A New Class of Remote N‐Heterocyclic Carbenes with Exceptionally Strong σ‐Donor Properties: Introducing Benzo[c]quinolin‐6‐ylidene

We make the case for benzo[c]quinolin‐6‐ylidene ( 1 ) as a strongly electron‐donating carbene ligand. The facile synthesis of 6‐trifluoromethanesulfonylbenzo[c]quinolizinium trifluoromethanesulfonate ( 2 ) gives straightforward access to a useful precursor for oxidative addition to low‐valent metals, to yield the desired carbene complexes. This concept has been achieved in the case of [Mn(benzo[c]quinolin‐6‐ylidene)(CO)₅]⁺ ( 15 ) and [Pd(benzo[c]quinolin‐6‐ylidene)(PPh₃)₂(L)]²⁺ L=THF ( 21 ), OTf ( 22 ) or pyridine ( 23 ). Attempts to coordinate to nickel result in coupling products from two carbene precursor fragments. The CO IR‐stretching‐frequency data for the manganese compound suggests benzo[c]quinolin‐6‐ylidene is at least as strong a donor as any heteroatom‐stabilised carbene ligand reported.     

A rapid heating and high magnetic field thermal analysis technique

Journal of Thermal Analysis and Calorimetry - A new thermal analysis technique is described that allows measurements to be performed on bulk samples at extreme heating and cooling rates and in high...     

Measurements of wave-breaking radiation from a laser-wakefield accelerator

Spectral analysis of radiation emitted transverse to laser propagation in laser-wakefield acceleration experiments shows broadband emission when electrons are accelerated to relativistic energies. The region over which emission occurs is short compared with the overall interaction length. The energy of the emission and location along the interaction length both vary with plasma density. A model for the radiation from self-trapped electrons indicates that the emission is a signature of the violent initial acceleration, and hence can be used as a diagnostic of the self-injection mechanism.     

Nickel‐Catalyzed Synthesis of Dialkyl Ketones from the Coupling of N‐Alkyl Pyridinium Salts with Activated Carboxylic Acids

While ketones are among the most versatile functional groups, their synthesis remains reliant upon reactive and low‐abundance starting materials. In contrast, amide formation is the most‐used bond‐construction method in medicinal chemistry because the chemistry is reliable and draws upon large and diverse substrate pools. A new method for the synthesis of ketones is presented here that draws from the same substrates used for amide bond synthesis: amines and carboxylic acids. A nickel terpyridine catalyst couples N‐alkyl pyridinium salts with in situ formed carboxylic acid fluorides or 2‐pyridyl esters under reducing conditions (Mn metal). The reaction has a broad scope, as demonstrated by the synthesis of 35 different ketones bearing a wide variety of functional groups with an average yield of 60±16 %. This approach is capable of coupling diverse substrates, including pharmaceutical intermediates, to rapidly form complex ketones.     

Highly charged ions in a new era of high resolution X-ray astrophysics

X-ray astronomy and ground-based atomic physics have a long history of fruitful collaboration: Sound understanding of the underlying atomic physics is the key to reliable interpretation of the spectra from celestial sources; conversely, astronomical spectra have been used to benchmark and advance atomic physics. This interplay is about to become even more important as we enter a new era of high-resolution X-ray astrophysics with large effective collection area. Although high-resolution observations with the gratings on the Chandra and XMM-Newton observatories continue to drive new science, upcoming planned and proposed missions will open up new discovery space in the near future that is currently challenging to access: high-resolution spectroscopy on extended sources, in the Fe K band, and on short time scales. This review summarizes open questions in these areas and the design parameters for the Hitomi, XRISM, Athena, and Arcus observatories. The expected high quality of spectra taken with these observatories puts new constraints on the accuracy of atomic reference data required to take full advantage of the diagnostic potential of these spectra.     

体内和体外生物测定在环境监测中的应用

生物测定在环境毒物学研究中普遍用于检测人为污染物对个别生物体和生态系统的影响.这些测定适用于个别化学品或复杂的混合物(如废水)对有代表性的生物系统或整个生物体所引起的影响,并普遍应用于环境监测项目.生物测定可在生物体外或生物体内进行,前者是在实验室内利用细胞培养技术,后者除可在实验室内进行还可应用在真实的环境中.体外生物测定往往是用来研究环境样品中的污染物对生物机制的具体影响,如受体结合特性.而体内活性生物测定则提供了一个更加具体化的综合生物反应.然而,这两种类型的生物测定法可以测量许多不同的生物指标,如对生物生长及发育的影响、内分泌功能和DNA损伤.无论是在体内和体外生物测定都分别有其特有的优点和缺点,其中一些测定法可以使用于毒性鉴定和评价程序.本文简要介绍了体内和体外生物测定方法的基本特点及其在环境监测中的应用实例,指出化学物质如何影响有机体及生态系统的结构和功能,认为广泛发展更能充分反映生态系统生物多样性的生物测定方法,将有助于更准确地了解环境污染物对环境的潜在影响.     

Negative ion tandem mass spectrometry of leukotriene E4, and LTE4, metabolites: Identification of LTE4, in human urine

The sulfidopeptide leukotrienes, leukotriene E₄, (LTE₄,) and its N-acetyl derivative and several ω? and β-oxidized metabolites of LTE₄, have been analyzed by tandem mass spectrometry. [M?H]^? ions were produced by continuous flow fast atom bombardment, and collision-induced dissociation of these ions was studied by using a triple quadrupole instrument. The product ion spectra obtained were characteristic of the structure of LTE₄, and mechanisms of ion formation were investigated by using deuterated compounds. β-Elimination of the peptide portion of LTE₄, by loss of CO₂, and ethylene amine leaves the C-l carboxyl group ionized in the most abundant fragment ion for LTE₄, and all metabolites. Tandem mass spectrometry of fast atom bombardment-generated anions from ω? and β-oxidized metabolites of LTE₄, produced similar ions with only a minor influence of the third carboxyl group at the omega terminus evident. Tandem mass spectrometry was used to identify unequivocally the presence of unmodified LTE₄, in a high performance liquid chromatography-purified fraction of urine from a normal healthy volunteer after infusion with LTE₄.     

Atomically resolved spin-dependent tunneling on the oxygen-terminated Fe3O4(111)

We employ spin-polarized STM to study the spin-dependent tunneling between a magnetite (111) sample and an antiferromagnetic tip through a vacuum barrier at room temperature. Atomic scale STM images show significant magnetic contrast corresponding to variations in the local surface states induced by oxygen vacancies. The estimated variations in tunneling magnetoresistance of 250% suggest that the spin-transport properties are significantly altered locally by the presence of surface defects.