Rattling in the Quadruple Perovskite CuCu3V4O12

Of particular interest is a peculiar motion of guest atoms or ions confined to nanospace in cage compounds, called rattling. While rattling provides unexplored physical properties through the guest–host interactions, it has only been observed in a very limited class of materials. Herein, we introduce an A‐site‐ordered quadruple perovskite, CuCu₃V₄O₁₂, as a new family of cage compounds. This novel AA′₃B₄O₁₂‐type perovskite has been obtained by a high‐pressure synthesis technique and structurally characterized to have cubic Im$\bar 3$ symmetry with an ionic model of Cu²⁺Cu²⁺₃V⁴⁺₄O₁₂. The thermal displacement parameter of the A‐site Cu²⁺ ion is as large as U_iso≈0.045 Ų at 300 K, indicating its large‐amplitude thermal oscillations in the oversized icosahedral cages. Remarkably, the presence of localized phonon modes associated with rattling of the A‐site Cu²⁺ ion manifests itself in the low‐temperature specific heat data. This work sheds new light on the structure–property relations in perovskites.     

Calibration transfer employing univariate correction and robust regression

This paper proposes a new method for calibration transfer, which was specifically designed to work with isolated variables, rather than the full spectrum or spectral windows. For this purpose, a univariate procedure is initially employed to correct the spectral measurements of the secondary instrument, given a set of transfer samples. A robust regression technique is then used to obtain a model with low sensitivity with respect to the univariate correction residuals. The proposed method is employed in two case studies involving near infrared spectrometric determination of specific mass, research octane number and naphthenes in gasoline, and moisture and oil in corn. In both cases, better calibration transfer results were obtained in comparison with piecewise direct standardization (PDS). The proposed method should be of a particular value for use with application-targeted instruments that monitor only a small set of spectral variables.     

Water revealed as molecular mirror when measuring low concentrations of sugar with near infrared light

Near infrared spectroscopy is an overtone spectroscopy regarded as a quick and non-destructive method that provides analytical solutions for components that represent approximately 1% or more of the total mass of the investigated composite samples. Aquaphotomics offers the possibility for disentanglement of information remaining hidden in the spectra when conventional data evaluation methods are used, since this concept utilizes changes of the water structure induced by the measured solute as specific molecular vibrations at water bands. Here, near infrared technique and aquaphotomics are applied for non-destructive identification and quantification of mono- and di-saccharide solutes at 100–0.02 mM concentration that is accepted as unachievable with near infrared spectroscopy. The results presented in this study support the aquaphotomics' water molecular mirror concept that explores spectral changes related to water molecular rearrangements caused by minute changes of the solutes in the aqueous systems. The method provides quick and accurate alternative for classical analytical measurements of saccharides even at millimolar concentration levels.     

Validated method using liquid chromatography-electrospray ionization tandem mass spectrometry for the determination of contamination of the exterior surface of vials containing platinum anticancer drugs

Contamination of the exterior surface of vials of cytostatic drugs by the drugs themselves is a potential hazard to human health. This study developed a validated method using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for the determination of contamination of the exteriors of vials of cisplatin and carboplatin. Large Alpha^® sampling swabs were employed to wipe the vial exterior. Cisplatin or carboplatin and gold(III) as an internal standard were derivatized by N,N-diethyldithiocarbamate (DDTC). Pt(DDTC)₃⁺ and Au(DDTC)₂⁺ were monitored by the respective transitions of m/z 639.3-490.9 and 493.0-345.0, respectively. Each separation was completed within 9 min using a 3 μm particle ODS-column. Calibration curves for cisplatin and carboplatin were linear over concentration ranges of 30-10,000 and 30-30,000 pg vial⁻¹, respectively. The accuracies and precisions were 96.1-102.5% and within 8.2% for intra-assay and 99.6-103.3% and within 7.6% for inter-assay, respectively. Their lower limit of quantification was 30 pg vial⁻¹. Amounts of 0.17-17.0 ng vial⁻¹ as cisplatin and 0.48-794 ng vial⁻¹ as carboplatin were detected from the exterior surface of the vials. This validated method using LC-ESI-MS/MS for the determination of platinum anticancer drugs is helpful for monitoring contamination of the exterior surface of drug vials.     

