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51.
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53.
Steffen Oroszi Torsten Jakob Christian Wilhelm Hauke Harms Thomas Maskow 《Journal of Thermal Analysis and Calorimetry》2011,104(1):223-231
Isothermal microcalorimetry can be used to investigate the photosynthetic energy conversion of autotrophic organisms. In this
study, for the first time a diatom alga was used to compare the calorimetrically measured heat flux with measurements of the
photosynthetic performance by oxygen evolution and pulse-amplitude modulated fluorescence. The presented experimental setup
proved suitable to compare calorimetric data with those of conventional methods of the determination of photosynthesis rates.
Special attention was paid to the contribution of energy dissipation via non-photochemical quenching (NPQ) of chlorophyll
fluorescence to the metabolic energy balance. This was achieved by a combination of different light conditions and the use
of an inhibitor of NPQ. Although NPQ is an important photoprotective mechanism in diatoms, the inhibition of NPQ resulted
in an activation of alternative, energy dissipating pathways for absorbed radiation which completely compensated for the fraction
of energy dissipation by NPQ. 相似文献
54.
Origin and Location of Electrons and Protons during the Formation of Intermetalloid Clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0, 1) 下载免费PDF全文
Dipl.‐Chem. Bastian Weinert B.Sc. Fabian Müller Dr. Klaus Harms Dr. Rodolphe Clérac Prof. Dr. Stefanie Dehnen 《Angewandte Chemie (International ed. in English)》2014,53(44):11979-11983
Reaction of [GaBi3]2? with [Sm(C5Me4H)3] yielded the first protonated ternary intermetalloid clusters [Sm@Ga3?xH3?2xBi10+x]3? ( 1 ; x=0,1). The presence of the Ga? H bonds and the transfer of electrons and protons during the formation of 1 were elucidated by a combination of experimental and quantum chemical methods, thereby rationalizing the role of the solvent ethane‐1,2‐diamine as a Brønsted acid. As an organic by‐product, we observed the previously unknown octamethylfulvene ( 2 ) upon C? C coupling of (C5Me4H)?. 相似文献
55.
Constrained‐Geometry Bisphosphazides Derived from 1,8‐Diazidonaphthalene: Synthesis,Spectroscopic Characteristics,Structural Features,and Theoretical Investigations 下载免费PDF全文
Julius F. Kögel Nuri C. Abacılar Felicia Weber Dr. Benjamin Oelkers Dr. Klaus Harms Dr. Borislav Kovačević Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5994-6009
Investigations on the Staudinger reaction between 1,8‐diazidonaphthalene and phosphorous(III) building blocks, a key step in the synthesis of superbasic bisphosphazene proton sponges, yielded a set of bisphosphazides with a constrained geometry 1,8‐disubstituted naphthalene backbone. This compound class has attracted our interest not only due to their surprisingly high stability, but in particular because of their theoretically predicted basicity in the range of their bisphosphazene analogues that can be referred to the constrained geometry interaction of two highly basic nitrogen atoms. Eleven new bisphosphazides bearing simple P‐amino groups as well as P‐guanidino substituents, azaphosphatrane moieties, P2 building blocks, or chiral P‐amino substituents derived from L ‐proline are presented. They were studied concerning their spectroscopic properties and partly also their chromophoric and structural features. In the case of the pyrrolidino‐substituted TPPN(2N2) (TPPN=1,8‐bis(trispyrrolidinophosphazenyl)naphthalene), the stepwise nitrogen elimination is investigated theoretically and experimentally, which led to the isolation and structural characterization of TPPN(1N2) bearing a phosphazide and a phosphazene functionality in one molecule. Attempts to protonate the obtained bisphosphazides and to prove the computationally predicted pKBH+ values through NMR titration reactions resulted in their decay, which again was rationalized by theoretical calculations. Altogether we present the so far most extensive spectroscopic, structural and theoretical investigation of constrained geometry bisphosphazides and their Brønsted and Lewis basic properties. 相似文献
56.
