基于2,5-二(4′-甲酰基苯基)苯乙烯的螺旋链光学活性聚合物的合成与表征

通过2,5-二溴苯乙烯与对甲酰基苯硼酸的Suzuki偶联反应得到2,5-二(4′-甲酰基苯基)苯乙烯.在催化剂量的冰乙酸存在下,与光学纯的(S)-(-)-α-甲基苄胺或(R)-(+)-α-甲基苄胺发生缩和反应,得到了一对手性非外消旋单体,(+)-2,5-二{4-′[(N-(S)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯和(-)-2,5-二{4′-[(N-(R)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯.以偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO)为引发剂,经自由基溶液聚合得到光学活性聚合物.比旋光度、紫外-可见吸收光谱以及圆二色光谱研究表明,聚合物主链可能形成了某一方向占优的稳定螺旋构象,且该螺旋构象的旋光方向与单体的旋光方向相反.聚合条件对聚合物的光学活性有很大影响,在极性较大的芳香族溶剂和较高温度下得到的聚合物具有和单体相差更大的比旋光度.侧基的手性基团脱除后,聚合物仍具有一定的旋光性,说明聚合过程中形成的螺旋手性具有一定的记忆效应.     

DECONVOLUTION OF THE RED P700 DIFFERENCE SPECTRUM BASED ON A SET OF THREE GAUSSIAN COMPONENTS: FURTHER EVIDENCE FROM LITERATURE SPECTRA

Abstract Literature data on the light induced difference spectrum of the photosynthetic reaction centre complex P700 were analysed in the spectral region from 670-700 nm. In accordance to our previous Gaussian deconvolution of the flash induced difference spectrum and the linear dichroism spectrum of photosystem I particles from green plants, we present here fits of three representative difference spectra that were recorded at room temperature and at low temperature conditions, respectively. These fits are generated by using the same set of only three Gaussian components that we specified previously: (1) a disappearing wide band around 695 nm representing the absorption of the reduced special-pair of chlorophyll- a ; (2) an appearing narrower band at slightly shorter wavelength (In agreement with our previous results, this band shows half the oscillatory strength of the former band. It is therefore attributed to the non-oxidized chlorophyll- a in the special pair); and (3) a bathochromic bandshift centered around 688 nm, which indicates the local electrochromic response of chlorophyll-a antennae molecule(s) close to the site of the primary donor. Among the reports by several authors we attribute the variation of the difference spectra of P700 in the region from 670-720 nm mainly to a variation in the magnitude of the third component, the local electrochromic one. We can also account for the peculiar shape of the low temperature spectra, mainly by alteration of the extent of the electrochromic component. It seems reasonable that the electrochromic component reacts most sensitively against structural changes of the reaction centre protein complex (brought forth by different degrees of depletion from antennae or by variation of the temperature).     

Isotope anomalies of carbon, hydrogen and nitrogen in peat from the area of the tunguska cosmic body explosion (1908)

Abstract Peat profiles from the area of the Tunguska explosion epicentre indicate significant carbon and hydrogen isotopic effects which are clearly associated with the zone of the 1908 "catastrophe", and which cannot be attributed to any known terrestrial processes. We explain them with the presence of extraterrestrial matter similar to carbonaceous chondrites or, more probably, to cometary matter. Initial data on nitrogen content and its isotope composition are consistent with the assumption of acid rainfall following the passage and explosion of the Tunguska cosmic body, as is known to have occurred during the Cretaceous-Tertiary boundary.     

Some estimates on entropy numbers

First we show that the Carl-Maurey inequality for entropy numbers

Synthesis and chiroptical analysis of optically active chiral shell dendrons

We have prepared a series of chiral dendrons (1-4) in which chiral subunits are placed in individual generational shells at varying distances from the focal point. The optical activity of these chiral dendritic structures is successfully modeled using structurally similar low-molecular weight model compounds. In dendrons 1a and 1b a chiral subunit is directly adjacent to the focal point, whereas in dendrons 2, 3, and 4a,b the chiral subunits are incorporated in the interior of the dendron. A marked difference in optical activity between the former 1a and 1b) and latter (2, 3, 4a,b) dendrons is mirrored in the optical activities of model compounds 12a, 12b, 19a, and 19b. These model compounds directly mimic the surrounding constitution of the chiral subunits in the dendrons. This successful analysis of the chiroptical data using low-molecular weight model compounds suggests that these dendrons do not possess conformational order in solution.     

An amino acid based system for CO2 capture and catalytic utilization to produce formates

Herein, we report a novel amino acid based reaction system for CO₂ capture and utilization (CCU) to produce formates in the presence of the naturally occurring amino acid l-lysine. Utilizing a specific ruthenium-based catalyst system, hydrogenation of absorbed carbon dioxide occurs with high activity and excellent productivity. Noteworthy, following the CCU concept, CO₂ can be captured from ambient air in the form of carbamates and converted directly to formates in one-pot (TON > 50 000). This protocol opens new potential for transforming captured CO₂ from ambient air to C1-related products.

A novel amino acid based reaction system for CO₂ capture and utilization (CCU) to produce formates is presented applying a ruthenium-based catalyst. Noteworthy, CO₂ can be captured from ambient air and converted to formates in one-pot (TON > 50 000).