Interactions of transition metal atoms in high-spin states: Cr2, Sc-Cr, and Sc-Kr

The high-spin van der Waals states are examined for the following dimers: Cr(2) ((13)Sigma(g)(+)), Sc-Cr ((8)Sigma(+), (8)Pi, (8)Delta), and Sc-Kr ((2)Sigma(+), (2)Pi, (2)Delta). These three systems offer a wide range of van der Waals interactions: anomalously strong, intermediate, and typically weak. The single-reference [coupled cluster with single, double, and noniterative triple excitations, RCCSD(T)] method is used in the calculations for all three systems. In addition, a range of configuration-interaction based methods is applied in Cr(2) and Sc-Cr. The three dimers are shown to be bound by the dispersion interaction of varying strength. In a related effort, the dispersion energy and its exchange counterpart are calculated using the newly developed open-shell variant of the symmetry-adapted perturbation theory (SAPT). The restricted open-shell time-dependent Hartree-Fock linear response function is used in the calculations of the dispersion energy in Sc-Cr and Sc-Kr calculations, while the restricted open-shell time-dependent density functional linear response function is used for Cr(2). A hybrid method combining the repulsive restricted open-shell Hartree-Fock (or complete active space self-consistent field) interaction energy with the dispersion and exchange-dispersion terms is tested against the RCCSD(T) results for the three complexes. The Cr(2) ((13)Sigma(g)(+)) complex has the well depth of 807.8 cm(-1) at the equilibrium distance of 6.18a(0) and the dissociation energy of 776.8 cm(-1). The octet-state Sc-Cr is about four times more strongly bound with the order of well depths of (8)Delta>(8)Pi>(8)Sigma(+) and a considerable anisotropy. The enhanced bonding is attributed to the unusually strong dispersion interaction. Sc-Kr ((2)Sigma(+), (2)Pi, (2)Delta) is a typical van der Waals dimer with well depths in the range of 81 cm(-1) ((2)Delta), 84 cm(-1) ((2)Sigma(+)), and 86 cm(-1) ((2)Pi). The hybrid model based on SAPT leads to results which are in excellent qualitative agreement with RCCSD(T) for all three interactions.     

Absorption and fluorescence of PRODAN in phospholipid bilayers: a combined quantum mechanics and classical molecular dynamics study

Absorption and fluorescence spectra of PRODAN (6-propionyl-2-dimethylaminonaphthalene) were studied by means of the time-dependent density functional theory and the algebraic diagrammatic construction method. The influence of environment, a phosphatidylcholine lipid bilayer and water, was taken into account employing a combination of quantum chemical calculations with empirical force-field molecular dynamics simulations. Additionally, experimental absorption and emission spectra of PRODAN were measured in cyclohexane, water, and lipid vesicles. Both planar and twisted configurations of the first excited state of PRODAN were taken into account. The twisted structure is stabilized in both water and a lipid bilayer, and should be considered as an emitting state in polar environments. Orientation of the excited dye in the lipid bilayer significantly depends on configuration. In the bilayer, the fluorescence spectrum can be regarded as a combination of emission from both planar and twisted structures.     

Stability of arsenic species in hydroponic media and its influence on arsenic uptake and distribution in White mustard (Sinapis alba L.)

The long-term uptake and distribution of arsenic compounds by hydroponically cultivated White mustard (Sinapis alba) was investigated with a special emphasis on controlling the stability of the arsenic compounds in nutrient solution during the experiment. It was concluded that arsenites are rapidly oxidised to arsenates during the 7-day cultivation of White mustard. The presence of plant roots increases the oxidation rate of arsenites. Dimethylarsinic acid (DMA) and arsenates remain stable during the exposition, while monomethylarsonic acid (MMA) is partially demethylated. When the nutrient solution containing arsenites is exchanged daily, the distribution of arsenic in White mustard is significantly different (translocation factor—TF—is 70 times higher) in comparison to the experiment without exchange of the medium. Speciation analysis of arsenic in plant tissues and in nutrient solutions was performed by high performance liquid chromatography with inductively coupled plasma-mass spectrometry (HPLC ICP-MS). The results obtained unquestionably illustrated that the uncontrolled conditions of hydroponic plant cultivation may be a source of misinterpretation of all the obtained data. Additionally, the synthesis of phytochelatins in plants exposed to different arsenic compounds was investigated. Phytochelatins were identified in tissues of plants exposed to arsenites and arsenates, and their presence was correlated with high arsenite content. Phytochelatin synthesis was not indicated in plants grown in the presence of MMA and DMA.     

