Polychloride monoanions from [Cl3]- to [Cl9]- : a Raman spectroscopic and quantum chemical investigation

Polychloride monoanions stabilized by quaternary ammonium salts are investigated using Raman spectroscopy and state-of-the-art quantum-chemical calculations. A regular V-shaped pentachloride is characterized for the [N(Me)(4)][Cl(5)] salt, whereas a hockey-stick-like structure is tentatively assigned for [N(Et)(4)][Cl(2)???Cl(3)(-)]. Increasing the size of the cation to the quaternary ammonium salts [NPr(4)](+) and [NBu(4)](+) leads to the formation of the [Cl(3)](-) anion. The latter is found to be a pale yellow liquid at about 40 °C, whereas all the other compounds exist as powders. Further to these observations, the novel [Cl(9)](-) anion is characterized by low-temperature Raman spectroscopy in conjunction with quantum-chemical calculations.     

Polychloride Monoanions from [Cl3]− to [Cl9]−: A Raman Spectroscopic and Quantum Chemical Investigation

Polychloride monoanions stabilized by quaternary ammonium salts are investigated using Raman spectroscopy and state‐of‐the‐art quantum‐chemical calculations. A regular V‐shaped pentachloride is characterized for the [N(Me)₄][Cl₅] salt, whereas a hockey‐stick‐like structure is tentatively assigned for [N(Et)₄][Cl₂???Cl₃^?]. Increasing the size of the cation to the quaternary ammonium salts [NPr₄]⁺ and [NBu₄]⁺ leads to the formation of the [Cl₃]^? anion. The latter is found to be a pale yellow liquid at about 40 °C, whereas all the other compounds exist as powders. Further to these observations, the novel [Cl₉]^? anion is characterized by low‐temperature Raman spectroscopy in conjunction with quantum‐chemical calculations.     

Suppressed speckle contrast of blue light emission out of white lamp with phosphors excited by blue laser diodes for high-brightness lighting applications

The speckle contrast of blue light emission out of high-brightness white lamps using phosphors excited by InGaN/GaN blue laser diodes is evaluated as a measure of coherence. As a result, speckle contrast of as low as 1.7%, the same level as a blue light emitting diode, is obtained. This implies that the original blue laser light can be converted into incoherent light through lamp structures without any dynamic mechanisms. This unique speckle-free performance is considered to be realized by multiple scattering inside the lamp structure, the multi-longitudinal mode operation of the blue laser diodes, and the use of multiple laser diodes. Such almost-incoherent white lamps can be applied for general lighting without any nuisance of speckle noise and should be categorized as lamps rather than lasers in terms of laser safety regulation.     

Synthesis, characterization and activity of Co and Ni catalysts supported on AlMe (Me?=?Zn, Zr, Ti) mixed oxides

Binary Al?CTi, Al?CZr and Al?CZn oxides, prepared by the sol?Cgel method were used as supports of catalytic systems. The catalysts were prepared by impregnation of these supports with the low cost Co or Ni nitrate salts and subsequent calcination at 700?°C. Catalysts have been characterized by S_BET, XRD and TPR techniques. The catalysts were tested in ethanol partial oxidation using a fixed-bed quartz reactor at atmospheric pressure and temperature at 600?°C. In test reactions a constant feed composition was used with O₂/EtOH molar ratio of 0.75 in nitrogen balance. The catalytic performance of the systems depends on type of support and type of promoter. Hydrogen and CO are the predominant products beside some by-products in different quantities (CO₂, methane, ethylene, acetaldehyde, acetone, acetic acid). The Co and Ni catalysts supported on AlZn binary oxide showed the highest selectivity to hydrogen and to carbon monoxide with full ethanol conversion. Selectivity of hydrogen follows the order of Co(Ni)AlZn?>?Co(Ni)AlTi?>?Co(Ni)AlZr. The best performance was obtained by NiAlZn catalyst with 89?% hydrogen selectivity.     

