Copper(II)–lanthanide(III) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platforms with Lewis amphoteric nature

Reaction of copper(II) acetate, lanthanium(III) or gadolinium(III) nitrate (1/5 equiv.) with pyrazinohydroxamic acid (H₂Pyzha) in DMF led to a series of new heterobimetallic 15-metallacrown-5 complexes. In a MeOH/H₂O solution the complexes exist as molecular unassociated metallacrowns. In solid state their structures are more complicated as it has been confirmed by X-ray analysis: discrete molecular metallacrowns [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(NO₃)] · 0.5C₆H₆ · H₂O (1), [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅](NO₃) · 1.5DMF · 0.5H₂O (2), [La(NO₃)₂{Cu(pyzha)}₅(DMF)₅]NO₃ · 1.5DMF · 2C₆H₆ (3) are solvates, whereas compound [{La(NO₃)₂{Cu(pyzha)}₅(DMF)₅}₂(μ²-NO₃)](NO₃) · 3DMF (4) is a dimer, where μ-bridged nitrate links two copper centres of the adjacent metallamacrocycles. Complex [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₂(H₂O)(NO₃)] · CH₂Cl₂ · DMF (5) self-associates into a polymer chain by means of one pyrazine moiety and the copper ring atom. Reaction of the molecular metallacrowns with excess of inorganic salts CdBr₂ or Cu(OAc)₂ proceeds as anion methathesis process affording heteroanionic metallacrowns: molecular [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅] [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(H₂O)][CdBr₄] · 1.5DMF (6), and 3D hydrogen bonded polymer [La(μ²-OAc)(H₂O)₃{Cu(pyzha)}₅ (H₂O)₄(NO₃)](NO₃) · 4H₂O (7).     

Spatial hydration maps and dynamics of naphthalene in ambient and supercritical water

The hydration structures and dynamics of naphthalene in aqueous solution are examined using molecular-dynamics simulations. The simulations are performed at several state points along the coexistence curve of water up to the critical point, and above the critical point with the density fixed at 0.3 g/cm(3). Spatial maps of local atomic pair-density are presented which show a detailed picture of the hydration shell around a bicyclic aromatic structure. The self-diffusion coefficient of naphthalene is also calculated. It is shown that water molecules tend to form pi-type complexes with the two aromatic regions of naphthalene, where water acts as the H-bond donor. At ambient conditions, the hydration shell of naphthalene is comprised, on average, of about 39 water molecules. Within this shell, two water molecules can be identified as pi-coordinating, forming close to one H-bond to the aromatic rings. With increasing temperature, the hydration of naphthalene changes dramatically, leading to the disappearance of the pi-coordination near the critical point.     

Analysis of gasoline contaminated water samples by means of dopant-assisted atmospheric pressure photoionization differential ion mobility spectrometry

In this study the influence of aromatic dopant benzene on the sensitivity of GC-APPI-DMS to gasoline related aromatic compounds was investigated. This influence was investigated on example of four gasolin related fingerprints (toluene, ethylbenzene, o-xylene, and 1,2,4-trimethylbenzene), which were found in high relative abundance in the water-soluble gasoline fraction. The analysis of calibration curves slopes demonstrats that the GC-APPI-DMS sensitivity to gasoline fingerprints can be improved by up to seven times when benzene concentration in nitrogen carrier gas is less than 10 ppm_v/v. The estimated detection limits (S/N?=?3) for the analyzed in this study compounds were found to be within the range of 33–105 μg L^?1 at benzene concentration in the carrier gas of 2.27 ppm_v/v (10 μL injection volume). These limits of detection may be reduced (at the cost of lower resolution) using the larger injection volumes. For example, increase of injection volume to 100 μL at benzene concentration in the carrier gas of 2.27 ppm_v/v leads to reduction of LOD values for toluene, ethylbenzene, and o-xylene to 11.1, 13.3, and 5.3 μg L^?1, respectively.     

Infrared spectroscopy and outer product analysis for quantification of fat, nitrogen, and moisture of cocoa powder

The combination of the near infrared (NIR) and Fourier-transform infrared (FTIR) absorbance spectra (1100-2500 nm and 4000-600 cm⁻¹) of 100 cocoa powder samples was used to build calibration models for the determination of the content of fat, nitrogen, and moisture. The samples that comprised the dataset had an average composition of 13.51% of fat, 3.77% nitrogen, and 3.98% moisture. The fat content ranged from 2.42 to 22.00%, the nitrogen from 0.88 to 4.48%, and moisture from 1.60 to 7.80%. For NIR, the relative root mean square error of cross-validation (RMSECV) was 7.0% (R² = 0.96) for fat, 1.7% (R² = 0.98) for nitrogen, and 5.2% (R² = 0.94) for moisture. For FTIR, the relative RMSECV was 10.4% (R² = 0.94) for fat and 3.9% (R² = 0.95) for nitrogen. However, for moisture, it was not possible to build a calibration model with suitable predictability. The combination of the NIR and FTIR domains (data fusion) by outer product analysis PLS1 allowed to predict these parameters and to characterise frequencies in one domain based on the information of the other domain. This work allows to conclude that the second derivative of NIR is the recommended procedure to quantify fat, nitrogen, and moisture content in cocoa powders by infrared spectroscopy.     

Polynomial automorphisms and hypercyclic operators on spaces of analytic functions

We consider hypercyclic composition operators on which can be obtained from the translation operator using polynomial automorphisms of . In particular we show that if C _S is a hypercyclic operator for an affine automorphism S on , then for some polynomial automorphism Θ and vectors a and b, where I is the identity operator. Finally, we prove the hypercyclicity of “symmetric translations” on a space of symmetric analytic functions on ℓ₁. Received: 8 June 2006 Revised: 26 September 2006     

The near-field effect in a quantum computer

It is shown that in principle it is possible to write optical information on individual quasiresonant atoms in a concentrated system by changing the angle of incidence of an external light wave. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 10, 750–754 (25 May 1999)     

Near-field effect in optics of small objects composed of dipole atoms

A self-consistent problem of interaction of two dipole atoms separated by an unrestricted distance with the field of a quasi-resonance light wave was solved on the assumption that the investigated atoms are Lorentz linear oscillators and the polarizing fields inside the system consist of the Coulomb and the retarded parts. The solution obtained was investigated for the case where the atoms have the same polarizability and the distance between them is much smaller than the length of the external light wave. Formulas for the electric fields inside a small object and outside it have been obtained. It is shown that inside a small two-atom object there can take place longitudinal and transverse optical vibrations accompanied by corresponding dispersion effects depending on the interatomic distance and the angle between the axis of the system and the direction of propagation of the external light wave. The field outside the small object in the wave zone is linearly polarized when the external wave has linear polarization. However, the direction of polarization of the corresponding waves is largely determined by their frequency. It is also shown that the amplitude of the field outside the small object in the wave zone depends greatly on the frequency of the external field and the interatomic distance. The effects observed are considered as a near-field effect in optics of small objects. This phenomena makes it possible to investigate the structure of small objects with the use of optical radiation. Ul'yanovsk Branch of the Institute of Radio Engineering and Electronics, Russian Academy of Sciences, 48 Goncharov Str., Ul'yanovsk, 432700, Russia; e-mail: gadomsky@quant.univ.simbirsk.su. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 765–770, November–December, 1999.