Synthetic approaches to 4,8‐dimethyl‐5′‐(N‐pyridiniummethyl)‐ 4′,5′‐dihydropsoralens and 4,8‐dimethyl‐5′‐ (N‐aminomethyl)‐ 4′,5′‐dihydropsoralens

New synthetic approaches to 4,8‐dimethyl‐5′‐(N‐pyridiniummethyl)‐4′,5′‐dihydropsoralens and 4,8‐dimemyl‐5′‐(N‐aminomethyl)‐4′,5′‐dihydropsoralens are described. The 5′‐halomethyl‐4′,5′‐dihydro‐psoralen precursors are formed by electrophilic ring closures of 4,8‐dimethyl‐6‐allyl‐7‐hydroxycoumarin. The ring‐closure reactions may also be applied to the synthesis of 5′‐halomethyl‐4‐methyl‐4′,5′‐dihydroangelicins. The compounds are potential therapeutic agents for improved psoralen ultraviolet A radiation treatment.     

Exploring the Bile Stress Response of Lactobacillus mucosae LM1 through Exoproteome Analysis

Lactobacillus sp. have long been studied for their great potential in probiotic applications. Recently, proteomics analysis has become a useful tool for studies on potential lactobacilli probiotics. Specifically, proteomics has helped determine and describe the physiological changes that lactic acid bacteria undergo in specific conditions, especially in the host gut. In particular, the extracellular proteome, or exoproteome, of lactobacilli contains proteins specific to host– or environment–microbe interactions. Using gel-free, label-free ultra-high performance liquid chromatography tandem mass spectrometry, we explored the exoproteome of the probiotic candidate Lactobacillus mucosae LM1 subjected to bile treatment, to determine the proteins it may use against bile stress in the gut. Bile stress increased the size of the LM1 exoproteome, secreting ribosomal proteins (50S ribosomal protein L27 and L16) and metabolic proteins (lactate dehydrogenase, phosphoglycerate kinase, glyceraldehyde-3-phosphate dehydrogenase and pyruvate dehydrogenases, among others) that might have moonlighting functions in the LM1 bile stress response. Interestingly, membrane-associated proteins (transporters, peptidase, ligase and cell division protein ftsH) were among the key proteins whose secretion were induced by the LM1 bile stress response. These specific proteins from LM1 exoproteome will be useful in observing the proposed bile response mechanisms via in vitro experiments. Our data also reveal the possible beneficial effects of LM1 to the host gut.     

Cave Plots: A Graphical Technique for Comparing Time Series

Abstract

Cave plots are a good way to compare data from two or more time series, even if the two series are observed at irregular times. Cave plots can show thousands of measurements, but they are readily understood, preserve individual values, highlight short-term, long-term, and periodic fluctuations, and make correlation (or lack of correlation) between two time series apparent. We have used a page of cave plots to show millions of measurements on network reliability and tens of thousands of measurements on air quality. The plots highlight features of the data that warrant a closer look.     

A re-investigation of the Fries rearrangement of 3-chlorophenyl acetate and synthesis of 2-azido-1-(4-(benzyloxy)-2-chlorophenyl)ethanone from 4-bromo-3-chlorophenol

The Fries rearrangement of 3-chlorophenyl acetate provided the expected 4-chloro-2-hydroxy-acetophenone as the major product and 2,4-diacetyl resorcinol and 2-chloro-4-hydroxy-acetophenone as minor products. 4-Benzyloxy-2-chloroacetophenone was prepared by a Heck reaction and then elaborated to 4-benzyloxy-2-chlorophenacyl azide.     

Mesoporous MnCo2O4 with a Flake‐Like Structure as Advanced Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A mesoporous flake‐like manganese‐cobalt composite oxide (MnCo₂O₄) is synthesized successfully through the hydrothermal method. The crystalline phase and morphology of the materials are characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller methods. The flake‐like MnCo₂O₄ is evaluated as the anode material for lithium‐ion batteries. Owing to its mesoporous nature, it exhibits a high reversible capacity of 1066 mA h g^?1, good rate capability, and superior cycling stability. As an electrode material for supercapacitors, the flake‐like MnCo₂O₄ also demonstrates a high supercapacitance of 1487 F g^?1 at a current density of 1 A g^?1, and an exceptional cycling performance over 2000 charge/discharge cycles.     

Cytotoxicity of new 5-phenyl-4,5-dihydro-1,3,4-thiadiazole analogues

A series of 5-phenyl-4,5-dihydro-1,3,4-thiadiazoles were synthesized and their cytotoxicity was examined against four human cancer cell lines, e.g. lung cancer (A549), ovarian cancer (SK-OV-3), skin cancer (SK-MEL-2), and colon cancer (HCT15). The title compounds were synthesized by condensation of thiosemicarbazide with substituted benzaldehydes, followed by cyclization with acetic anhydrides in good yields. Most of the compounds exhibited significant suppressive activity against the growth of all of the cancer cell lines. The 4-hydroxy analogue of 5-phenyl-4,5-dihydro-1,3,4-thiadiazole (2h) was most active in the inhibition of growth of the SK-MEL-2 cell line, with an IC(50) value of 4.27 μg/ml; followed by compound 2a (IC(50) 5.16 μg/ml). The compounds 2j, 2h, and 2b, bearing 3-methoxy-4-hydroxy-, 4-hydroxy- and 4-methyl substituents in the C-5 phenyl ring respectively, exhibited the highest activity against the SK-OV-3 (IC(50) 7.35 μg/ml), HCT15 (IC(50) 8.25 μg/ml) and A549 (IC(50) 9.40 μg/ml) cell lines, respectively. A structure-activity relationship study revealed that an optimal electron density on the C-5 phenyl ring of 1,3,4-thiadiazoles is crucial for their cytotoxic activity against the human cancer cell lines used in the present study.     

A New Hybrid Cmpo/Nopopo Ligand: Synthesis and Selected Lanthanide Coordination Chemistry

Abstract

A two-step synthesis for 2,6-bis[(diphenyl)-N,N-diethylcarbamoylmethylphosphine oxide]pyridine N-oxide (3) from 2,6-bis[(diphenylphosphinoyl)methyl]pyridine is reported along with coordination chemistry with Dy(III) and Yb(III). Crystal structure determinations for the ligand 3_S,S and 1:1 complexes [Dy(3_R,S )(NO₃)₃]·(Me₂CO) and [Yb(3_R,S )(NO₃)₃]·(Me₂CO) are described. In these complexes, the pentafunctional ligand 3 coordinates in a tridentate NOPOPO chelate mode.     

Photoresponsive hyaluronate nanogel as an anticancer drug carrier

In this study, we introduced photolabile 4‐(4‐(1‐hydroxyethyl)‐2‐methoxy‐5‐nitrophenoxy)butyric acid (HMNB) to prepare photoresponsive nanogels. Hyaluronate (HA) grafted with 4‐(4‐(1‐hydroxyethyl)‐2‐methoxy‐5‐nitrophenoxy)butyric acid (HA‐g‐HMNB) was self organized in aqueous solution. Interestingly, HA‐g‐HMNB nanogels exhibited caging and photo‐uncaging properties for an encapsulated antitumor drug. Photoactivation allowed accelerated antitumor drug release from uncaged nanogels. We found a significant improvement in KB tumor‐cell‐killing efficacy when this system was associated with local light irradiation. Copyright © 2013 John Wiley & Sons, Ltd.