7Li NMR as probe for solvent–cellulose interactions in cellulose dissolution

Molten salt hydrates proved to be alternative solvents to cellulose. Toinvestigate the reasons for this dissolving ability, information about thesolvent–cellulose interactions is essential. As well as ¹³CHR NMR, ⁷Li NMR was used to obtain further insight into thisproblem.After comparing several molten salt hydrates, the ⁷Li NMR spectrarevealed a smaller shielding of the lithium cation for not dissolving than fordissolving and swelling cellulose systems. In most solvent systems theshieldingat the ⁷Li nuclei increases with the cellulose concentration. 2D⁷Li-¹H HOESY NMR was successfully applied to verify thepresence of cellobiose, used as a model compound for cellulose, in the firstco-ordination sphere of the lithium cation.     

Comparative Analysis of the Antitumor Activity of Cis- and Trans-Resveratrol in Human Cancer Cells with Different p53 Status

Resveratrol, a natural plant phytoalexin, is produced in response to fungal infection or− UV irradiation. It exists as an isomeric pair with cis- and trans-conformation. Whereas multiple physiological effects of the trans-form, including a pronounced anti-tumoral activity, are nowadays elucidated, much less knowledge exists concerning the cis-isomer. In our work, we analyzed the antiproliferative and cytotoxic properties of cis-resveratrol in four different human tumor entities in direct comparison to trans-resveratrol. We used human cell lines as tumor models for hepatocellular carcinoma (HCC; HepG2, Hep3B), colon carcinoma (HCT-116, HCT-116/p53^(−/−)), pancreatic carcinoma (Capan-2, MiaPaCa-2), and renal cell carcinoma (A498, SN12C). Increased cytotoxicity in all investigated tumor cells was observed for the trans-isomer. To verify possible effects of the tumor suppressor p53 on resveratrol-induced cell death, we used wild type and p53-deleted or -mutated cell lines for every tested tumor entity. Applying viability and cytotoxicity assays, we demonstrated a differential, dose-dependent sensitivity towards cis- or trans-resveratrol among the respective tumor types.     

Antibodies as Tailor-Made Chiral Selectors: an Interdisciplinary Approach to Enantiomer Separation and Detection

 It has long been known that the configurational isomers of biologically active compounds, e.g., nutrients, pesticides, and drugs, may exhibit different activities in a chiral environment such as the human body. Although the majority of drugs presently in development are chiral, analytical and preparative methods for the quantitative determination and purification of stereoisomers still lag behind. One reason is that commonly used chiral selectors for the direct resolution of enantiomers are not tailor-made for a specific analyte. The identification of suitable selectors for a particular pair of enantiomers still requires considerable experimentation and is generally demanding with regard to material, time and labor. The rational design of chiral host molecules, therefore, represents a challenge in facilitating enantiomer analysis. In this article, we describe how a combination of techniques ranging from organic synthesis to molecular biology yields antibodies of predetermined specificity and stereoselectivity that can be used as tailor-made chiral selectors for the chromatographic separation of enantiomers and their sensitive detection in immunosensors.     

High-resolution laser ablation inductively coupled plasma mass spectrometry used to study transport of metallic nanoparticles through collagen-rich microstructures in fibroblast multicellular spheroids

We have efficiently produced collagen-rich microstructures in fibroblast multicellular spheroids (MCSs) as a three-dimensional in vitro tissue analog to investigate silver (Ag) nanoparticle (NP) penetration. The MCS production was examined by changing the seeding cell number (500 to 40,000 cells) and the growth period (1 to 10 days). MCSs were incubated with Ag NP suspensions with a concentration of 5 μg mL⁻¹ for 24 h. For this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to visualize Ag NP localization quantitatively. Thin sections of MCSs were analyzed by LA-ICP-MS with a laser spot size of 8 μm to image distributions of ¹⁰⁹Ag, ³¹P, ⁶³Cu, ⁶⁶Zn, and ⁷⁹Br. A calibration using a NP suspension was applied to convert the measured Ag intensity into the number of NPs present. The determined numbers of NPs ranged from 30 to 7200 particles in an outer rim of MCS. The particle distribution was clearly correlated with the presence of ³¹P and ⁶⁶Zn and was localized in the outer rim of proliferating cells with a width that was equal to about twice the diameter of single cells. Moreover, abundant collagens were found in the outer rim of MCSs. For only the highest seeding cell number, NPs were completely captured at the outer rim, in a natural barrier reducing particle transport, whereas Eosin (⁷⁹Br) used as a probe of small molecules penetrated into the core of MCSs already after 1 min of exposure.

Fibroblast MCS could build up the barrier only for nanoparticles