Cephalosporin-3'-diazeniumdiolates: Targeted NO-Donor Prodrugs for Dispersing Bacterial Biofilms

Just say NO to biofilms: NO-donors are used to disperse a bacterial biofilm so that co-administered antibiotics will kill the more susceptible unattached cells. The chemically stable cephalosporin-3'-diazeniumdiolate NO-donor prodrug is activated by bacterial β-lactamases and facilitates this two-step biofilm erradication.     

Steady vortical flow around a finite plate

An explicit solution for a layer of fluid with constant vorticitysurrounding a thin plate of finite length is obtained usingelementary conformal mapping methods. In the limit of largeplate length the behaviour of the solution near the ends ofthe plate tends to that of the previously known solution fora semi-infinite plate. Contour dynamics is used to investigatethe stability of the steady solutions.     

Oxidative coupling of indoles using thallium(III) trifluoroacetate

The oxidative coupling of polysubstituted electron-rich indoles mediated by thallium trifluoroacetate was found to be a facile, clean, and high yielding reaction. Indolic coupling sites were determined by the nature of the substituents present, with dimerisation at the indole 2-position being the dominant outcome. Indoles bearing two potential reaction sites with similar reactivity were additionally found to undergo heterocoupling.     

Reactions of electron-rich indoles with triflic anhydride

The reaction of electron-rich 3-aryl-substituted 4,6-dimethoxyindoles in the presence of base with triflic anhydride results in biaryl coupling, producing both 2,2′- and 2,7′-biindoles. Further, if acetone is present, the corresponding vinyl triflate is formed and subsequent reaction yields the known indolylpyrroloindoles and dimeric spiroindoles. This is the first reported synthesis of these compounds under basic conditions.     

Monitoring the phase evolution in LiCoO2 electrodes during battery cycles using in-situ neutron diffraction technique

LiCoO₂ (LCO) with average particle distribution of 8 μm (LCO-A) and 11 μm (LCO-B) exhibit substantial differences in cycle performance. The half-cells have similar first-cycle discharge capacities of 173 and 175 mAh/g at 0.25 C, but after 100 cycles, the discharge capacities are substantially different, that is, 114 and 141 mAh/g for LCO-A and LCO-B, respectively. Operando neutron powder diffraction of full LCO||Li₄Ti₅O₁₂ batteries show differences in the LCO reaction mechanism underpinning the electrochemical behavior. LCO-A follows a purely solid solution reaction during cycling compared to the solid solution and two-phase reaction mechanism in LCO-B. The absence of the two-phase reaction in LCO-A is consistent with a homogeneous distribution of Li throughout the particle. The two-phase reaction in LCO-B reflects two distinguishable distributions of Li within the particles. The faster capacity decay in LCO-A is correlated to an increase in electrode cracking during battery cycles.     

Quantitative analysis of deuterium using the isotopic effect on quaternary C NMR chemical shifts

Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual ¹H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D₂O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary ¹³C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing ¹³C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve ¹³C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei (¹H, ²H) resolves closely separated quaternary ¹³C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up.     

Chemoselective Thioacetalisation of Aldehydes Catalysed by Fe3+-Montmorillonite #

Aldehydes were cleanly and selectively converted to the corresponding dithioacetals almost quantitatively with catalytic amounts of Fe³⁺-exchanged montmorillonite (Fe³⁺-mont) even in the presence of ketones.