Copper-catalyzed propargylic C-H functionalization for allene syntheses.

Allenenitriles bearing different synthetically versatile functional groups have been prepared smoothly from 5-alkynyl fluorosulfonamides in decent yields with an excellent chemo- and regio-selectivity under redox neutral conditions. The resulting allenenitriles can be readily converted to useful functionalized heterocycles. Based on mechanistic study, it is confirmed that this is the first example of radical-based non-activated propargylic C-H functionalization for allene syntheses.

Palladium-catalysed construction of butafulvenes.

Butafulvene is a constitutional isomer of benzene, comprising a cyclobutene skeleton bearing two exocyclic conjugated methylene units. As a result of the intrinsic high strain energy and anti-aromaticity, the preparation of butafulvene compounds has been a fundamental issue for the development of butafulvene chemistry. Here an efficient palladium-catalysed coupling protocol involving propargylic compounds has been developed, providing a solid and versatile strategy for the rapid assembly of symmetric butafulvene derivatives. Based on mechanistic studies, two complementary mechanisms, both involving palladium catalysis, have been confirmed. With the mechanism unveiled, the synthesis of non-symmetric butafulvenes has also been achieved. Advantages of this strategy include tolerance to a wide range of propargylic molecules, mild reaction conditions, simple catalytic systems and easy scalability. The synthetic potential of the products as platform molecules for cyclobutene derivatives has also been demonstrated.

Enhancing Water-Splitting Efficiency Using a Zn/Sn-Doped PN Photoelectrode of Pseudocubic α-Fe2O3 Nanoparticles.

α-Phase hematite photoelectrodes can split water. This material is nontoxic, inexpensive, and chemically stable; its low energy gap of 2.3 eV absorbs light with wavelengths lower than 550 nm, accounting for approximately 30% of solar energy. Previously, we reported polyhedral pseudocubic α-Fe2O3 nanocrystals using a facile hydrothermal route to increase spatial charge separation, enhancing the photocurrent of photocatalytic activity in the water-splitting process. Here, we propose a p-n junction structure in the photoanode of pseudocubic α-Fe2O3 to improve short carrier diffusion length, which limits its photocatalytic efficiency. We dope Zn on top of an Fe2O3 photoanode to form a layer of p-type semiconductor material; Sn is doped from the FTO substrate to form a layer of n-type semiconductor material. The p-n junction, n-type Fe2O3:Sn and p-type Fe2O3:Zn, increase light absorption and charge separation caused by the internal electric field in the p-n junction.

Lanthanide Functionalized Metal-Organic Coordination Polymer: Toward Novel Turn-On Fluorescent Sensing of Amyloid ß-Peptide.

Metal-organic coordination polymers (MOCPs) have been emerging as very attractive nanomaterials due to their tunable nature and diverse applications. Herein, using Tb3+ as the luminescence center, 1,3,5-benzenetricarboxylate (BTC) as building block and Cu2+ as the signal modulator as well as a recognition unit, we propose a novel and effective lanthanide functionalized MOCP (LMOCP) fluorescent sensor (Cu-BTC/Tb) for amyloid ß-peptide (Aß) monomer, a biomarker for Alzheimer disease (AD). Specifically, Cu-BTC/Tb, created by postsynthesis modification strategy under room temperature, is almost nonemissive due to the quenching effect of Cu2+ in the MOCP, exhilaratingly, the presence of Aß1-40 triggered a significant emission enhancement of Cu-BTC/Tb assay due to the high binding affinity of Aß1-40 for Cu2+ and the subsequent suppression of the quenching effect. In the assay, this LMOCP sensor shows high sensitivity with detection limit of 0.3 nM. Due to its capability to eliminate autofluorescence, Cu-BTC/Tb was also applied to the time-gated detection of Aß1-40 in human plasma with promising results. This work presents a novel strategy for the construction of functional luminescent LMOCP for sensitively turn-on fluorescent sensing of Aß1-40. We believe the proposed strategy would inspire the development of various LMOCP-based fluorescent assays or medical imaging platforms for advanced biological implementations.

Lanthanide coordination polymer probe for time-gated luminescence sensing of pH in undiluted human serum.

Lanthanide coordination polymers (LCPs) have emerged as fascinating materials because of their specific structure and properties. In this work, utilizing hydrosoluble biomolecule of guanosine-5'-monophosphate (GMP) as bridging linker, lanthanide terbium ions (Tb3+) as metal nodes, and silver ions (Ag+) as sensitizers, we synthesized a pH responsive luminescent lanthanide CP probe of Tb/GMP/Ag. The probe possesses high luminescence due to the sensitization of Ag+; While in alkaline solutions, Ag+ in Tb/GMP/Ag immediately binds to OH-, forming Ag2O precipitation and resulting in a distinct fluorescence quenching of Tb/GMP/Ag. This probe displays high selectivity for OH- and a broader pH detection range of 7.5-13.0. In addition, based on the high anti-interference ability in serum, we applied Tb/GMP/Ag to measure pH in undiluted human serum samples, yielding satisfactory results.

Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination.

Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg(2+) detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb(3+) from the quenching effect of O-H vibration in water molecules. The subsequent addition of Hg(2+) into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg(2+). As a kind of Hg(2+) nanosensor, the probe exhibited excellent selectivity for Hg(2+) and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg(2+) in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging.

In-channel simplified decoupler with renewable electrochemical detection for microchip capillary electrophoresis.

Electrochemical (EC) detection is comparable to fluorescence detection in that it is simple to perform, economical, and highly sensitive. In this study, we used replica molding to fabricate a PDMS microchip for microchip capillary electrophoresis (CE). A decoupler electrode and a working electrode were implanted into the PDMS chip during the molding process to prevent leakage into the electrode channel. The working electrode could be renewed readily through its slight withdrawal (ca. 3 mm) from the PDMS; its detection ability was highly reproducible in the microchip CE-EC system. The relative standard deviation (R.S.D.) of the detecting current for the renewed working electrode was 1.2% (n=5). The calibration curves were linear for both dopamine and catechol analytes over the concentration range 10-1000 microM, with coefficients of determination (R(2)) of 0.999 and 0.976, respectively. The number of theoretical plates (N/m) for these analytes was greater than 133,000.