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71.
A series of six open-chain tetrapyrroles has been synthesized and used as chromophores for the plant photoreceptor protein phytochrome. The novel chromophores vary in the size of substituents 17 and 18 at ring D. This ring undergoes maximal conformational change upon light excitation ( Z --> E photoisomerization of the 15,16-double bond). Instead of methyl and vinyl substituents (positions 17, 18) as present in the native chromophore phytochromobilin, dimethyl, methyl and isopropyl, methyl and tert-butyl, ethyl and methyl, vinyl and methyl, and isopropyl and methyl substituents have been generated. All novel chromophores assemble with the apoprotein. The obtained chromoproteins show hypsochromic shifts of the absorbance maxima by 10 nm maximally, compared to the native pigment, except for the 17-isopropyl-18-methyl-substituted compound which showed a 100 nm hypsochromic shift of selectively the P r form. The assembly kinetics were slowed down in correlation to the increasing size of the substituents, with stronger effects for modified substituents at position 17. The thermal stability of the photoinduced P fr form for the 18-isopropyl and the 18- tert butyl substituents was even greater than that of the native pigments. Those chromophores carrying substituents at position 17 larger than the methyl group (ethyl and isopropyl) showed a very low stability of the respective P fr forms. Time-resolved detection of the P r to P fr conversion (laser-induced flash photolysis) revealed a slower formation of the P fr form for those chromophores carrying larger substituents at position 18, whereas the rise and decay kinetics of the early intermediates are only moderately changed. Introduction of larger substituents at position 17 (ethyl, vinyl, and isopropyl) causes drastic changes in the kinetics; in particular the formation of the first thermally stable intermediate, I 700, is significantly slowed, making a detection of its rise possible. 相似文献
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73.
Christel Hempen Liane Glsle-Schwarz Ulrich Kunz Uwe Karst 《Analytica chimica acta》2006,560(1-2):35-40
Telmisartan is an angiotensin II receptor antagonist and a known drug against high blood pressure. In this report, the development of a new and rapid analytical technique, an enzyme-linked immunosorbent assay (ELISA) for the determination of telmisartan in human blood plasma is described. The immunoassay is based on a conversion of 4-(N-methylhydrazino)-7-nitro-2,1,3-benzooxadiazole (MNBDH) to 4-(N-methylamino)-7-nitro-2,1,3-benzooxadiazole (MNBDA), which is detected by fluorescence spectroscopy. The limit of detection was 0.1 ng/mL, the limit of quantification was 0.3 ng/mL and the working range extended from 0.3 ng/mL to 300 ng/mL. 相似文献
74.
Jean-Jacques Filippi Elisabet Duñach Xavier Fernandez Uwe J. Meierhenrich 《Tetrahedron》2008,64(42):9999-10003
A series of thiolanes were prepared by cyclodehydration of sulfanylalcohols in the presence of catalytic amounts of p-toluenesulfonic acid or by using K10 clay. The sulfur heterocycles were synthesised in good to excellent yields using either a conventional Dean-Stark method or microwave irradiation under solvent-free conditions. The reaction could be performed regio- and stereoselectively and its mechanism was investigated by means of enantio- and diastereomerically enriched substrates. In contrast to previous studies, our results are consistent with an intramolecular SN2-type mechanism as a general pathway. 相似文献
75.
de Sousa M de Castro B Abad S Miranda MA Pischel U 《Chemical communications (Cambridge, England)》2006,(19):2051-2053
A simple set of five components was used to design molecular logic gates based on phthalimide-sensitised Tb(III) luminescence, including the first report of an enabled NOR (EnNOR) gate. 相似文献
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78.
Hao Zhang Dr. Benhua Wang Dr. Kai Seehafer Prof. Dr. Uwe H. F. Bunz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7779-7782
A cross-reactive optical sensor array based on poly(p-phenyleneethynylene)s (PPEs) determines Edman degraded amino acids. We report a sensor array composed of three anionic PPEs P1–P3 , and their electrostatic complexes with metal ions (Fe2+, Cu2+, Co2+). We recorded distinct fluorescence intensity response patterns as “fingerprints” of this chemical tongue toward standard phenylthiohydantoin (PTH) amino acids—degradation products of the Edman process. These “fingerprints” were converted into canonical scores by linear discrimination analysis (LDA), which differentiates all of the PTH-amino acids. This array discriminates PTH-amino acid residues degraded from an oligopeptide through Edman sequencing. This approach is complementary to chromatography approaches which rely on mass spectrometry; our array offers the advantage of simplicity. 相似文献
79.
Dr. José A. González-Delgado Dr. Miguel A. Romero Dr. Francisco Boscá Dr. Jesús F. Arteaga Prof. Dr. Uwe Pischel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(62):14229-14235
The light-gated organocatalysis via the release of 4-N,N-dimethylaminopyridine (DMAP) by irradiation of the [Ru(bpy)2(DMAP)2]2+ complex with visible light was investigated. As model reaction the acetylation of benzyl alcohols with acetic anhydride was chosen. The pre-catalyst releases one DMAP molecule on irradiation at wavelengths longer than 455 nm. The photochemical process was characterized by steady-state irradiation and ultrafast transient absorption spectroscopy. The latter enabled the observation of the 3MLCT state and the spectral features of the penta-coordinated intermediate [Ru(bpy)2(DMAP)]2+. The released DMAP catalyzes the acetylation of a wide range of benzyl alcohols with chemical yields of up to 99 %. Control experiments revealed unequivocally that it is the released DMAP which takes the role of the catalyst. 相似文献
80.
Patze C Broedner K Rominger F Trapp O Bunz UH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13720-13725
We demonstrate that aldehyde-substituted donor-acceptor cruciforms [1,4-bis(arylethynyl)-2,5-distyrylbenzenes] are useful dosimeters for primary amines, primary diamines, and secondary amines. The 1,n-diamines are particularly reactive towards this dosimeter and can be detected in less than 100 ppm concentration. Using a single aldehyde-functionalized cruciform in seven different solvents allowed us to discern fourteen different amines by digital photography and statistical evaluation of the response patterns extracted as red, green, blue (RGB) values. 相似文献