Photografting as a versatile,localizable, and single‐step surface functionalization of silica‐based monoliths dedicated to microscale separation techniques

In this work, we developed a surface functionalization way of silica monoliths with a rapid, simple, versatile, and localizable photografting step. The elaboration of a photoreactive layer at the surface of monoliths was first optimized. The functionalization with [γ‐(methacryloyloxy)propyl]trimethoxysilane at 80°C in a hydro‐organic solution containing triethylamine as catalyst allows reachng the highest density of methacrylate photoactive moieties on silica surfaces. These methacrylate reactive surfaces were subsequently photografted within few minutes with acrylate monomers bearing alkyl chains (C₁₂ and C₁₈). The photografting efficiency was determined by monitoring the retentive properties of monoliths in the RP mode. The retention factors are of the same order of magnitude as highly retentive columns obtained by modification of silica surface with long‐alkyl chain silanes or by thermal polymerization of long‐alkyl chain monomers. It was also verified that such grafting neither impaired the efficiency of the monolithic stationary phase (H_min = 6–8 μm in nano‐LC) nor its permeability (about 6 × 10^?14 m²). Further, it was also demonstrated that photografting is localizable in nonmasked defined areas. Results obtained in anion‐exchange chromatography after photopolymerization of [2‐(methacryloyloxy)ethyl]trimethylammonium chloride are presented as well to demonstrate the versatility of the developed approach.     

DIC Challenge 2.0: Developing Images and Guidelines for Evaluating Accuracy and Resolution of 2D Analyses

Experimental Mechanics - The DIC Challenge 2.0 follows on from the work accomplished in the first Digital Image Correlation (DIC) Challenge Reu et al. (Experimental Mechanics 58(7):1067, 1). The...     

Spatial DIC Errors due to Pattern-Induced Bias and Grey Level Discretization

Digital image correlation (DIC) is an optical metrology method widely used in experimental mechanics for full-field shape, displacement and strain measurements. The required strain resolution for engineering applications of interest mandates DIC to have a high image displacement matching accuracy, on the order of 1/100th of a pixel, which necessitates an understanding of DIC errors. In this paper, we examine two spatial bias terms that have been almost completely overlooked. They cause a persistent offset in the matching of image intensities and thus corrupt DIC results. We name them pattern-induced bias (PIB), and intensity discretization bias (IDB). We show that the PIB error occurs in the presence of an undermatched shape function and is primarily dictated by the underlying intensity pattern for a fixed displacement field and DIC settings. The IDB error is due to the quantization of the gray level intensity values in the digital camera. In this paper we demonstrate these errors and quantify their magnitudes both experimentally and with synthetic images.

     

Retention of β blockers on native titania stationary phase

In recent years, metal oxides such as titania have been commercially available as chromatographic beds that can potentially be used to achieve novel separations of polar compounds. For example β blockers, which are more often encountered in environmental sciences, have a wide range of polarity, and their basic character leads to difficult sample treatment and separation on conventional silica‐based sorbents. The contribution of titania to the selective analysis of nine β blockers was evaluated in terms of retention mechanisms observed in hydrophilic interaction LC using acetonitrile/water mobile phases with various additives. The mobile phase additives enabled to control the β blocker charge as well as the titania surface charge. Depending on their respective ionic state, various retention mechanisms were identified at low water contents (<40%), including mainly adsorption mixed with hydrophilic interaction LC partition, ion exchange and ion exclusion. An unexpected retention was also observed for high water content and high pH, changing the selectivity of the support.     

Structure and Biosynthesis of Crocagins: Polycyclic Posttranslationally Modified Ribosomal Peptides from Chondromyces crocatus

Secondary metabolome mining efforts in the myxobacterial multiproducer of natural products, Chondromyces crocatus Cm c5, resulted in the isolation and structure elucidation of crocagins, which are novel polycyclic peptides containing a tetrahydropyrrolo[2,3-b]indole core. The gene cluster was identified through an approach combining genome analysis, targeted gene inactivation in the producer, and in vitro experiments. Based on our findings, we developed a biosynthetic scheme for crocagin biosynthesis. These natural products are formed from the three C-terminal amino acids of a precursor peptide and thus belong to a novel class of ribosomally synthesized and post-translationally modified peptides (RiPPs). We demonstrate that crocagin A binds to the carbon storage regulator protein CsrA, thereby inhibiting the ability of CsrA to bind to its cognate RNA target.     

Total microcystins analysis in water using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry

A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (<15 s sample⁻¹). Several oxidation and LDTD parameters were optimized to improve recoveries and signal intensity. MCs oxidation recovery yield was 103%, showing a complete reaction. Internal calibration with standard addition was achieved with the use of 4-phenylbutyric acid (4-PB) as internal standard and showed good linearity (R² > 0.999). Limits of detection and quantification were 0.2 and 0.9 μg L⁻¹, respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 μg L⁻¹ for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices.     

The He(I) photoelectron spectra of BrF and IF

The vacuum ultraviolet photoelectron spectra of BrF (X¹Σ⁺) and IF (X¹ Σ⁺) have been recorded and interpreted with the aid of both MS — Xα — SCF calculations and ab initio calculations. For both BrF and IF the first band is split by spin—orbit coupling into two components corresponding to ionization to the X²Π$\text{3}\text{2}$ Phytochemistry and X²Π$\text{1}\text{2}$ ionic states. Estimates of re, ?we and De for these states have been made.     

KAM-tori near an analytic elliptic fixed point

We study the accumulation of an elliptic fixed point of a real analytic Hamiltonian by quasi-periodic invariant tori. We show that a fixed point with Diophantine frequency vector ω ₀ is always accumulated by invariant complex analytic KAM-tori. Indeed, the following alternative holds: If the Birkhoff normal form of the Hamiltonian at the invariant point satisfies a Rüssmann transversality condition, the fixed point is accumulated by real analytic KAM-tori which cover positive Lebesgue measure in the phase space (in this part it suffices to assume that ω ₀ has rationally independent coordinates). If the Birkhoff normal form is degenerate, there exists an analytic subvariety of complex dimension at least d + 1 passing through 0 that is foliated by complex analytic KAM-tori with frequency ω ₀. This is an extension of previous results obtained in [1] to the case of an elliptic fixed point.