Rh-catalyzed intramolecular aromatic C–H insertion of α-diazo β-ketoesters: synthesis of 4-carbonyl chroman derivatives

A Rh-catalyzed intramolecular aromatic C–H insertion of α-diazo β-ketoesters was developed. This protocol offers a practical strategy for the synthesis of 4-carbonyl chroman derivatives with high yield and is compatible with a wide variety of substituents. Synthetic applications of the 4-carbonyl chroman were also demonstrated.     

X-ray crystal structure of the copper(II)bis(2,2′-dipyridyl)dithiocarbamate,produced by an unusual reaction of CS2 with Cu−N bonds

The title compound was obtained from a CS₂ solution of bis(2,2-dipyridylamido)copper(II), by insertion of solvent into this complex. In the structure of the dithiocarbamate the metal atom is approximately square-planar coordinated by four S atoms from two chelating ligands. Considering the long interactions between the metal center and the S(2) atom from a centrosymmetrically related complex [Cu(1)...S(2)=3.230 Å], double bridged dimers are formed with the copper atoms in an elongated square-pyramidal coordination. The crystals are monoclinic, space groupP2 ₁/n witha=14.549(3),b=11.662(3)c=15.329(4) Å and =114.79(2)°.     

Spectroscopy on photografted polyethylene surfaces using a perfluorophenyl azide: Evidence for covalent attachment

The present study was conducted in order to confirm C―H insertion of a perfluorophenyl nitrene, produced by UV‐irradiation of a perfluorophenyl azide, to polyethylene surfaces. It was shown previously that water‐repelling, oil‐repelling, and dirt‐repelling polyethylene surfaces can be created by “grafting to” of perfluoroalkanes using a photoreactive surface modifier based on azide/nitrene chemistry. The abrasion resistance of the new surfaces was enhanced compared with a coating using a simple, long‐chain perfluoroalkane. However, covalent binding of the surface modifier was not unequivocally demonstrated. Here, spectroscopic information is presented suggesting that, indeed, a monomolecular, covalently bound grafted layer is formed from the photodecomposition of a perfluorophenyl azide on polyethylene surfaces. Infrared spectroscopy showed that the peak from the azide moiety disappeared upon UV‐irradiation, and the light dose for completion of the photo decomposition was determined to be approximately 322 mJ/cm². A model compound mimicking the grafted nitrene species was synthesized, having a λ_max of 281 nm in hexane. The photografted and washed layer had a λ_max of 286 nm, indicating a good conformity with the model compound. X‐ray photoelectron spectroscopy of the nitrogen species from the photografted layer showed a peak at 400.0 eV. The model compound had a N 1s binding energy of 399.7 eV, thus being comparable.     

Preparation,Post‐Modification,and Antibacterial Application of Gelatin Electrospun Membranes

Two bis(diaryldiazomethane)s substituted with amino groups are synthesized and used for the surface modification of membranes electrospun from gelatin. These membranes are then reacted with tolylene‐2,4‐diisocyanate to give urea‐functionalized materials, so that hydrogen peroxide can be reversibly bound onto their surface. These membranes are characterized by scanning electron microscopy, XPS, differential scanning calorimeter, and tensile test to show their surface properties and bulk properties. The surface modification with amino‐substituted diazomethanes and the subsequent cross‐linking reaction with diisocyanates contribute to high loadings of hydrogen peroxide, and greatly increase the antibacterial activity of gelatin‐derived membranes, which open a new horizon in the preparation of high loading antiseptic/antibacterial biomacromolecular surfaces and interfaces.     

基于磁性光子晶体的宽频带低损耗环行器

设计了一种基于光子晶体的结构紧凑、损耗低、频带宽的三端口三光路光环行器,该环行器由Y型光子晶体波导及配置在中心位置的磁光材料星形柱构成。通过对结构参数进行优化,该结构可以分别实现194~196GHz、198.2~199.4GHz和197~197.6GHz三个频段内稳定的顺时针单向环行传输,隔离度分别大于24、15.21和14.5dB,插入损耗分别小于0.18、0.11和0.38dB。该环行器结构简单,特别适用于结构复杂的光子集成系统,同时可提高光路的抗干扰性和稳定性等。     

Amplifying Nanoparticle Targeting Performance to Tumor via Diels–Alder Cycloaddition

Traditional targeting approach utilizing biological ligands has to face the problems of limited receptors and tumor heterogeneity. Herein, a two‐step tumor‐targeting and therapy strategy based on inverse electron‐demand [4+2] Diels–Alder cycloaddition (iEDDA) is described. Owing to the unique acidic tumor microenvironment, an intravenous injection of tetrazine modified pH (low) insertion peptide could efficiently target and incorporate onto various cell surfaces in tumor tissue, such as cancer cells, vascular endothelial cells, and tumor‐associated fibroblasts. The “receptor‐like” tetrazine groups with a large amount and homogeneous intratumoral distribution could then serve as the baits to greatly amplify the tumor‐targeting ability of indocyanine green (ICG)‐loaded and trans‐cyclooctene (TCO)‐conjugated human serum albumin (HSA) nanoparticles (TCO‐HSA‐ICG NPs) via iEDDA after the second intravenous injection. Compared with the passive enhanced permeability and retention (EPR) effect and traditional active targeting approaches, the targeting performance and photothermal therapeutic effect based on the two‐step strategy are significantly enhanced, while no notable toxicity is observed. As acidity is a characteristic of solid tumor, the two‐step strategy can serve as a universal and promising modality for safe and high‐performance nanoparticle‐based antitumor therapy.     

一种新型Ka频段功率合成放大器的设计

为了提高Ka频段功率放大器的输出功率,设计了一种新型的毫米波波导内空间功率合成放大器.采用魔T功率合成器和波导-微带双探针转换实现的波导内空间功率分配/合成网络,在毫米波频段实现了宽带、低损耗、幅相对称的四路功率合成放大器.该毫米波功率合成放大器的合成效率,在25~29 GHz高于82%,在25~28 GHz高于86%.     

A new look at some classical theorems on continuous functions on normal spaces

A sufficient condition for the strict insertion of a continuous function between two comparable upper and lower semicontinuous functions on a normal space is given. Among immediate corollaries are the classical insertion theorems of Michael and Dowker. Our insertion lemma also provides purely topological proofs of some standard results on closed subsets of normal spaces which normally depend upon uniform convergence of series of continuous functions. We also establish a Tietze-type extension theorem characterizing closed G _δ -sets in a normal space. This research was supported by the Ministry of Education and Science of Spain and FEDER under grant MTM2006-14925-C02-02. The first named author also acknowledges financial support from the University of the Basque Country under grant UPV05/101.     

Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene

The mechanism is investigated for Cp^tBuRh(OH)₂-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional. The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—C σ bonds. After the coordination/insertion of alkenes, respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of Cp^tBuRh. The promotion of Cp^tBuRh(OH)₂ lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive elimination. The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone. The role of Rh(III) catalyst and release of Rh(I) is supported by Multiwfn analysis on frontier molecular orbital(FMO) of specific transiton states(TSs) and Mayer bond order(MBO) value of vital bonding, breaking.