• Winstead Beebe posted an update 21 hours, 46 minutes ago

    Quantitative chirality sensing of terpenes and terpenoids exhibiting a single double bond as the only functional group, such as α-pinene, β-pinene and camphene, or two alkene moieties like limonene, valencene, and β-caryophyllene is among the most difficult molecular recognition tasks. In this work, a fast chiroptical sensing method that accomplishes determination of the enantiomeric excess and overall amount of a large variety of terpenes and terpenoids using readily available phosphine derived late transition metal complexes is presented. The terpene coordination is complete within 10 min and coincides with spontaneous induction of strong CD signals at long wavelengths and distinct UV changes which together allow accurate ee and concentration quantification.The new nanoporous framework [Gd4(di-nitro-BPDC)4(NO2)3(OH)(H2O)5]·(solvent) (I; di-nitro-BPDC2- = 2,2′-dinitrobiphenyl-4,4′-dicarboxylate) has been designed and synthesized through a simple one-pot reaction. In addition to its exceptional thermal and water stabilities, I exhibited multifunctional properties. A sudden CO2 uptake to a maximum of 4.51 mmol g-1 (195 K and 1 bar) with notable selectivity over O2 and N2 (CO2/O2 = 39 at 195 K and 0.10 bar, CO2/N2 = 46 at 195 K and 0.10 bar) and an isosteric adsorption enthalpy of 20.7(4) kJ mol-1 have been revealed. Depending on the temperature and humidity, I also showed distinguished superprotonic conductivities with a maximum value and activation energy of 6.17 × 10-2 S cm-1 (55 °C, 99 RH%, and 1 V AC voltage) and 0.43 eV, respectively. With respect to the linear dependence of conductivities on both temperature (25-55 °C at 99 RH%) and humidity (55-99 RH% at 25 °C), the potential of I in temperature and humidity sensing was evaluated, disclosing an excellent sensing resolution and exceptional accuracy, precision, and repeatability for the measurements.Chloroboron subphthalocyanines (Cl-BsubPc) are robust compounds that can be readily modified at the axial and peripheral positions. Peripherally chlorinated derivatives were recently found to be advantageous regarding integration into organic electronic devices. We now report on the effects of fluorides introduced on both the peripheral and axial positions of BsubPcs. Specific attention on the reduction of these compounds revealed that the much fewer electronegative chlorides still shift the redox potentials as much as fluorides. The main advantage of the fluorinated derivatives was deduced to be their stability, allowing for the spectroscopic characterization of mono-anionic and even bis-anionic subphthalocyanines. This study sets the precedence for further tuning of the electrochemical properties of BsubPcs through molecular design, thus increasing their applicability regarding organic electronic devices that undergo multiple redox cycles during operational lifetime.Atherosclerosis is one of the leading causes of mortality in developed and developing countries. The onset of atherosclerosis development is accompanied by overexpression of several inflammatory chemokines. Neutralization of these chemokines by chemokine-binding agents attenuates atherosclerosis progression. Here, we studied structural binding features of the tick protein Evasin-3 to chemokine (C-X-C motif) ligand 1 (CXCL1). We showed that Evasin-3-bound CXCL1 is unable to activate the CXCR2 receptor, but retains affinity to glycosaminoglycans. This observation was exploited to detect inflammation by visualizing a group of closely related CXC-type chemokines deposited on cell walls in human endothelial cells and murine carotid arteries by a fluorescent Evasin-3 conjugate. This work highlights the applicability of tick-derived chemokine-binding conjugates as a platform for the development of new agents for inflammation imaging.Materials in the paint layers of an early 16th-century painted and glazed terracotta sculpture by Giovanni della Robbia, Pietà, were identified. The presence of the rare lead chloride salts cotunnite (PbCl2) and challacolloite (KPb2Cl5) was confirmed using Raman spectroscopy and electron backscatter diffraction. The well-formed habit of large crystals of challacolloite indicates slow growth from solution. The stability and potential pathways for the in situ formation of lead chloride compounds are discussed. The presence of lead chloride phases in the Pietà indicates the conditions of high chloride ion concentrations (i.e., activities) and/or low pH led to the alteration of the pigment lead white (hydrocerussite, 2PbCO3·Pb(OH)2). This work highlights the role of ion transport in the alteration of materials in cultural heritage objects, emphasizes the importance of considering the role of treatments and environmental factors in changes in materials, and reinforces our awareness of the ongoing chemistry occurring in works of art.Proteome characterization relies heavily on tandem mass spectrometry (MS/MS) and is thus associated with instrumentation complexity, lengthy analysis time, and limited duty cycle. It was always tempting to implement approaches that do not require MS/MS, yet they were constantly failing to achieve a meaningful depth of quantitative proteome coverage within short experimental times, which is particularly important for clinical or biomarker-discovery applications. Here, we report on the first successful attempt to develop a truly MS/MS-free method, DirectMS1, for bottom-up proteomics. The method is compared with the standard MS/MS-based data-dependent acquisition approach for proteome-wide analysis using 5 min LC gradients. Specifically, we demonstrate identification of 1 000 protein groups for a standard HeLa cell line digest. The amount of loaded sample was varied in a range from 1 to 500 ng, and the method demonstrated 10-fold higher sensitivity. Combined with the recently introduced Diffacto approach for relative protein quantification, DirectMS1 outperforms most popular MS/MS-based label-free quantitation approaches because of significantly higher protein sequence coverage.Here, the effect of morphology on the electrocatalytic activity of metal-organic framework (MOF) was investigated. Post synthetic gold (Au) insertion was done into hollow PCN-222 (HPCN-222) and solid PCN-222 (SPCN-222) frameworks by a simple hydrothermal method. read more The crystalline nature, chemical composition, and morphologies of the synthesized MOFs were characterized by PXRD, XPS, and TEM. Electrochemical characterizations were done by cyclic voltammetry and electrochemical impedance spectroscopy. The excellent electrocatalytic activity of highly small-sized Au(0) with the enhancement of electrical conductivity through a hopping mechanism combined with a hollow structure and high surface area in the HPCN-222 MOF hugely alters the electrochemical properties. Overall, a better electrocatalytic surface area, charge transfer coefficient, and catalytic activity were generated at the modified electrode. The hollow structure MOF showed better electrocatalytic activity than solid structured MOF. The AuHPCN-222 modified glassy carbon electrode (AuHPCN-222/GCE) electrochemical sensor was employed for the analytical analysis of estradiol (ED) in an optimum experimental condition.