Measuring salty samples without adducts with MALDI MS

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) has been used for the discovery of hundreds of novel cell to cell signaling peptides. Beyond its advantages of sensitivity and minimal sample preparation requirements, MALDI MS is attractive for biological analyses as high quality mass spectra may be obtained directly from specific locations within prepared tissue sections. However, due to the large quantity of salts present in physiological tissues, these mass spectra often contain many adducts of cationic salts such as sodium and potassium, in addition to the molecular ion [M + H]⁺. To reduce the presence of cation adducts in MALDI mass spectra obtained directly from tissues, we present a methodology that uses a slow condensation procedure to enable the formation of distinct regions of matrix/analyte crystals and cation (salt) crystals. Secondary ion mass spectrometric imaging suggests that the salts and MALDI matrix undergo a mutually exclusive crystallization process that results in the separation of the salts and matrix in the sample.     

Comparison of a range of rhodium-based catalysts for the hydroformylation of selected alkenes

Four rhodium-based catalyst systems 1, 2, 3, and [Rh(OAc)₂]₂/PPh₃ have been used in the hydroformylation of 1-hexene, styrene and some phosphino-, amino- and amido-alkenes. In general the catalysts showed very similar reactivity and selectivity.     

From laser-induced line narrowing to electro- magnetically induced transparency: closed system analysis

The laser-induced line-narrowing effect, discovered more than thirty years ago, can also be applied to recent studies in high resolution spectroscopy based on electromagnetically induced transparency. In this paper we first present a general form of the transmission width of electromagnetically induced transparency in a homogeneously broadened medium. We then analyze a Doppler broadened medium by using a lorentzian function as the atomic velocity distribution. The dependence of the transmission linewidth on the driving field intensity is discussed and compared to the laser-induced line-narrowing effect. This dependence can be characterized by a parameter which can be regarded as “the degree of optical pumping.” Received: 17 December 2001 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. E-mail: hwang.Lee@jpl.nasa.gov RID="**" ID="**"Present address: Jet Propulsion Laboratory, MS 126-347, California Institute of Technology, Pasadena, CA 91109, USA     

Proton magnetic resonance spectra and conformation of some trisubstituted cyclopropane compounds

The n.m.r. spectra of some 1,2,2-trisubstituted cyclopropanes are reported. Coupling constants and chemical shifts of the cyclopropane protons and their dependence on substituent effects are discussed. Conformations of benzylcyclopropane derivatives are investigated by long range magnetic shielding. The concentration dependence of the n.m.r. spectra of some 1,3-diols is explained by inter- and intramolecular hydrogen bonding.     

Experimental analysis of plates using the method of model curing

The method of model curing is applicable to the analysis of plates. When the polymerization process is complete and model is unloaded, the deflection and the birefringence remain permanent. The stereometric method is used for evaluation of bending and torsion moments, and photoelastic method is used as a control method. The example given of the method of curing is a square plate supported at three points and loaded by a concentrated load.     

An integrated quantum chemical and experimental approach for exploring the structures and properties of insensitive munitions interacting with ions in bulk water

Structural Chemistry - Alternatives to legacy munitions and explosives, materials that feature increased stability against external stimuli without compromising their energetic yields are currently...     

Adoption as a social marker: Innovation diffusion with outgroup aversion

Social identities are among the key factors driving behavior in complex societies. Signals of social identity are known to influence individual behaviors in the adoption of innovations. Yet the population-level consequences of identity signaling on the diffusion of innovations are largely unknown. Here we use both analytical and agent-based modeling to consider the spread of a beneficial innovation in a structured population in which there exist two groups who are averse to being mistaken for each other. We investigate the dynamics of adoption and consider the role of structural factors such as demographic skew and communication scale on population-level outcomes. We find that outgroup aversion can lead to adoption being delayed or suppressed in one group, and that population-wide underadoption is common. Comparing the two models, we find that differential adoption can arise due to structural constraints on information flow even in the absence of intrinsic between-group differences in adoption rates. Further, we find that patterns of polarization in adoption at both local and global scales depend on the details of demographic organization and the scale of communication. This research has particular relevance to widely beneficial but identity-relevant products and behaviors, such as green technologies, where overall levels of adoption determine the positive benefits that accrue to society at large.     

NMR Crystallography of an Oxovanadium(V) Complex by an Approach Combining Multinuclear Magic Angle Spinning NMR,DFT, and Spin Dynamics Simulations

Bioinorganic vanadium(V) solids are often challenging for structural analysis. Here, we explore an NMR crystallography approach involving multinuclear ¹³C/⁵¹V solid‐state NMR spectroscopy, density functional theory (DFT), and spin dynamics numerical simulations, for the spectral assignment and the 3D structural analysis of an isotopically unmodified oxovanadium(V) complex, containing 17 crystallographically inequivalent ¹³C sites. In particular, we report the first NMR determination of C–V distances. So far, the NMR observation of ¹³C–⁵¹V proximities has been precluded by the specification of commercial NMR probes, which cannot be tuned simultaneously to the close Larmor frequencies of these isotopes (100.6 and 105.2 MHz for ¹³C and ⁵¹V, respectively, at 9.4 T). By combining DFT calculations and ¹³C–⁵¹V NMR experiments, we propose a complete assignment of the ¹³C spectrum of this oxovanadium(V) complex. Furthermore, we show how ¹³C–⁵¹V distances can be quantitatively estimated.     

First-row transition-metal chloride complexes of the wide bite-angle diphosphine (iPr)DPDBFphos and reactivity studies of monovalent nickel

The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as (iPr)DPDBFphos) has been metalated with transition metal dichlorides of zinc, cobalt, and nickel to yield ((iPr)DPDBFphos)MCl(2) complexes. Within these compounds, the diphosphine (iPr)DPDBFphos adapts a wide range of bite angles (115 to 180°) as determined by X-ray crystallography. A three-coordinate planar Ni(I) species was isolated from the reduction of ((iPr)DPDBFphos)NiCl(2) with KC(8). Low-temperature electron paramagnetic resonance (EPR) measurements of ((iPr)DPDBFphos)NiCl allow the determination of g values (2.09, 2.14, 2.37) and hyperfine coupling constants to two (31)P nuclei, A(iso) = 46 × 10(-4) cm(-1), and one (37)Cl/(35)Cl nucleus, A = (12, 0.7, 35) × 10(-4) cm(-1). Density functional theory (DFT) studies reveal the nature of the magnetic orbital to be d(xy), which has σ-antibonding and π(∥)-antibonding interactions with the phosphorus and chloride atoms, respectively. The monovalent nickel complex reacts with substrates containing C-X bonds; and in the case of vinyl chloride, a Ni(II) vinyl species ((iPr)DPDBFphos)Ni(CH═CH(2))Cl is generated along with the Ni(II) dichloride complex. The monovalent Ni(I) chloride is an active catalyst in the Kumada cross-coupling reaction of vinyl chloride and phenyl Grignard reagent.     

Non-classical hydrogen bonding in [K(1-aza-18-crown-6)]BH4 and its 18-crown-6 counterpart

The extended structures of [K(1-aza-18-crown-6)]BH(4) and its 18-crown-6 analogue exhibits significantly different primary and secondary stabilizing interactions. However, their respective ion pairs display similar cation-to-anion interactions, in spite of the differences in the nature of the crown ether ligand.