A modification of the successive projections algorithm for spectral variable selection in the presence of unknown interferents

This work proposes a modification to the successive projections algorithm (SPA) aimed at selecting spectral variables for multiple linear regression (MLR) in the presence of unknown interferents not included in the calibration data set. The modified algorithm favours the selection of variables in which the effect of the interferent is less pronounced. The proposed procedure can be regarded as an adaptive modelling technique, because the spectral features of the samples to be analyzed are considered in the variable selection process. The advantages of this new approach are demonstrated in two analytical problems, namely (1) ultraviolet–visible spectrometric determination of tartrazine, allure red and sunset yellow in aqueous solutions under the interference of erythrosine, and (2) near-infrared spectrometric determination of ethanol in gasoline under the interference of toluene. In these case studies, the performance of conventional MLR-SPA models is substantially degraded by the presence of the interferent. This problem is circumvented by applying the proposed Adaptive MLR-SPA approach, which results in prediction errors smaller than those obtained by three other multivariate calibration techniques, namely stepwise regression, full-spectrum partial-least-squares (PLS) and PLS with variables selected by a genetic algorithm. An inspection of the variable selection results reveals that the Adaptive approach successfully avoids spectral regions in which the interference is more intense.     

Potential energy curve for ring-opening reactions: comparison between broken-symmetry and multireference coupled cluster methods

The spin-unrestricted Hartree-Fock (UHF)-based coupled cluster singles and doubles (UHF-CCSD) and Mukherjee's state-specific multireference CCSD (MkCCSD) methods are applied to four ring-opening reactions. The spin-restricted Hartree-Fock (RHF)-based CCSD (RHF-CCSD) calculations are also performed for comparison. In the case of the UHF-CCSD method, an approximate spin-projection (AP) method is applied to the broken-symmetry (BS) singlet solution to remove the spin contamination effect. For potential energy curves (PECs) of all reactions presented in this study, the results of RHF-CCSD and UHF-CCSD are substantially different from those of MkCCSD, while the results after the AP method (AP-UCCSD) reproduce the MkCCSD results well. It strongly suggests that the spin contamination effect should be removed by the AP correction even at the UHF-CCSD level to predict reliable energetics of these reactions.     

Properties of ionic liquids containing silver(I) or protic alkylethylenediamine cations with a bis(trifluoromethanesulfonyl)amide anion

Ionic liquids of an N-alkylethylenediamine-silver(I) complex cation (alkyl=hexyl, 2-ethylhexyl, and octyl) or a protic N-alkylethylenediaminium cation (alkyl=butyl, hexyl, 2-ethylhexyl, octyl, decyl, and dodecyl) with a bis(trifluoromethanesulfonyl)amide counter anion (Ag-ILs and PILs, respectively) were prepared and their physicochemical properties were investigated. The trend of solidification decreased in the order octyl?hexyl>2-ethylhexyl for the Ag-ILs, and butyl>dodecyl>decyl>octyl>hexyl?2-ethylhexyl for the PILs. The diffusion coefficients of the cations indicated stronger intermolecular interactions in PILs than in the Ag-ILs because of hydrogen-bonding networks, and it has been revealed that the intermolecular interactions increase in the order, hexyl相似文献   

Fluidic shear-assisted formation of actuating multilamellar lipid tubes using microfabricated nozzle array device

Molecular self-assemblies exhibiting automatic motions have received much attention as potential artificial models of living organisms. We have developed a microfluidic picolitre nozzle-array device to form multilamellar lipid tubes (MLTs) under fluidic shear stress, which transformed into different two patterns (yarn-balls and double-helixes) and also exhibited unique self-actuation behaviors.