excited states of molecules from the singlet oxygen luminescence

We have pioneered a method of determining the rate constant of quenching of the excited electronic states of molecules by molecular oxygen from measurements of the kinetics of photosensitized luminescence of singlet molecular oxygen (^lδ_g). The method can be used in the case where the lifetime of the excited electronic state in an air-saturated solution is comparable with or larger than the luminescence time of the singlet molecular oxygen in the given solvent. It is shown that this situation is implemented on quenching, by molecular oxygen, of the excited triplet states associated with the biopolymers of tetrapyrrole molecules in aqueous (H₂O and D₂O) solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 401–404, May–June, 2000.     

Determination and tailoring the pore entrance size in ordered silicas with cage-like mesoporous structures

A practical approach to the determination of the pore entrance size in ordered silicas with cage-like mesoporous structures (OSCMSs) is proposed. A fundamental insight into the OSCMS pore connectivity is gained, including the control of the pore entrance size by post-synthesis surface modification, and by selection of appropriate synthesis temperature. These findings show a new promise for the synthesis of mesoporous solids with molecular size- and shape-selective properties.     

Internal dynamics of hydroxymethyl rotation from CH2 cross-correlated dipolar relaxation in methyl-beta-D-glucopyranoside

Conventional relaxation parameters (T1(-1), T2(-1), and NOE), obtained at different temperatures and magnetic fields, are reported for the hydroxymethyl (C6) carbon in methyl-beta-D-glucopyranoside in a D2O/DMSO cryosolvent. These data are interpreted with the Lipari-Szabo model. In addition, two-field measurements of longitudinal and spin-locked relaxation rates related to the cross-correlated carbon-proton dipole-dipole interactions for the same carbon are reported. The complete data set consisting the conventional and cross-correlated relaxation parameters is interpreted using a new "hybrid" approach, in which the Lipari-Szabo model for the auto-correlated spectral densities is combined with the two-site jump model for the cross-correlated spectral densities, with the global correlation time as a common parameter. The two-site jump rates thus obtained are in reasonable agreement with the ultrasonic relaxation measurements, and have reasonable temperature dependence.     

Phosphorescence studies of the Pt(thpy)<Subscript>2</Subscript> complex for use in single molecule spectroscopy

The spectral and kinetic characteristics of the complex Pt(thpy)₂ (thpy^? is the doubly protonated form of 2-(2-thienyl)pyridine) in solid and liquid solutions are studied. It is found that this compound phosphoresces intensively in the temperature range 4.2–293 K. The effects of temperature and molecular oxygen on the photophysical parameters of the complex are studied. It is shown that the phosphorescence of the Pt(thpy)₂ complex is efficiently quenched by molecular oxygen, with the quenching rate constant being equal to k _q = (2.2–5.1) × 10⁹ (M s)^?1. Under direct selective excitation of the complex in isotropic media at 4.2 K via the channel S₀ → T₁, fine structure phosphorescence spectra are observed.     

Evolution of solid state systems containing mutually coupled dipolar and quadrupole spins: perturbation treatment

Perturbation approach to time evolution of multi-spin systems containing quadrupole and dipolar spins has been presented and discussed. The treatment comprises polarization transfer effects, field-dependent relaxation processes of dipolar as well as quadrupole spins and combined results of both of them. Complete theories dealing with various aspects of the spin dynamic processes have been proposed. Because of an educational character of this paper, relevant assumptions, limitations and even particular steps of the proposed treatments have been discussed in detail. Special emphasis is put on understanding of validity regimes of the perturbation treatment, depending on relative strengths of spin interactions and timescales of relevant motional processes affecting them. Motional regimes required for spins to be involved in essentially different evolution pathways like polarization transfers or relaxation have been illustrated by experimental examples.     

An improved nonlinear optical pulse propagation equation

A new equation for self-focusing of extremely focused short-duration intense pulses is derived using a method that treats diffraction and dispersion to all orders with nonlinearity present, and self-consistently determines the nonlinear derivative terms present in the propagation equation. It generalizes both the previous formulation of linear optical pulse propagation to the nonlinear regime, and the cw nonlinear regime propagation to the pulsed regime by including temporal characteristics of the pulse. We apply the new equation and propagate a tightly focused picosecond pulse in silica and explicitly show the effects of spatial-derivative nonlinear coupling terms.     

Spectral Manifestations of Anion-Cation Interactions of Water-Soluble Porphyrins

The influence of anion-cation interactions on the structure and electronic absorption spectra of cationic 5,10,15,20-tetrakis-(4-N-methylpyridyl)porphyrin and anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin has been investigated by absorption spectroscopy and molecular modeling. It is shown that the shifts of bands in the electronic absorption spectra appearing when passing from aqueous solutions to solutions in organic solvents are due to the interaction of ionized peripheral substituents of the porphyrin macrocycle with counterions. The bathochromic shift of the Q _x transition is due to the influence of counterions on the energy characteristics of the molecule itself, primarily, as a result of Coulomb interactions changing the relative position of the orbitals and the distribution of electron density on them. The hypsochromic shift of the Q _y transition is a consequence of the increase in the dihedral angle between the plane of the porphyrin macrocycle and the aromatic rings with ionized groups due to the decrease in the -electron interaction between them under the action of counterions.