Isoquinoline skeleton synthesis via chelation-assisted C−H activation

Transition-metal-catalyzed isoquinoline synthesis that profits from the strategy of chelation-assisted C−H activation has flourished over the past decade. By virtue of the directed C−H bond cleavage of imines, amines, amidines, oximes, hydroximoyl halides, hydrazones, or azines, diverse isoquinoline derivatives have been accessed from alkynes, conjugated dienes, or diazo compounds under the catalysis of rhodium, ruthenium, palladium, nickel, or manganese. This digest summarizes the annulation reactions via chelation-assisted C−H activation leading to isoquinolines, isoquinolinium salts, or isoquinoline N-oxides.     

Phosphine-mediated synthesis of trifluoromethyl substituted pyrroles using TFAA as the CF3 source

A phosphine-mediated synthesis of trifluoromethyl substituted pyrrole derivatives was achieved. The method described here is very fast, operationally simple, and easily amenable to scale-up, and commercially available trifluoroacetic anhydride (TFAA) is used as the only trifluoromethyl source. A wide range of products were obtained with good yields under mild condition using this method.     

Modified 2-window approach for rapid determination of 90Sr and 90Y at low quench level using liquid scintillation counting

⁹⁰Sr is a product of nuclear fission, the radioactivity of which can be determined by liquid scintillation counting (LSC). Because the LSC spectra of ⁹⁰Sr and its daughter ⁹⁰Y overlap each other, the following methods are usually used: (1) measuring immediately after ⁹⁰Sr/⁹⁰Y separation; (2) waiting to reach radioactive equilibrium; (3) adopting the conventional 2-window approach; and (4) using the spectra deconvolution technique. The first one requires ⁹⁰Sr/⁹⁰Y separation and immediate measurement; the second one is time-consuming; the third one is valid only for samples with the same quench level as the calibration standard; the last one is somewhat complicated, and in some cases it is not convenient to export the experimental data to some deconvolution software. Therefore, we have developed a modified 2-window approach to rapidly determine ⁹⁰Sr and ⁹⁰Y in either equilibrium or disequilibrium at low quench level. The key modification of the approach is to provide an LSC spectrum of pure ⁹⁰Y with the same quench level as the sample to be determined. This modification eliminates the need to conduct ⁹⁰Sr/⁹⁰Y separation for the sample itself, to prepare the quench curves, and to fit the LSC spectra with some deconvolution software.     

Rapid quantitative analysis of individual anthocyanin content based on high‐performance liquid chromatography with diode array detection with the pH differential method

A new quantitative technique for the simultaneous quantification of the individual anthocyanins based on the pH differential method and high‐performance liquid chromatography with diode array detection is proposed in this paper. The six individual anthocyanins (cyanidin 3‐glucoside, cyanidin 3‐rutinoside, petunidin 3‐glucoside, petunidin 3‐rutinoside, and malvidin 3‐rutinoside) from mulberry (Morus rubra) and Liriope platyphylla were used for demonstration and validation. The elution of anthocyanins was performed using a C₁₈ column with stepwise gradient elution and individual anthocyanins were identified by high‐performance liquid chromatography with tandem mass spectrometry. Based on the pH differential method, the high‐performance liquid chromatography peak areas of maximum and reference absorption wavelengths of anthocyanin extracts were conducted to quantify individual anthocyanins. The calibration curves for these anthocyanins were linear within the range of 10–5500 mg/L. The correlation coefficients (r²) all exceeded 0.9972, and the limits of detection were in the range of 1–4 mg/L at a signal‐to‐noise ratio ≥5 for these anthocyanins. The proposed quantitative analysis was reproducible with good accuracy of all individual anthocyanins ranging from 96.3 to 104.2% and relative recoveries were in the range 98.4–103.2%. The proposed technique is performed without anthocyanin standards and is a simple, rapid, accurate, and economical method to determine individual anthocyanin contents.     

Sensitive detection of T4 polynucleotide kinase activity based on coupled exonuclease reaction and nicking enzyme-assisted fluorescence signal amplification

As a prominent member of the 5′-kinase family, T4 polynucleotide kinase (PNK) plays an important role in gene function regulations, and the study of PNK activity and its potential inhibitors is significant for research related to the DNA phosphorylation process. Here, we proposed a novel strategy for the detection of PNK activity and its inhibition, which combines exonuclease enzyme reaction and nicking enzyme-assisted fluorescence signal amplification. Through recycling cleavage of DNA fluorescence probe for signal amplification, a highly sensitive PNK sensing platform is developed, and a very low detection limit of 0.05 mU/mL is achieved, which is better than or comparable to that of the previously reported PNK assays. The present approach adopts a simple separation-free procedure in which the enzyme assay is conducted in homogeneous solutions. Additionally, the inhibitory effects of several known kinase inhibitors on PNK have been successfully detected. Since the proposed assay exhibits the advantages of high sensitivity and simplicity, it holds great potential in providing a promising platform for convenient and highly sensitive detection of PNK activity and its inhibitors.

