Manganese(I) poly(mercaptoimidazolyl)borate complexes: spectroscopic and structural characterization of Mn...H-B interactions in solution and in the solid state

The manganese(I) tricarbonyl complexes (Bm(R))Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhBmMe)Mn(CO)3, the first bis(mercaptoimidazolyl)borate derivatives for this metal, have been readily prepared and fully characterized. In particular, the presence of three-center-two-electron Mn...H-B interactions in these species, both in solution and in the solid state, has been investigated using a combination of IR and NMR spectroscopies and, in the case of the methyl-, tert-butyl- and para-tolyl-substituted derivatives, by X-ray crystallography. To complement these synthetic and structural studies, the tris(mercaptoimidazolyl)borate complexes (TmMe)Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhTm(Me))Mn(CO)3, as well as the related pyrazolylbis(mercaptoimidazolyl)borate (pzBmMe)Mn(CO)3, have also been synthesized and characterized by a combination of analytical and spectroscopic techniques.     

The mechanism of formation of amide-based interlocked compounds: prediction of a new rotaxane-forming motif

Molecular modeling of four different reagent systems shows that the (free) energies of supramolecular interactions in the gas phase and in solution can explain the different reaction products (i.e., various sized macrocycles, catenanes, and linear oligomers) that are formed in classic amide-catenane-forming reactions. Self-assembly of the catenanes requires the formation of ordered intertwined chains and is driven by bifurcated hydrogen bonds, with pi stacking only playing a lesser role. The understanding gained from the computational study was used to predict the possibility of a new rotaxane-forming system that does not permit catenane formation. The predictions were confirmed by the successful synthesis and characterization (including X-ray crystallography) of two novel rotaxanes.     

Shuttling through reversible covalent chemistry

The first stimuli-responsive molecular shuttle that functions through reversible C-C bond formation is reported.     

Relaxation and imaging of lithium in vivo

It has recently been demonstrated that NMR imaging can be used to record the distribution of lithium. We now report on the parameters pertinent to this imaging. Specifically, the relaxation of Li in aqueous solution, in agarose gel, and in vivo has been investigated. In the latter case, both the longitudinal and transverse relaxations were biexponential, consistent with the behavior expected for a spin 3/2 quadrupole relaxed nucleus. The overall relaxation rate was quite slow in vivo with T'1 = 3.5 sec and T'1 = 6.6 sec.     

Fluorescent CXCR4 chemokine receptor antagonists: metal activated binding

The copper(II) complex of a novel rhodamine-azamacrocycle conjugate binds to the CXCR4 chemokine receptor and competes effectively against anti-CXCR4 monoclonal antibodies. The copper macrocycle unit adopts a trans-II configuration in the solid state.     

Analysis of polyfluoroalkyl substances and bisphenol A in dried blood spots by liquid chromatography tandem mass spectrometry

Dried blood spots (DBS), collected as part of the newborn screening program (NSP) in the USA, is a valuable resource for studies on environmental chemical exposures and associated health outcomes in newborns. Nevertheless, determination of concentrations of environmental chemicals in DBS requires assays with great sensitivity, as the typical volume of blood available on a DBS with 16-mm diameter disc is approximately 50 μL. In this study, we developed a liquid–liquid extraction and high-performance liquid chromatography/tandem mass spectrometry method for the detection of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and bisphenol A (BPA) in DBS. The method was validated for accuracy, precision, and sensitivity, by spiking of target chemicals at different levels on Whatman 903 filter cards, which is used in the collection of DBS by the NSP. Contamination arising from collection, storage, and handling of DBS is an important issue to be considered in the analysis of trace levels of environmental chemicals in DBS. For the evaluation of the magnitude of background contamination, field blanks were prepared from unspotted portions of DBS filter cards collected by the NSP. The method was applied for the measurement of PFOS, PFOA, and BPA in 192 DBS specimens provided by NSP of New York State. PFOS and PFOA were detected in 100 % of the specimens analyzed. The concentrations of PFOS and PFOA measured in DBS were similar to those reported earlier in the whole blood samples of newborns. BPA was also found in 86 % of the specimens at concentrations ranging from 0.2 to 36 ng/mL (excluding two outliers). Further studies are needed to evaluate the sources of BPA exposures and health outcomes in newborns.