Online comprehensive two-dimensional liquid chromatography (LC × LC) offers ways to achieve high-performance separations in terms of peak capacity (exceeding 1000) and additional selectivity to ...realize applications that cannot be addressed with one-dimensional chromatography (1D-LC). However, the greater resolving power of LC × LC comes at the price of higher dilutions (thus, reduced sensitivity) and, often, long analysis times (>100 min). The need to preserve the separation attained in the first dimension (1D) causes greater dilution for LC × LC, in comparison with 1D-LC, and long analysis times to sample the 1D with an adequate number of second dimension separations. A way to significantly reduce these downsides is to introduce a concentration step between the two chromatographic dimensions. In this work we present a possible active-modulation approach to concentrate the fractions of 1D effluent. A typical LC × LC system is used with the addition of a dilution flow to decrease the strength of the 1D effluent and a modulation unit that uses trap columns. The potential of this approach is demonstrated for the separation of tristyrylphenol ethoxylate phosphate surfactants, using a combination of hydrophilic interaction and reversed-phase liquid chromatography. The modified LC × LC system enabled us to halve the analysis time necessary to obtain a similar degree of separation efficiency with respect to UHPLC based LC × LC and of 5 times with respect to HPLC instrumentation (40 compared with 80 and 200 min, respectively), while at the same time reducing dilution (DF of 142, 299, and 1529, respectively) and solvent consumption per analysis (78, 120, and 800 mL, respectively).
Online comprehensive two‐dimensional liquid chromatography has become an attractive option for the analysis of complex nonvolatile samples found in various fields (e.g. environmental studies, food, ...life, and polymer sciences). Two‐dimensional liquid chromatography complements the highly popular hyphenated systems that combine liquid chromatography with mass spectrometry. Two‐dimensional liquid chromatography is also applied to the analysis of samples that are not compatible with mass spectrometry (e.g. high‐molecular‐weight polymers), providing important information on the distribution of the sample components along chemical dimensions (molecular weight, charge, lipophilicity, stereochemistry, etc.). Also, in comparison with conventional one‐dimensional liquid chromatography, two‐dimensional liquid chromatography provides a greater separation power (peak capacity). Because of the additional selectivity and higher peak capacity, the combination of two‐dimensional liquid chromatography with mass spectrometry allows for simpler mixtures of compounds to be introduced in the ion source at any given time, improving quantitative analysis by reducing matrix effects. In this review, we summarize the rationale and principles of two‐dimensional liquid chromatography experiments, describe advantages and disadvantages of combining different selectivities and discuss strategies to improve the quality of two‐dimensional liquid chromatography separations.
SARS-CoV-2 cellular infection is mediated by the heavily glycosylated spike protein. Recombinant versions of the spike protein and the receptor-binding domain (RBD) are necessary for seropositivity ...assays and can potentially serve as vaccines against viral infection. RBD plays key roles in the spike protein’s structure and function, and thus, comprehensive characterization of recombinant RBD is critically important for biopharmaceutical applications. Liquid chromatography coupled to mass spectrometry has been widely used to characterize post-translational modifications in proteins, including glycosylation. Most studies of RBDs were performed at the proteolytic peptide (bottom-up proteomics) or released glycan level because of the technical challenges in resolving highly heterogeneous glycans at the intact protein level. Herein, we evaluated several online separation techniques: (1) C2 reverse-phase liquid chromatography (RPLC), (2) capillary zone electrophoresis (CZE), and (3) acrylamide-based monolithic hydrophilic interaction chromatography (HILIC) to separate intact recombinant RBDs with varying combinations of glycosylations (glycoforms) for top-down mass spectrometry (MS). Within the conditions we explored, the HILIC method was superior to RPLC and CZE at separating RBD glycoforms, which differ significantly in neutral glycan groups. In addition, our top-down analysis readily captured unexpected modifications (e.g., cysteinylation and N-terminal sequence variation) and low abundance, heavily glycosylated proteoforms that may be missed by using glycopeptide data alone. The HILIC top-down MS platform holds great potential in resolving heterogeneous glycoproteins for facile comparison of biosimilars in quality control applications.