Octahedral Chiral‐at‐Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions 下载免费PDF全文
Xiaodong Shen Haohua Huo Chuanyong Wang Bo Zhang Dr. Klaus Harms Prof. Dr. Eric Meggers 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9720-9726
Octahedral iridium(III) complexes containing two bidentate cyclometalating 5‐tert‐butyl‐2‐phenylbenzoxazole ( IrO ) or 5‐tert‐butyl‐2‐phenylbenzothiazole ( IrS ) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5–5.0 mol % catalyst loading) for a variety of reactions with α,β‐unsaturated carbonyl compounds, namely Friedel–Crafts alkylations (94–99 % ee), Michael additions with CH‐acidic compounds (81–97 % ee), and a variety of cycloadditions (92–99 % ee with high d.r.). Mechanistic investigations and crystal structures of an iridium‐coordinated substrates and iridium‐coordinated products are consistent with a mechanistic picture in which the α,β‐unsaturated carbonyl compounds are activated by two‐point binding (bidentate coordination) to the chiral Lewis acid. 相似文献
57.
Alex R. Petrov Konstantin A. Rufanov Klaus Harms Jörg Sundermeyer 《Journal of organometallic chemistry》2009,694(7-8):1212-1218
The influence of the ether ligand in [LnCl3(solv)n], solv = THF, DME; n = 1–3 in reactions with ortho-lithiated dimethyl-benzylamine Li(dmba) has been studied. An improved protocol towards homoleptic tris-aryl complexes of the type [Ln(dmba)3], Ln = Y, Er and Yb has been developed and molecular structures of these complexes have been established by X-ray crystallography. For the first time stable homoleptic lithium ate-complexes of the type Li[Ln(dmba)4] (Ln = Gd, Nd) have been isolated and structurally characterized. The success in their synthesis strongly depends on the choice of the appropriate [LnCl3(solv)n] precursor, such as [GdCl3(dme)2], [NdCl3(dme)], and THF-free reaction conditions. Factors influencing on possible degradation pathways of lanthanide tris-aryl complexes with dmba-type ligands are discussed. 相似文献
58.
The novel thiophenolato hydrido iron(II) complexes [cis-Fe(H)(SAr)(PMe3)4] (4–6) (Ar = p-BrC6H4 (4), p-MeOC6H4 (5) and o-MeC6H4 (6)) were prepared through the reaction of Fe(PMe3)4 with thiophenols ArSH (1–3). Reaction of 6 with trimethylsilylacetylene and phenylacetylene afforded bisalkynyl iron(II) complexes [Fe(PMe3)4(CCSiMe3)2] (7) and [Fe(PMe3)4(CCPh)2] (9) through elimination of dihydrogen and the formation of thiophenol. The reaction of 5 with 2-methyl-3-butyn-2-ol gave [Fe(PMe3)4(CCCMe2OH)2] (10). The crystal structures of complexes 4, 7 and 10 were determined by X-ray diffraction. A mechanism for the formation of 7 is proposed. 相似文献
59.
A cobalt(I)-catalyzed [2 + 2 + 2] cycloaddition reaction between an internal acceptor-substituted alkyne and a terminal alkene leads to the formation of regiochemically enriched polysubstituted 1,3-cyclohexadiene derivatives in acceptable yields when methyl butynoate is used, whereas regiochemically pure products are formed in good yields form phenyl propyonate. The concurrent cyclotrimerization reaction of the alkyne to the corresponding benzene derivative is dependent on the sterical bulk of the alkyne and is considerably reduced with the sterically more hindered alkyne. 相似文献
60.
Driller KM Libnow S Hein M Harms M Wende K Lalk M Michalik D Reinke H Langer P 《Organic & biomolecular chemistry》2008,6(22):4218-4223
N-glycosides of 6H-indolo[2,3-b]quinoxalines were prepared and structurally characterized. The synthesis relies on the cyclocondensation of isatine-N-glycosides with 1,2-diaminobenzenes. Some products exhibit weak cytotoxic activity against human ceratinocytes (HaCaT). 相似文献