Highly asymmetric intramolecular cyclopropanation of acceptor-substituted diazoacetates by Co(II)-based metalloradical catalysis: iterative approach for development of new-generation catalysts

3,5-Di(t)Bu-QingPhyrin, a new D(2)-symmetric chiral porphyrin derived from a chiral cyclopropanecarboxamide containing two contiguous stereocenters, has been developed using an iterative approach based on Co(II)-catalyzed asymmetric cyclopropanation of alkenes. The Co(II) complex of 3,5-Di(t)Bu-QingPhyrin, [Co(P2)], has proved to be a general and effective catalyst for asymmetric intramolecular cyclopropanation of various allylic diazoacetates (especially including those with α-acceptor substituents) in high yields with excellent stereoselectivities. The [Co(P2)]-based intramolecular metalloradical cyclopropanation provides convenient access to densely functionalized 3-oxabicyclo[3.1.0]hexan-2-one derivatives bearing three contiguous quaternary and tertiary chiral centers with high enantiomeric purity.     

Determination of polyphenols in Mentha longifolia and M. piperita field-grown and in vitro plant samples using UPLC-TQ-MS

Nine polyphenols in the aerial parts of Mentha longifolia have been separated by chromatographic techniques. Their structures have been confirmed by HPLC/electrospray ionization-MS/MS. The compounds identified included rosmarinic acid, salvianolic acid L, dedihydro-salvianolic acid, luteolin-glucuronide, luteolin-diglucuronide, luteolin-glucopyranosyl-rhamnopyranoside, and eriodictyol-glucopyranosyl-rhamnopyranoside. The extracts of M. longifolia and M. piperita field plants, in vitro plants, callus tissues, and cell suspension cultures were profiled, and their polyphenol composition was compared in different tissues and quantified using ultra-performance column liquid chromatography (UPLC)/triple-quadrupole-MS in the selected-ion recording detection mode. Determination of desired compounds was based on calibration curves obtained for standards, which were previously isolated from M. longifolia aerial parts. The UPLC profiles revealed considerable differences in the synthesis of secondary metabolites among samples coming from field plants, in vitro plants, callus tissues, and cell suspension cultures. Plant tissues coming from field cultivation (for both M. piperita and M. longifolia) contained several phenolic compounds (flavonoids and phenolic acids), whereas plants from in vitro conditions, callus tissues, and suspension cultures contained only a few of them. Rosmarinic acid dominated in all of these samples. These results show that under in vitro conditions, the metabolism of phenolics undergoes a fundamental change.     

Nonlinear dynamics of a planar beam–spring system: analytical and numerical approaches

The multiple timescales method is applied to the exact partial differential equations of the planar motion of a hinged–simply supported beam with a linear axial spring of arbitrary stiffness. The forced-damped and free oscillations of the system around frequencies corresponding to nth natural bending mode are examined thoroughly and compared with numerical simulations as well as with already published results obtained by Lindstedt–Poincaré method. A special numerical technique using explicit finite element method to draw the frequency–response curves is appositely developed. The well-known jump phenomena between resonant and non-resonant branches, as well as superharmonic resonances, have been detected numerically.     

Gold-Catalyzed Amine Cascade Addition to Diyne-Ene: Enantioselective Synthesis of 1,2-Dihydropyridines

With the well-documented chemical and biological applications, piperidine and pyridine are among the most important N-heterocycles, and a new synthetic strategy, especially one with an alternative bond-forming design, is of general interest. Using the gold-catalyzed intermolecular condensation of amine and diyne-ene, we report herein the first example of enantioselective 1,2-dihydropyridine synthesis through a formal [3+2+1] fashion (up to 95 % yield, up to 99 % e.e.).     

Photophysics of Iridium(III) (2-phenylpyridine)(2,2’,6,2”-terpyridine) Chloride Encapsulated within the Zinc(II) Polyhedral MOF,USF-2

Photoactive metal-organic frameworks (MOFs) provide an important class of functional porous materials for a wide range of applications including light harvesting, photocatalysis and photodynamic therapy. Two strategies have been employed in the development of photoactive MOFs, one in which the photoactive element is incorporated as an element of the framework itself and the other in which the photoactive element serves as a guest within the MOF cavities. Transition metal polyimines have now been non-covalently incorporated within the cavities of a large number of MOFs with the Ru^II-polyimine being the most widely examined guest complex. Previous studies have demonstrated that the nature of the cavity modulates the Ru-polyimine photophysics. Here, an Ir^III(terpyridine)(phenylpyridine)Cl complex has been encapsulated within the Zn-polyhedral MOF, USF-2. Unlike the Ru-polyimines, the excited state photophysics associated with the encapsulated Ir polyimine shows very little change in either the steady state emission and emission lifetime. The slight decrease in emission lifetime is attributed to energy transfer between encapsulated Ir complexes. These results indicate that transition metal polyimines that exhibit excited state structural changes demonstrate the largest perturbations upon confinement.