Isomerization of (all‐E)‐Cucurbitaxanthin A

Cucurbitaxanthin A (=(all‐E,3S,5R,6R,3′R)‐3,6‐epoxy‐5,6‐dihydro‐β,β‐carotene‐5,3′‐diol; 1 ) was submitted to thermal isomerization and to I₂‐catalysed photoisomerization. The structure of the main reaction products (9Z)‐ ( 2 ), (9′Z)‐ ( 3 ), (13Z)‐ ( 4 ), and (13′Z)‐cucurbitaxanthin A ( 5 ) was determined by their UV/VIS, CD, ¹H‐NMR, and mass spectra.     

Aesculaxanthin,a New Carotenoid Isolated from Pollens of Aesculus hippocastanum

From the pollens of Aesculus hippocastanum, a new apocarotenoid was isolated as the main carotenoid and, based on the spectroscopic data, identified as (all-E,3R)-3-hydroxy-6′-apo-β-caroten-6′-al ( 4 , aesculaxanthin). In addition, (all-E)-lutein ( 3 ) and (all-E)-β-citraurin ( 5 ) were isolated. Furthermore, 6 (aesculaxanthol) was prepared by reduction of 4 with NaBH₄ and tentatively identified as natural carotenoid.     

Polycapillary‐optics‐based micro‐XANES and micro‐EXAFS at a third‐generation bending‐magnet beamline

A focusing system based on a polycapillary half‐lens optic has been successfully tested for transmission and fluorescence µ‐X‐ray absorption spectroscopy at a third‐generation bending‐magnet beamline equipped with a non‐fixed‐exit Si(111) monochromator. The vertical positional variations of the X‐ray beam owing to the use of a non‐fixed‐exit monochromator were shown to pose only a limited problem by using the polycapillary optic. The expected height variation for an EXAFS scan around the Fe K‐edge is approximately 200 µm on the lens input side and this was reduced to ～1 µm for the focused beam. Beam sizes (FWHM) of 12–16 µm, transmission efficiencies of 25–45% and intensity gain factors, compared with the non‐focused beam, of about 2000 were obtained in the 7–14 keV energy range for an incoming beam of 0.5 × 2 mm (vertical × horizontal). As a practical application, an As K‐edge µ‐XANES study of cucumber root and hypocotyl was performed to determine the As oxidation state in the different plant parts and to identify a possible metabolic conversion by the plant.     

微量热法研究二价铅对两种不同土壤微生物的毒性作用

本次研究采用微量量热技术分析了铅对两种常见土壤微生物（假丝酵母菌、枯草杆菌）的毒性作用。实验结果表明,低浓度Pb(Ⅱ) (10.0 µg mL-1) 对两种土壤微生物的生长均有促进作用;而当Pb(Ⅱ) 浓度较高时（假丝酵母菌 20.0~320.0 µg mL-1、枯草杆菌20.0~160.0 µg mL-1）,微生物的生长则明显被抑制了,此时微生物的生长速率常数k与Pb(Ⅱ) 的浓度c呈现线性相关。同时,细胞干重法和浊度法也应用于本次研究中,并与微量量热曲线拟合,充分证明了微量量热技术对研究铅对土壤微生物毒性作用的准确性和有效性。     

Elementary Graphs with Respect to <Emphasis Type="Italic">f</Emphasis>-Parity Factors

This note concerns the f-parity subgraph problem, i.e., we are given an undirected graph G and a positive integer value function \({f : V(G) \rightarrow \mathbb{N}}\), and our goal is to find a spanning subgraph F of G with deg _F ≤ f and minimizing the number of vertices x with \({\deg_F(x) \not\equiv f(x) \, {\rm mod} \, {2}}\) . First we prove a Gallai–Edmonds type structure theorem and some other known results on the f-parity subgraph problem, using an easy reduction to the matching problem. Then we use this reduction to investigate barriers and elementary graphs with respect to f-parity factors, where an elementary graph is a graph such that the union of f-parity factors form a connected spanning subgraph.     

Accurate measurement of long-range heteronuclear coupling constants from undistorted multiplets of an enhanced CPMG-HSQMBC experiment

Here, we present a modified CPMG-HSQMBC experiment which is capable to reduce the detrimental phase twists in the "long-range" connectivity multiplets caused by proton-proton couplings. We demonstrate that concerted CPMG pulse trains applied on both nuclei in the starting CPMG-INEPT transfer step can considerably be improved by composite pi pulses that compensate for pulse imperfections and off-resonance effects. Experimental optimization of the interpulse delay within the CPMG cycle was found to be crucial in order to achieve the best possible "decoupling" of homonuclear coupling modulation.     

Application of the Systems Chemistry Approach on the Ammonolysis of 1-Ethoxycarbonyl- and 1-Phenoxycarbonyl-3-(2-thienyl)oxindoles. A Method to Predict Reactivity

The routine prediction of the reactivity of a complex, multifunctional molecule is a challenging and time-consuming procedure. In the last step of the synthesis of the well-known drug substance tenidap, a nonexpected difference was observed between the reactivities of two closely related carbamate moieties, the N-ethoxycarbonyl and the N-phenoxycarbonyl group. A detailed kinetic study, necessitating a significant computational effort, is described in the present paper for this reaction step. On the other hand, the systems chemistry concept, by analyzing the details of the electronic structure and the connections between functional groups in a fast and simple way, is also able to answer this question using various "-icity" parameters (aromaticity, carbonylicity, olefinicity). The complete systems chemistry approach involves all these conjugativicity parameters, while its further simplified version is based on only one key parameter, which is carbonylicity in the present case. The above methods were compared in terms of their predictive power. The results show that the systems chemistry concept, even its one-parameter version, is applicable for the characterization of this challenging reactivity issue.