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The metal-catalyzed hydrofunctionalization reaction of allenes is an efficient approach for the construction of new allyl compounds. This work described a palladium-catalyzed/ligand-controlled asymmetric hydrosulfonylation of simple alkylallenes and arylallenes in the presence of Pd 2 dba 3 . Using a Josiphos or Segphos ligand, the alkylallenes or arylallenes could render the corresponding branched chiral allylsulfones with high yields and high enantioselectivities up to 90% and 99% ee, respectively.

We have developed an ultrasound-assisted remote benzylic C(sp 3 )-H alkylation of N -fluorobenzamides with enol silanes; a series of β-aryl substituted propiophenones was generated in good to high yields. This reaction represents a formal C(sp 3 )-C(sp 3 ) coupling and features simplicity, high efficiency, and wide substrate scope in a multiple-step sequential process, which involves N-F homolysis, 1,5-hydrogen atom transfer, benzylic radical addition, oxidation by copper(II) salt, and removal of the trimethylsilyl group. Also, DFT theoretical calculations and Marcus theory were employed to consolidate the proposed reaction mechanism.

An efficient catalytic asymmetric cascade cycloaddition reaction of arylalkynols with dioxopyrrolidines was developed. This reaction was achieved using Au(I) and ( R )-BINOL-Ti(IV) bimetallic catalysts and exclusively delivered a series of chiral oxo-bridged bicyclic benzooxacine compounds in up to 86% yield with 96% ee as well as >33:1 dr . Meanwhile, three new σ bonds and three new stereogenic centers were formed in a one-pot process.

Manganese dioxide (MnO 2 ) nanostructures have aroused great interest among analytical and biological medicine researchers as a unique type of tumor microenvironment (TME)-responsive nanomaterial. However, reliable approaches for synthesizing yolk-shell nanostructures (YSNs) with mesoporous MnO 2 shell still remain exciting challenges. Herein, a YSN (size, ∼75 nm) containing a mesoporous MnO 2 shell and Er 3+ -doped upconversion/downconversion nanoparticle (UCNP) core with a large cavity is demonstrated for the first time. This nanostructure not only integrates diverse functional components including MnO 2 , UCNPs, and YSNs into one system but also endows a size-controllable hollow cavity and thickness-tunable MnO 2 layers, which can load various guest molecules like photosensitizers, methylene blue (MB), and the anticancer drugs doxorubicin (DOX). NIR-II fluorescence and photoacoustic (PA) imaging from UCNP and MB, respectively, can monitor the enrichment of the nanomaterials in the tumors for guiding chemo-photodynamic therapy (PDT) in vivo . In the TME, degradation of the mMnO 2 shell by H 2 O 2 and GSH not only generates Mn 2+ for tumor-specific T 1 -MR imaging but also releases O 2 and drugs for tumor-specific treatment. The result confirmed that imaging-guided enhanced chemo-PDT combination therapy that benefited from the unique structural features of YSNs could substantially improve the therapeutic effectiveness toward malignant tumors compared to monotherapy.

Early detection of drug-induced acute kidney injury (AKI) is crucial for effective treatment and prevention of further injury. It remains challenging, however, because of the lack of activatable indicators with multimodality imaging capability that could increase the accuracy of diagnosis by mutual verification. Herein, we report an activatable probe, FDOCl-22 , that enabled dual-modality detection of the early-stage drug-induced AKI. FDOCl-22 was completely soluble in water and highly sensitive to hypochlorous acid (HOCl). Dramatic increases of both near-infrared (NIR) emission and absorption were observed after reaction with HOCl. A correlation between HOCl concentration and drug-induced AKI was established using FDOCl-22 as a tool. As a consequence, the HOCl-activated probe was able to detect the early-stage drug-induced AKI by dual-modality imaging, irrespective of the drug stimulation time or dosage, by combining NIR fluorescence and photoacoustic imaging.

We reported a novel two-step stereoselective synthesis of functionalized pyrrolidines from homopropargylic sulfonamides and nucleophiles via an isolable N , O -acetal intermediates. This reaction features mild conditions and good scope of substrates. In addition, the use of hexafluoroisopropanol, acting as a solvent, an additive, a weak nucleophile, and a good leaving group, is pivotal to the success of the method. Moreover, reactions of chiral homopropargylic sulfonamides afford only 2,5- cis -disubstituted pyrrolidines with high diastereoselectivity (up to >99:1 dr) and enantioselectivity (up to >99% ee). The overall reaction constitutes a formal 1,1-bifunctionalization of terminal alkynes, which has hitherto been reported only rarely. Additionally, this method provides efficient access to pharmaceutical intermediate and to carry out postmodification of natural products.

The diversified temperature-controlled hydroamination cyclization cascade reactions of homopropargylic amines and 2-butynedioates were developed for the construction of various pyrrolo- b-cyclobutenes and dihydro-1 H-azepines, respectively. This reaction actually involved an intramolecular hydroamination cyclization of homopropargylic amines to give the active dihydropyrroles intermediates, which subsequently underwent [2+2]-cycloaddition with 2-butynedioates to generate the pyrrolo- b-cyclobutenes at no more than 120 °C. Alternatively, the dihydro-1 H-azepines were directly produced at 150 °C in the reactions of homopropargylic amines and 2-butynedioates. The application of substrate scope was wide, and the corresponding products were obtained in high to excellent yields.