Tissue imaging and serum lipidomic profiling for screening potential biomarkers of thyroid tumors by matrix-assisted laser desorption/ionization-Fourier transform ion cyclotron resonance mass spectrometry

Changes in serum lipidome and in tissue lipidome are associated with cancer. In this study, tissue mass spectrometry imaging (MSI) and serum lipid profiling by matrix-assisted laser desorption/ionization-Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR MS) were performed to investigate significantly changed lipids in both tumor (malignant thyroid cancer (MTC) and benign thyroid tumor (BTT)) tissues and sera. Y-scatterplots of variable importance in the projection (VIP) values vs. fold change values indicate that change trends in the levels of ten lipids (i.e., phosphatidylcholine (PC)(34:1), PC(36:1), PC(38:6), phosphatidic acid (PA) (36:2), PA(36:3), PA(38:3), PA(38:4), PA(38:5), PA(40:5), and sphingomyelin (SM)(34:1)) in both tissues and sera from MTC patients, BTT patients, and normal individuals are significantly associated with these three types of pathophysiological status. In order to examine their diagnostic ability, 289 serum samples from 124 MTC patients, 43 BTT patients, and 122 normal controls were randomly divided into the training set and validation set. A biomarker of PC(34:1) exhibited excellent diagnostic ability to differentiate both MTC and BTT patients from normal individuals, with an area under the receiver operating characteristic (ROC) curve value of 0.984, a sensitivity of 96.4 %, and a specificity of 92.7 %. A panel which included PA(36:3) and SM(34:1) could distinguish between MTC and BTT, with an area under receiver operating characteristic curve (AUC) of 0.961, a sensitivity of 87.8 %, and a specificity of 92.9 %. It is worth noting that a panel consisting of PC(34:1), PA(36:3), and SM(34:1) could differentiate MTC patients from both BTT patients and normal individuals, with an AUC of 0.841, a sensitivity of 86.6 %, and a specificity of 75.5 %.

A wide range optical pH sensor for living cells using Au@Ag nanoparticles functionalized carbon nanotubes based on SERS signals

p-Aminothiophenol (pATP) functionalized multi-walled carbon nanotubes (MWCNTs) have been demonstrated as an efficient pH sensor for living cells. The proposed sensor employs gold/silver core-shell nanoparticles (Au@Ag NPs) functionalized MWCNTs hybrid structure as the surface-enhanced Raman scattering (SERS) substrate and pATP molecules as the SERS reporters, which possess a pH-dependent SERS performance. By using MWCNTs as the substrate to be in a state of aggregation, the pH sensing range could be extended to pH 3.0～14.0, which is much wider than that using unaggregated Au@Ag NPs without MWCNTs. Furthermore, the pH-sensitive performance was well retained in living cells with a low cytotoxicity. The developed SERS-active MWCNTs-based nanocomposite is expected to be an efficient intracellular pH sensor for bio-applications.     

Chiral Monolithic Absorbent Constructed by Optically Active Helical‐Substituted Polyacetylene and Graphene Oxide: Preparation and Chiral Absorption Capacity

Chiral monolithic absorbent is successfully constructed for the first time by using optically active helical‐substituted polyacetylene and graphene oxide (GO). The preparative strategy is facile and straightforward, in which chiral‐substituted acetylene monomer (Ma), cross‐linker (Mb), and alkynylated GO (Mc) undergo copolymerization to form the desired monolithic absorbent in quantitative yield. The resulting monoliths are characterized by circular dichroism, UV–vis absorption, scanning electron microscopy (SEM), FT‐IR, Raman, energy‐dispersive spectrometer (EDS), X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET), XPS, and thermogravimetric analysis (TGA) techniques. The polymer chains derived from Ma form chiral helical structures and thus provide optical activity to the monoliths, while GO sheets contribute to the formation of porous structures. The porous structure enables the monolithic absorbents to demonstrate a large swelling ratio in organic solvents, and more remarkably, the helical polymer chains provide optical activity and further enantio‐differentiating absorption ability. The present study establishes an efficient and versatile methodology for preparing novel functional materials, in particular monolithic chiral materials based on substituted polyacetylene and GO.

     

Raman spectroscopy measurement of levofloxacin lactate in blood using an optical fiber nano‐probe

Liquid chromatography and mass spectrometry were time‐consuming and expensive as the main methods for the drug analysis at present, and the samples must be pretreated. The Raman spectroscopy measurement methods were fast and simple, so the Raman spectroscopy methods for the drug analysis were explored in this paper. An optical fiber nano‐probe coated with gold nanoparticles was fabricated and used with surface‐enhanced Raman spectroscopy (SERS) to measure levofloxacin lactate. The resulting SERS spectra of levofloxacin lactate in mouse blood that was detected by the optical fiber nano‐probe clearly showed the characteristic wave numbers of levofloxacin lactate, indicating that optical fiber nano‐probes can be used with spectral techniques to analyze drugs in vitro or potentially even in vivo. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectra of proton order of thin ice Ih film

The polarized Raman spectra of the upper part of a thin ice Ih film were obtained in the range of 150 cm⁻¹ to 3800 cm⁻¹. The spectra showed clear polarization dependence; several new peaks were also observed. The longitudinaloptic–tranverseoptic (LO–TO) splitting of the mode near 220 cm⁻¹ in the translational vibration region was experimentally confirmed at 133 K. The Fermi resonance between the bending overtone (around 3270 cm⁻¹) and symmetry stretching fundamental (around 3350 cm⁻¹) in the stretching vibration region appeared at nearly the same temperature. Results showed that ice XI (i.e. proton‐ordered phase of ice Ih) slowly formed in the upper part of a thin ice Ih film without KOH as the temperature gradually decreased below 133 K. Copyright © 2015 John Wiley & Sons, Ltd.