Total Synthesis of (+)-Erogorgiaene and the Pseudopterosin A−F Aglycone via Enantioselective Cobalt-Catalyzed Hydrovinylation

Due to their pronounced bioactivity and limited availability from natural resources, metabolites of the soft coral Pseudopterogorgia elisabethae, such as erogorgiaene and the pseudopterosines, represent important target molecules for chemical synthesis. We have now developed a particularly short and efficient route towards these marine diterpenes exploiting an operationally convenient enantioselective cobalt-catalyzed hydrovinylation as the chirogenic step. Other noteworthy C−C bond forming transformations include diastereoselective Lewis acid-mediated cyclizations, a Suzuki coupling and a carbonyl ene reaction. Starting from 4-methyl-styrene the anti-tubercular agent (+)-erogorgiaene (>98 % ee) was prepared in only 7 steps with 46 % overall yield. In addition, the synthesis of the pseudopterosin A aglycone was achieved in 12 steps with 30 % overall yield and, surprisingly, was found to exhibit a similar anti-inflammatory activity (inhibition of LPS-induced NF-κB activation) as a natural mixture of pseudopterosins A−D or iso-pseudopterosin A, prepared by β-D-xylosylation of the synthetic aglycone.     

Far‐Red Emitting Fluorescent Dyes for Optical Nanoscopy: Fluorinated Silicon–Rhodamines (SiRF Dyes) and Phosphorylated Oxazines

Far‐red emitting fluorescent dyes for optical microscopy, stimulated emission depletion (STED), and ground‐state depletion (GSDIM) super‐resolution microscopy are presented. Fluorinated silicon–rhodamines (SiRF dyes) and phosphorylated oxazines have absorption and emission maxima at about λ≈660 and 680 nm, respectively, possess high photostability, and large fluorescence quantum yields in water. A high‐yielding synthetic path to introduce three aromatic fluorine atoms and unconventional conjugation/solubilization spacers into the scaffold of a silicon–rhodamine is described. The bathochromic shift in SiRF dyes is achieved without additional fused rings or double bonds. As a result, the molecular size and molecular mass stay quite small (<600 Da). The use of the λ=800 nm STED beam instead of the commonly used one at λ=750–775 nm provides excellent imaging performance and suppresses re‐excitation of SiRF and the oxazine dyes. The photophysical properties and immunofluorescence imaging performance of these new far‐red emitting dyes (photobleaching, optical resolution, and switch‐off behavior) are discussed in detail and compared with those of some well‐established fluorophores with similar spectral properties.     

Phosphatase reactivity of a dicopper(ii) complex of a patellamide derivative - possible biological functions of cyclic pseudopeptides

A possible biological function of cyclic pseudo-octapeptides is presented. The dinuclear copper(ii) complex of a synthetic analogue ([Cu(2)(H(2)Pat(1))(μ-OH)(OH(2))(2)]) of the naturally occurring ascidiacyclamide is known to have a hydroxo-bridged dicopper(ii) site which is able to catalytically transform CO(2) into CO(3)(2-). This complex is shown here to function as a phosphatase mimic, suggesting that the so far unknown biological function of these macrocycles within the ascidians may involve phosphoester hydrolysis.     

Low-temperature light detectors: Neganov–Luke amplification and calibration

The simultaneous measurement of phonons and scintillation light induced by incident particles in a scintillating crystal such as CaWO₄ is a powerful technique for the active rejection of background induced by γ?s and β  ?s and even neutrons in direct Dark Matter searches. However, ?1%$?1\text{\%}$ of the energy deposited in a CaWO₄ crystal is detected as light. Thus, very sensitive light detectors are needed for an efficient event-by-event background discrimination. Due to the Neganov–Luke effect, the threshold of low-temperature light detectors based on semiconducting substrates can be improved significantly by drifting the photon-induced electron–hole pairs in an applied electric field. We present measurements with low-temperature light detectors based on this amplification mechanism. The Neganov–Luke effect makes it possible to improve the signal-to-noise ratio of our light detectors by a factor of ∼9 corresponding to an energy threshold of ∼21 eV$\sim 21\text{eV}$. We also describe a method for an absolute energy calibration using a light-emitting diode.     

磁性隧道结中自旋相关输运的势垒影响

为了研究势垒对铁磁/绝缘层/半导体/绝缘层/铁磁(FM/I/SM/I/FM)双隧道结中自旋相关电子输运特性的影响,提出了在半导体层厚度合适的情况下,非对称势垒对于提高平行结构磁性双隧道结的自旋注入效率SIE(spin injection efficiency)更具优势.数值计算结果表明,当两势垒强度的比率达到合适数值时双结的SIE和隧穿磁电阻TMR(tunneling magnetore resistance)都将达到最大,这给提高从铁磁到半导体的SIE带来新选择.研究还表明,非对称势垒结构磁性隧道结中增大铁磁交换能对提高SIE和TMR都是有益的,而且铁磁交换能的增加对SIE的提高要比对TMR的提高更显著.     