In this paper we extend some recent results on an operatorial approach to the description of alliances between political parties interacting among themselves and with a basin of electors. In ...particular, we propose and compare three different models, deducing the dynamics of their related decision functions, i.e. the attitude of each party to form or not an alliance. In the first model the interactions between each party and their electors are considered. We show that these interactions drive the decision functions toward certain asymptotic values depending on the electors only: this is the perfect party, which behaves following the electors’ suggestions. The second model is an extension of the first one in which we include a rule which modifies the status of the electors, and of the decision functions as a consequence, at some specific time step. In the third model we neglect the interactions with the electors while we consider cubic and quartic interactions between the parties and we show that we get (slightly oscillating) asymptotic values for the decision functions, close to their initial values. This is the real party, which does not listen to the electors. Several explicit situations are considered in details and numerical results are also shown.
•We show how some operatorial tools can be used in the analysis of social systems.•We propose a comparison between three different models, and we consider several explicit examples.•We discuss the role of a “rule” acting on the system as a non-Hamiltonian term.
Trifluoroacetic acid (TFA) is commonly used as mobile phase additive to improve retention and peak shape characteristics in hydrophilic interaction liquid chromatography (HILIC) of intact proteins. ...However, when using electrospray ionization-mass spectrometry (ESI-MS) detection, TFA may cause ionization suppression and adduct formation, leading to reduced analyte sensitivity. To address this, we describe a membrane-based microfluidic chip with multiple parallel channels for the selective post-column removal of TFA anions from HILIC. An anion-exchange membrane was used to physically separate the column effluent from a stripper flow solution comprising acetonitrile, formic acid, and propionic acid. The exchange of ions allowed the post-column removal of TFA used during HILIC separation of model proteins. The multichannel design of the device allows the use of flow rates of 0.2 mL/min without the need for a flow splitter, using mobile phases containing 0.1% TFA (13 mM). Separation selectivity and efficiency were maintained (with minor band broadening effects) while increasing the signal intensity and peak areas by improving ionization and reducing TFA adduct formation.
Graphical abstract
In this paper, we show that the position and the derivative operators,
q
^
and
D
^
, can be treated as ladder operators connecting various vectors of two biorthonormal families,
F
φ
and
F
ψ
. In ...particular, the vectors in
F
φ
are essentially monomials in
x
,
x
k
, while those in
F
ψ
are weak derivatives of the Dirac delta distribution,
δ
(
m
)
(
x
)
, times some normalization factor. We also show how bi-coherent states can be constructed for these
q
^
and
D
^
, both as convergent series of elements of
F
φ
and
F
ψ
, or using two different displacement-like operators acting on the two vacua of the framework. Our approach generalizes well- known results for ordinary coherent states.
Dynamics for a quantum parliament Bagarello, F.; Gargano, F.
Studies in applied mathematics (Cambridge),
20/May , Volume:
150, Issue:
4
Journal Article
Peer reviewed
Open access
In this paper, we propose a dynamical approach based on the Gorini–Kossakowski–Sudarshan–Lindblad equation for a problem of decision making. More specifically, we consider what was recently called a ...quantum parliament, asked to approve or not a certain law, and we propose a model of the connections between the various members of the parliament, proposing in particular some special form of the interactions giving rise to a collaborative or noncollaborative behavior.
We constructed a high-performance biosensor for detecting uric acid by immobilizing an engineered urate oxidase on gold nanoparticles deposited on a carbon-glass electrode. This biosensor showed a ...low limit-of-detection (9.16 nM), a high sensitivity (14 μA/μM), a wide range of linearity (50 nM-1 mM), and more than 28 days lifetime.
Abstract
All known small solar system bodies have diameters between a few meters and a few thousands of kilometers. Based on the collisional evolution of solar system bodies, a larger number of ...asteroids with diameters down to ∼2 m is thought to exist. As all solar system bodies, small bodies can be passive sources of high-energy gamma-rays, produced by the interaction of energetic cosmic rays impinging on their surfaces. Since the majority of known asteroids are in orbits between Mars and Jupiter (in a region known as the Main Belt), we expect them to produce a diffuse emission close to the ecliptic plane. In this work, we have studied the gamma-ray emission coming from the ecliptic using the data collected by the Large Area Telescope (LAT) onboard the Fermi satellite. We have fit the results with simulations of the gamma-ray intensity at the source level (calculated with the software
FLUKA
) to constrain the small solar system bodies population. Finally, we have proposed a model describing the distribution of asteroid sizes and we have used the LAT data to constrain the gamma-ray emission expected from this model and, in turn, on the model itself.
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