Laser Ablation Molecular Isotopic Spectrometry: Parameter influence on boron isotope measurements

Laser Ablation Molecular Isotopic Spectrometry (LAMIS) was recently reported for optical isotopic analysis of condensed samples in ambient air and at ambient pressure. LAMIS utilizes molecular emissions which exhibit larger isotopic spectral shits than in atomic transitions. For boron monoxide ¹⁰BO and ¹¹BO, the isotopic shifts extend from 114 cm⁻¹ (0.74 nm) to 145–238 cm⁻¹ (5–8 nm) at the B²Σ⁺ (v = 0) → X²Σ⁺ (v = 2) and A²Π_i (v = 0) → X²Σ⁺ (v = 3) transitions, respectively. These molecular isotopic shifts are over two orders of magnitude larger than the maximum isotopic shift of approximately 0.6 cm⁻¹ in atomic boron. This paper describes how boron isotope abundance can be quantitatively determined using LAMIS and how atomic, ionic, and molecular optical emission develops in a plasma emanating from laser ablation of solid samples with various boron isotopic composition. We demonstrate that requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric analysis of spectra. Sensitivity can be improved by using a second slightly delayed laser pulse arriving into an expanding plume created by the first ablation pulse.     

Insights into hydrogen bonding and stacking interactions in cellulose

In this quantum chemical study, we explore hydrogen bonding (H-bonding) and stacking interactions in different crystalline cellulose allomorphs; namely, cellulose I(β) and cellulose III(I). We consider a model system representing a cellulose crystalline core made from six cellobiose units arranged in three layers with two chains per layer. We calculate the contributions of intrasheet and intersheet interactions to the structure and stability in both cellulose I(β) and cellulose III(I) crystalline cores. Reference structures for this study were generated from molecular dynamics simulations of water-solvated cellulose I(β) and III(I) fibrils. A systematic analysis of various conformations describing different mutual orientations of cellobiose units is performed using the hybrid density functional theory with the M06-2X with 6-31+G(d,p) basis sets. We dissect the nature of the forces that stabilize the cellulose I(β) and cellulose III(I) crystalline cores and quantify the relative strength of H-bonding and stacking interactions. Our calculations demonstrate that individual H-bonding interactions are stronger in cellulose I(β) than in cellulose III(I); however, the total H-bonding contribution to stabilization is larger in cellulose III(I) because of the highly cooperative nature of the H-bonding network. In addition, we observe a significant contribution from cooperative stacking interactions to the stabilization of cellulose I(β). The theory of atoms-in-molecules (AIM) has been employed to characterize and quantify these intermolecular interactions. AIM analyses highlight the role of nonconventional CH···O H-bonding in the cellulose assemblies. Finally, we calculate molecular electrostatic potential maps for the cellulose allomorphs that capture the differences in chemical reactivity of the systems considered in our study.     

Scope of the inverse electron demand Diels-Alder reactions of 1,2,3-triazine

An examination of the scope of the inverse electron demand Diels-Alder reactions of the parent unsubstituted 1,2,3-triazine is described including the first report of its unique capabilities for participating in previously unexplored [4 + 2] cycloaddition reactions with heterodienophiles.     

CVD graphene electrochemistry: biologically relevant molecules

We investigate the electrochemical properties of CVD grown graphene towards the detection of various biologically prevalent analytes including l-ascorbic acid (AA), dopamine hydrochloride (DA), β-nicotinamide adenine dinucleotide (NADH), uric acid (UA) and epinephrine (EP). We find that the observed electrochemical response of the CVD-graphene towards these select analytes does not originate from the graphene, however, from various other contributions including the presence of 'graphitic islands' on the surface of the CVD-graphene which dominate its electrochemistry. In the systems studied within, it appears at best, CVD-graphene acts akin to that of an edge plane pyrolytic graphite (EPPG) electrode constructed from highly ordered pyrolytic graphite. However, in other cases, the response of the CVD-graphene is worse than that of an EPPG electrode, which is likely due to the low O/C ratio.     

Structural evidence of anomeric effects in the anesthetic isoflurane

The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.     

CVD graphene electrochemistry: the role of graphitic islands

Graphitic islands are shown to dominate the electrochemical response at CVD grown graphene electrodes.     

Controlled electrodeposition of Cu-Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells

The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency.     

Misidentification of major constituents by automatic qualitative energy dispersive X-ray microanalysis: a problem that threatens the credibility of the analytical community.

Automatic qualitative analysis for peak identification is a standard feature of virtually all modern computer-aided analysis software for energy dispersive X-ray spectrometry with electron excitation. Testing of recently installed systems from four different manufacturers has revealed the occasional occurrence of misidentification of peaks of major constituents whose concentrations exceeded 0.1 mass fraction (10 wt%). Test materials where peak identification failures were observed included ZnS, KBr, FeS2, tantalum-niobium alloy, NIST Standard Reference Material 482 (copper-gold alloy), Bi2Te3, uranium-rhodium alloys, platinum-chromium alloy, GaAs, and GaP. These misidentifications of major constituents were exacerbated when the incident beam energy was 10 keV or lower, which restricted or excluded the excitation of the high photon energy K- and L-shell X-rays where multiple peaks, for example, Kalpha (K-L2,3)-Kbeta (K-M2,3); Lalpha (L3-M4,5)-Lbeta (L2-M4)-Lgamma (L2-N4), are well resolved and amenable to identification with high confidence. These misidentifications are so severe as to properly qualify as blunders that present a serious challenge to the credibility of this critical analytical technique. Systematic testing of a peak identification system with a suite of diverse materials can reveal the specific elements and X-ray peaks where failures are likely to occur.