关于加强青年农民工的思想道德建设的思考

青年农民工是我国工业化、城市化进程中的一支重要力量,他们在为我国经济社会发展做出巨大贡献的同时,却遭受着不公正的待遇,不能取得与拥有城镇户口身份的劳动者平等的地位并享受相应权益等等,这些问题在一定程度上造成青年农民工在思想和道德素质上表现出种种不足,给社会和谐稳定带来了隐患。为此,加强青年农民工的思想道德建设,成为和谐社会发展中的一个重要课题。     

Study of alternating current conduction mechanism in polypyrrole-magnesium ferrite hybrid nanocomposite through correlated barrier hopping model

In the present work, both polypyrrole (PPy) and optimized polypyrrole–magnesium ferrite (PPy-MgFe₂O₄) hybrid nanocomposite were synthesized separately by simple oxidative chemical polymerization method and then structurally characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The FTIR spectrum of the composite showed the presence of characteristic absorption bands of both PPy and MgFe₂O₄ in the composite confirming interfacial interaction of PPy with MgFe₂O₄. That this interaction is not affected by crystalline behaviour of predominant MgFe₂O₄ particles but that MgFe₂O₄ has embedded in PPy matrix was confirmed by XRD studies. Agglomerated granular spherical morphology of the composite was confirmed by SEM studies. Decrease in AC conductivity of the composite as compared to PPy due to the formation of interfacial heterojunction barrier between p-type PPy and n-type MgFe₂O₄ was confirmed experimentally and well supported theoretically by calculating binding energy, hopping distance and density of states at Fermi level of PPy and the composite as per CBH model.     

Surface species in the direct amination of methanol over Brønsted acidic mordenite catalysts

Quantitative in situ infrared spectroscopy in combination with kinetic analysis is utilized to derive mechanistic aspects for the reaction of methanol with ammonia on Brønsted acidic mordenite. Under non-reactive conditions, a coadsorption complex between methanol and ammonia is found, in which only ammonia is in direct interaction with the Brønsted acid sites of the zeolite. This complex is proposed to be the precursor for the formation of protonated methylamines in the zeolite pores which are formed in sequential order up to tetramethylammonium ions. These methylamines are unable to desorb under reaction conditions in the absence of ammonia. They leave the surface either by ammonia adsorption assisted desorption or by scavenging of methyl groups from protonated methylamines by ammonia. Both steps are concluded to be potentially rate determining.     

Epr-und emissionsspektroskopische untersuchungen an chinoxalinen und s-triazolo-[4,3-a]chinoxalinen

The electronic excited states of quinoxalines and s-triazolo[4,3-a]quinoxalines have been investigated by EPR and emission spectroscopy. The zero-field parameters D^* and the maxima of emission of the studied substances are stated and their emission behaviour is discussed. On the basis of simplified term schemes and by the aid of analogue considerations a discussion is given of the influence of substitution and the rate of condensation on relaxation processes after optically excitation and on the electronic interactions in the lowest triplet states.     

Preparation of peanut butter suspension for determination of peanuts using enzyme-linked immunoassay kits

Peanuts are one of the 8 most common allergenic foods and a large proportion of peanut-allergic individuals have severe reactions, some to minimal exposure. Specific protein constituents in the peanuts are the cause of the allergic reactions in sensitized individuals who ingest the peanuts. To avoid accidental ingestion of peanut-contaminated food, methods of analysis for the determination of the allergenic proteins in foods are important tools. Such methods could help identify foods inadvertently contaminated with peanuts, thereby reducing the incidence of allergic reactions to peanuts. Commercial immunoassay kits are available but need study for method performance, which requires reference materials for within- and between-laboratory validations. In this study, National Institute of Standards and Technology Standard Reference Material 2387 peanut butter was used. A polytron homogenizer was used to prepare a homogenous aqueous Peanut Butter suspension for the evaluation of method performance of some commercially available immunoassay kits such as Veratox for Peanut Allergen Test (Neogen Corp.), Ridascreen Peanut (R-Biopharm GmbH), and Bio-Kit Peanut Protein Assay Kit (Tepnel). Each gram of the aqueous peanut butter suspension contained 20 mg carboxymethylcellulose sodium salt, 643 microg peanut, 0.5 mg thimerosal, and 2.5 mg bovine serum albumin. The suspension was homogenous, stable, reproducible, and applicable for adding to ice cream, cookies, breakfast cereals, and chocolate for recovery studies at spike levels ranging from 12 to 90 microg/g.