Ultra high pressure liquid chromatography for crude plant extract profiling

Ultra high pressure liquid chromatography (UHPLC) systems operating at very high pressures and using sub-2 microm packing columns have allowed a remarkable decrease in analysis time and increase in peak capacity, sensitivity, and reproducibility compared to conventional HPLC. This technology has rapidly been widely accepted by the analytical community and is being gradually applied to various fields of plant analysis such as QC, profiling and fingerprinting, dereplication, and metabolomics. For many applications, an important improvement of the overall performances has been reported. In this review, the basic principles of UHPLC are summarized, and practical information on the type of columns used and phase chemistry available is provided. An overview of the latest applications to natural product analysis in complex mixtures is given, and the potential and limitations as well as some new trends in the development of UHPLC are discussed.     

Sound transmission of cavity walls due to structure borne transmission via point and line connections

The author has published equations for predicting the air borne sound transmission of double leaf cavity walls due to the structure borne sound transmission across the air cavity via (possibly resilient) line connections, but has never published the full derivation of these equations. The author also derived equations for the case when the connections are rigid point connections but has never used them or published them or their derivations. This paper will present the full derivation of the author's theory of the air borne sound transmission of double leaf cavity walls due to the structure borne sound transmission across the air cavity via point or line connections which are modeled as four pole networks. The theoretical results will be compared with experimental results on wooden stud cavity walls from the National Research Council of Canada because the screw spacing is given for these results. This enables connections via studs and screws to be modeled as point connections and avoids the need to make any assumptions about the compliance of the equivalent point or line connections.     

Intense Bessel-like beams arising from pyramid-shaped microtips

We show both numerically and experimentally that intense, narrow, and low-divergence beams of light are produced at the apex of dielectric pyramid-shaped microtips. These beams exhibit a Bessel transverse profile but are narrower than the usual Bessel beam, allowing for a significant enhancement of the light intensity inside the beam. They are generated by axicon-like structures with submicrometric height imprinted in glass by combining optical lithography and chemical etching. The resulting beams are experimentally imaged using fluorescence microscopy, in remarkable agreement with numerical computations.     

Metabolite profiling of plant extracts by ultra-high-pressure liquid chromatography at elevated temperature coupled to time-of-flight mass spectrometry

Detailed metabolite profiling of crude plant extracts, mandatory for both quality control and metabolomics purposes, requires high-resolution separation and sensitive detection with a reasonable sample throughput. In this respect, the use of ultra-high-pressure liquid chromatography (UHPLC) working at high temperature (HT) and coupled to time-of-flight mass spectrometry (TOF-MS) was evaluated in the present study in terms of achievable peak capacities for given analysis times. Prior to the analysis of complex mixtures, the effects of TOF-MS detection on peak capacity were evaluated, and a loss of 15–30% compared to UV was observed due to the additional band broadening generated by this detector. Extracts from a model plant Arabidopsis thaliana and from a widely used phytochemical preparation Ginkgo biloba, as well as a standard mixture of representative natural products (NPs), have been analyzed. As expected from the theory, the increase in mobile phase temperature of up to 90 °C for the profiling of extracts containing metabolites spread over a large polarity range (e.g., Arabidopsis thaliana) generated similar peak capacities to those obtained at room temperature, but with a 2- to 3-fold reduction in analysis time, demonstrating the power of this approach for such applications. On the other hand, for the analysis of more polar extracts (e.g., Ginkgo biloba), the use of higher temperature was not beneficial, as it induced a significant decrease in retention, and thus resolving power, because of the increase in elution strength. The use of HT-UHPLC–TOF-MS raised the question of NP stability under high temperature conditions. This work demonstrated that no apparent degradation was evidenced at high temperature for a representative mixture of NPs and also for the different metabolites detected in the selected plant extracts.     

Importance of the Position of the Chromophore Group on the Dissociation Process of Light Sensitive Alkoxyamines

New photosensitive alkoxyamines have been designed using molecular orbital calculations to improve the selective C O versus N O cleavage. The targeted light‐sensitive alkoxyamine is synthesized in one step and its reactivity under UV has been investigated using both ESR and LFP. The ability of this alkoxyamine to control the photopolymerization of n‐butyl acrylate is evidenced through a process called nitroxide‐mediated photopolymerization NMP². The selected alkoxyamine is finally used to prepare covalently bonded multilayered micropatterns. This original application highlights the high potential of this technique for some specific applications that require spatial control.

