Classification of spectroscopically encoded resins by Raman mapping and infrared hyperspectral imaging

Barcoded resins (BCRs) were recently introduced as a potential platform for pre-encoded multiplexed synthesis, screening, and biomedical diagnostics. A key step toward the development of this strategy is the ability to rapidly interrogate and classify the BCRs in a high-throughput, noninvasive manner. Here, we describe a one-step strategy based on Raman mapping and Fourier transform infrared imaging to classify and spatially resolve randomly distributed BCRs. To illustrate this methodology, mixtures of up to 25 different BCRs were imaged and classified with 100% confidence. This strategy can be readily extended to a larger pool of resins, provided each BCR features a unique vibrational fingerprint (spectroscopic barcode). We have also established that reliable single-bead Raman spectra can be recorded in 10 ms, thus confirming that Raman mapping, in particular, could be a very fast method to classify the BCRs.     

Structural characteristics of a 0.23 mole fraction aqueous solution of tetrahydrofuran at 20 degrees C

Hydrogen/deuterium isotopic substitution neutron diffraction techniques were used to measure the structural correlation functions in a 0.23 mole fraction solution of tetrahydrofuran in water at room temperature. Empirical potential structure refinement (EPSR) was used to build a three-dimensional model of the liquid structure that is consistent with the experimental data. Detailed analysis shows a preference for nonpolar interactions between the cyclic ether molecules plus polar interactions between the ether and solvent water and hydrophobic hydration of the nonpolar regions of the solute. The increase in the number of hydrogen-bond-acceptor sites relative to the number of hydrogen-bond-donor sites in this system, compared to the balanced situation that would be found in pure water, has a marked compressive effect on the structure of the solvent. Despite the small size of the solvent water molecules, the 0.23 mole fraction aqueous solution is still found to contain small voids akin to those in pure liquid tetrahydrofuran. In contrast to the positive surface charge of the voids in the pure system, the average void in this aqueous solution is found to have a net negative charge. This is due to contributions from the water oxygen atoms that are negatively polarized by their intramolecular bonding.     

Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes

The spin state in heterobimetallic complexes heavily influences both reactivity and magnetism. Exerting control over spin states in main group-based heterobimetallics requires a different approach as the orbital interactions can differ substantially from that of classic coordination complexes. By deliberately engendering an energetic mismatch within the two metals in a bimetallic complex we can mimic the electronic structure of lanthanides. Towards this end, we report a new family of complexes, [^Ph,MeTpMSnPh₃] where M = Mn (3), Fe (4), Co (5), Ni (6), Zn (7), featuring unsupported bonding between a transition metal and Sn which represent an unusual high spin electronic structure. Analysis of the frontier orbitals reveal the desired orbital mismatch with Sn 5s/5p primarily interacting with 4s/4p M orbitals yielding localized, non-bonding d orbitals. This approach offers a mechanism to design and control spin states in bimetallic complexes.

We report a series of high spin bimetallic transition metal–tin complexes. The unusual high spin configuration in a bimetallic complex is enabled by an energetic mismatch in the orbital energies, leading to lanthanide-like nonbonding interactions.     

Gas chromatographic method for the analysis of allelopathic natural products in rye (Secale cereale L.)

Accurate and reproducible methods for the analysis of plant allelochemicals are a requirement for the study of chemical interactions between plants. This paper describes a method for sample preparation and quantitative analysis of the allelopathic chemical content of rye (Secale cereale L.) using gas chromatography (GC). Sample preparation consists of extraction of freeze-dried rye vegetative tissue with aqueous ethanol followed by partitioning of the allelochemicals into ethyl acetate, evaporation, and derivatization using the trimethylsilylating reagent N-methyl-N-trimethylsilyltrifluoroacetamide. GC analysis of the silylated mixture was performed using flame ionization detection. This method permits analysis of all known rye allelopathic agents including 2,4-dihydroxy-1,4-benzoxazin-3-one, its corresponding glucoside, 2-benzoxazolinone, beta-hydroxybutyric acid, and beta-phenyllactic acid. Identities of all compounds were confirmed by GC/MS analysis.     

Characterisation of models of multicomponent amorphous metals: The radical alternative to the Voronoi polyhedron

A generalisation of the Voronoi polyhedron procedure for examining the detailed local structures in multicomponent metallic glass models is described. The resulting radical plane polyhedra depend upon the relative sizes of the model atoms and form an assembly of polyhedra which completely fill space. Application of the method to two slightly different models of amorphous Pd₄Si illustrates the sensitivity of the technique to changes in local structure, and how such changes in polyhedron topology may relate to the changes in real space The method may be particularly useful in examining local changes on structural relaxation.     

Structures of high and low density amorphous ice by neutron diffraction

Neutron diffraction with isotope substitution is used to determine the structures of high (HDA) and low (LDA) density amorphous ice. Both "phases" are fully hydrogen bonded, tetrahedral networks, with local order similarities between LDA and ice Ih, and HDA and liquid water. Moving from HDA, through liquid water and LDA to ice Ih, the second shell radial order increases at the expense of spatial order. This is linked to a fifth first neighbor "interstitial" that restricts the orientations of first shell waters. This "lynch pin" molecule which keeps the HDA structure intact has implications for the nature of the HDA-LDA transition that bear on the current metastable water debate.     

Solute-solute correlations in aqueous solutions of tetramethylammonium chloride

Neutron diffraction with hydrogen/deuterium isotope substitution on the methyl group hydrogen atoms of the solute is used to investigate the distribution of the tetramethylammonium (TMA) ion, (CH₃)₄N⁺, in aqueous solution of 4·0 molal tetramethylammonium chloride at room temperature. The centre-centre correlation function for TMA ions is calculated from the HH correlation function for the solute by deconvolution of a spherical form factor representing the distribution of methyl hydrogen atoms. The centre-centre function shows a broad distribution of TMA … TMA distances, but indicates that close contacts occur frequently. This suggests that the charge interaction of TMA is not important in determining the distribution and that the TMA ion behaves more like an apolar solute.