Cryptand-containing alternative copolymers were first made from copolymerization of styrenic derivatives and maleic anhydride and then chemically modified in this work by grafting methoxy poly(ethylene glycol) (MPEG) onto the maleic functional groups. These graft copolymers show interesting multistep soluble-insoluble-soluble (S-I-S) transitions in acidic aqueous media at a cloud point ( T cp ) and a subsequent mixing temperature ( T mix ). Turbidity measurements and dynamic light scattering studies indicate that such complex transitions may be attributed to the entropic contribution associated with the dehydration and aggregation of the MPEG groups and then the enthalpic contribution associated with the hydrogen bonding between ethylene glycol and carboxylic acid groups. More importantly, the phase transition temperatures and insoluble temperature ranges are very sensitive to changes in subtle hydrophobic-hydrophilic balance of the copolymers, such as the variation of pH, the cryptand size, and the length of the MPEG graft. The understanding of the S-I-S transition in relation to the structure of the copolymers and the external conditions may be useful in the design of smart materials and sensors., Competing Interests: The authors declare no competing financial interest.

The mining and burning of low-rank coal in Xuanwei, China have attracted a great deal of research attention because of the generated polyaromatic hydrocarbons (PAHs) and the high incidence of lung cancer in this region. Given the abundant transition metals in the allitic soil, we hypothesized that environmentally persistent free radicals (EPFRs) are formed in this region and the potential risk had not been addressed. Strong electron paramagnetic resonance (EPR) signals of 3.20 × 10 17 - 3.10 × 10 19 spins/g were detected in environmental samples, including chimney soot, coal, soil and total suspended particles (TSP). These EPR signals did not significantly change after 18-months storage and had g-values in the range of 2.0039-2.0046, suggesting typical organic free radicals. Similar strong EPR signals were observed in PAH (anthracene and pyrene as model compounds) degradation on simulated soil particles and lasted over one month even when the applied PAHs were 100% degraded. Based on g-value and bond width, we propose that EPR signals detected in TSP and soot originated from both coal combustion and PAH photodegradation. Further research is thus urgently required to investigate EPFR generation, exposure and risk in Xuanwei to better understand the cause of high lung cancer incidence.

A new one-pot cascade reaction of homopropargylic amines with simple imines is developed in the presence of Cu(OTf)2 and affords a series of hexahydro-1H-pyrrolo[3,2-c]quinoline derivatives in good to high yields. This reaction proceeds through an intramolecular hydroamination cyclization of homopropargylic amine to generate a highly reactive dihydropyrrole intermediate in situ. It subsequently reacts with imine via an intermolecular inverse-electron-demand aza-Diels-Alder reaction and a 1,3-H shift to give the fused pyrroloquinoline structures, forming two new C-C bonds and one C-N bond and one N-H bond.

A novel dimethyl acrylate 18-membered macrocycle (DMECE), acting as both bifunctional monomer and cross-linker, was designed and synthesized, and thus employed to construct a series of macrocycle-containing amphiphilic hyperbranched polymers (HBPs). The macrocyclic recognition effect between the HBPs and alkali metal ions showed that Na(+) was introduced in 1:1 interactive mode, whereas K(+) and Rb(+) were in 2:1 ratio. Through the formation of the DMECE/K(+) = 2:1 rigid "sandwich" complex of amphiphilic hyperbranched polymers, dimple-shaped aggregates were observed by TEM, SEM and AFM. Moreover, the initial concentration, the nature of solvent, the mode and affinity of the macrocyclic recognition effect as well as the amount of K(+), were essential control factors for the formation of dimple-shaped aggregates. Most importantly, the macrocyclic recognition effect endows the reversibility of the dimple-shaped aggregates and the size controllability of its circular opening, which provides a new strategy for design novel macrocycle-containing HBPs and great potential application in the field of capture and release.

Metabolite identification in the complex NMR spectra of biological samples is a challenging task due to significant spectral overlap and limited signal-to-noise. In this study we present a new approach, RANSY (ratio analysis NMR spectroscopy), which identifies all the peaks of a specific metabolite on the basis of the ratios of peak heights or integrals. We show that the spectrum for an individual metabolite can be generated by exploiting the fact that the peak ratios for any metabolite in the NMR spectrum are fixed and proportional to the relative numbers of magnetically distinct protons. When the peak ratios are divided by their coefficients of variation derived from a set of NMR spectra, the generation of an individual metabolite spectrum is enabled. We first tested the performance of this approach using one-dimensional (1D) and two-dimensional (2D) NMR data of mixtures of synthetic analogues of common body fluid metabolites. Subsequently, the method was applied to (1)H NMR spectra of blood serum samples to demonstrate the selective identification of a number of metabolites. The RANSY approach, which does not need any additional NMR experiments for spectral simplification, is easy to perform and has the potential to aid in the identification of unknown metabolites using 1D or 2D NMR spectra in virtually any complex biological mixture., (© 2011 American Chemical Society)