     

Adsorption and recovery issues of recombinant monoclonal antibodies in reversed‐phase liquid chromatography†

The poor recovery of large biomolecules is a well‐known issue in reversed‐phase liquid chromatography. Several papers have reported this problem, but the reasons behind this behavior are not yet fully understood. In the present study, state‐of‐the‐art reversed‐phase wide‐pore stationary phases were used to evaluate the adsorption of therapeutic monoclonal antibodies. These biomolecules possess molar mass of approximately 150 000 g/mol and isoelectric points between 6.6 and 9.3. Two types of stationary phases were tested, the Phenomenex Aeris Widepore (silica based), with 3.6 μm superficially porous particles, and the Waters Acquity BEH300 (ethylene‐bridged hybrid), with 1.7 μm fully porous particles. A systematic investigation was carried out using 11 immunoglobulin G1, G2, and G4 antibodies, namely, panitumumab, natalizumab, cetuximab, bevacizumab, trastuzumab, rituximab, palivizumab, belimumab, adalimumab, denosumab, and ofatumumab. All are approved by the Food and Drug Administration and the European Medicines Agency in various therapeutic indications and are considered as reference antibodies. Several test proteins, such as human serum albumin, transferrin, apoferritin, ovalbumin, and others, possessing a molar mass between 42 000 and 443 000 g/mol were also evaluated to draw reliable conclusions. The purpose of this study was to find a correlation between the adsorption of monoclonal antibodies and their physicochemical properties. Therefore, the impact of isoelectric point, molar mass, protein glycosylation, and hydrophobicity was investigated. The adsorption of intact antibodies on the stationary phase was significantly higher than that of proteins of similar size, isoelectric point, or hydrophobicity. The present study also demonstrates the unique behavior of monoclonal antibodies, contributing some unwanted and unpredictable strong secondary interactions.     

An asymptotic solution of an initial value problem for a non-linear viscoelastic rod

Stress wave propagation in a one-dimensional materai, described by the non-linear constitutive law

$\text{?σ}\text{?t}\text{? E}\text{?ε}\text{?t}\text{+ k[σ ? E'g3 + βε}{}^2\text{] = 0}$

, is analyzed by a two-time variable perturbation method. Secular terms are “cast out” by employing special orthogonality conditions. The resulting expansion reveals a “mode coupling”, due to the non-linearity, and displays the significance of the three parameters present in the constitutive law. Numerical values for the parameters are assumed and the resulting displacements computed.     

The influence of promoters and poisons on carbon monoxide adsorption on Rh(100): a DFT study.

Density functional theory calculations were performed to determine the pairwise lateral interaction energies between carbon monoxide and coadsorbed elements from the first three rows of the periodic table on a Rh(100) surface. The atoms were placed in a c(2x2) arrangement of fourfold hollow sites and the carbon monoxide probe molecule in a p(2x2) arrangement, so that each CO molecule had four atoms as nearest neighbours. The alkali atoms show an attractive interaction with CO while the other atoms show a repulsive interaction. For second-row elements the maximum repulsion is at nitrogen and for third-row elements at sulphur. Attempts to correlate the interaction energies with properties of the system, such as electronegativity, distances, or change in work function, failed, which implies that each combination of adsorbates needs to be calculated separately.     

A Rhodium Nanoparticle–Lewis Acidic Ionic Liquid Catalyst for the Chemoselective Reduction of Heteroarenes

We describe a catalytic system composed of rhodium nanoparticles immobilized in a Lewis acidic ionic liquid. The combined system catalyzes the hydrogenation of quinolines, pyridines, benzofurans, and furan to access the corresponding heterocycles, important molecules present in fine chemicals, agrochemicals, and pharmaceuticals. The catalyst is highly selective, acting only on the heteroaromatic ring, and not interfering with other reducible functional groups.