Dissociation Mode Research Articles

Operative slip systems and their critical resolved shear stresses in η-Fe2Al5 investigated by micropillar compression at room temperature

The plastic deformation behavior of single crystals of orthorhombic η-Fe2Al5 has been investigated by micropillar compression at room temperature as a function of crystal orientation and specimen size. Plastic flow is observed even at room temperature by the operation of six slip systems; (001)<010>, (001)<110>, (001)<130>, {22‾3}<110>, {311}<1‾03> and {301}<1‾03>. The CRSS values for the six identified slip systems are very high all in the range of 1.1∼1.5 GPa and do not vary much with specimen size. In the middle of the stereographic projection, the (001)<010>, (001)<110>, (001)<130> and {22‾3}[110] slip systems operate according to the relative Schmid factors with the similar CRSS values in the range of 1.08∼1.23 GPa. In orientations close to [001], the {311}<1‾03> slip system as well as the {301}<1‾03> slip system operate with a much higher CRSS values around 1.5 GPa, producing wavy slip traces due to the occurrence of frequent cross-slip among these slip planes. In orientations close to the [100]-[110]-[010] symmetry line, on the other hand, premature failure occurs without the operation of any slip systems, although, the Schmidt factor-wise, the {311}<1‾03> and {301}<1‾03> slip systems could operate. The selection of slip systems, their CRSS values and the possible dislocation dissociation modes are discussed based on the overlapped atomic volume that occurs during shear along the slip direction on the slip plane, taking into account the partial occupancies of Al atoms in the linear atomic chain along the orthorhombic c-axis direction.

Numerical characterization of capacitively coupled CF4 plasmas modulated by anion beam injection

In the study of electronegative CF4 capacitively coupled plasmas (CCP), plasma modulation is typically achieved by varying parameters such as pressure and voltage. In this work, the particle-in-cell/Monte Carlo (PIC/MC) method is used to simulate modulation of CF4 CCP with injection of anions (F−) ion beam (FB). The results demonstrate that FB injection effectively enhances the dissociation collision process between F− ions and neutral molecules, thus altering the densities of electrons and ions. An effective modulation of the characteristic parameters of the plasma of CF4 can be achieved by controlling the current and energy of FB. Particularly noteworthy is the transition of the heating mode from the DA mode to the dissociation mode as the FB current increases to 0.038 A (energy fixed at 10 keV) or when the FB energy exceeds 10 keV (current fixed on 0.038 A). This transition is attributed to the generation of a substantial number of electrons through dissociative collisions. This approach provides insight into the controlled modulation of plasma characteristics in CF4 CCP, offering potential applications in various plasma-based technologies.

Exploring hydrogen binding and activation on transition metal-modified circumcoronene

AbstractGraphene-based materials modified with transition metals, and their potential utilization as hydrogen storage devices, are extensively studied in the last decades. Despite this widespread interest, a comprehensive understanding of the intricate interplay between graphene-based transition metal systems and H2 molecules remains incomplete. Beyond fundamental H2 adsorption, the activation of H2 molecule, crucial for catalytic reactions and hydrogenation processes, may occur on the transition metal center. In this study, binding modes of H2 molecules on the circumcoronene (CC) decorated with Cr or Fe atoms are investigated using the DFT methods. Side-on (η2-dihydrogen bond), end-on and dissociation modes of H2 binding are explored for high (HS) and low (LS) spin states. Spin state energetics, reaction energies, QTAIM and DOS analysis are considered. Our findings revealed that CC decorated with Cr (CC-Cr) emerges as a promising material for H2 storage, with the capacity to store up to three H2 molecules on a single Cr atom. End-on interaction in HS is preferred for the first two H2 molecules bound to CC-Cr, while the side-on LS is favored for three H2 molecules. In contrast, CC decorated with Fe (CC-Fe) demonstrates the capability to activate H2 through H–H bond cleavage, a process unaffected by the presence of other H2 molecules in the vicinity of the Fe atom, exclusively favoring the HS state. In summary, our study sheds light on the intriguing binding and activation properties of H2 molecules on graphene-based transition metal systems, offering valuable insights into their potential applications in hydrogen storage and catalysis. Graphical abstract

Enhancing Metabolome Annotation by Electron Impact Excitation of Ions from Organics-Molecular Networking.

Liquid chromatography-high-resolution mass spectrometry (LC-HRMS) is widely used in untargeted metabolomics, but large-scale and high-accuracy metabolite annotation remains a challenge due to the complex nature of biological samples. Recently introduced electron impact excitation of ions from organics (EIEIO) fragmentation can generate information-rich fragment ions. However, effective utilization of EIEIO tandem mass spectrometry (MS/MS) is hindered by the lack of reference spectral databases. Molecular networking (MN) shows great promise in large-scale metabolome annotation, but enhancing the correlation between spectral and structural similarity is essential to fully exploring the benefits of MN annotation. In this study, a novel approach was proposed to enhance metabolite annotation in untargeted metabolomics using EIEIO and MN. MS/MS spectra were acquired in EIEIO and collision-induced dissociation (CID) modes for over 400 reference metabolites. The study revealed a stronger correlation between the EIEIO spectra and metabolite structure. Moreover, the EIEIO spectral network outperformed the CID spectral network in capturing structural analogues. The annotation performance of the structural similarity network for untargeted LC-MS/MS was evaluated. For the spiked NIST SRM 1950 human plasma, the annotation coverage and accuracy were 72.94 and 74.19%, respectively. A total of 2337 metabolite features were successfully annotated in NIST SRM 1950 human plasma, which was twice that of LC-CID MS/MS. Finally, the developed method was applied to investigate prostate cancer. A total of 87 significantly differential metabolites were annotated. This study combining EIEIO and MN makes a valuable contribution to improving metabolome annotation.

Characterizations and molecular docking mechanism of the interactions between peptide FDGDF (Phe-Asp-Gly-Asp-Phe) and SOD enzyme

In this study, we investigated the antioxidant properties of dry-cured beef crude peptide (BPH) at different storage periods. The combination characteristics of different concentrations of Phe-Asp-Gly-Asp-Phe (FDGDF) and superoxide dismutase (SOD) at different temperatures were analyzed by ultraviolet–visible spectroscopy, fluorescence spectroscopy, and FT-IR spectroscopy, combined with the detection of a SOD activity detection box. It was found that FDGDF could improve the activity of SOD by changing its secondary structure. Bonds were formed at O32/O40/O52 using quantum chemical simulation calculations, and the Fukui index was higher than that of most atoms, indicating that these atoms were more likely to participate in the reaction. SPR biological force analysis showed that FDGDF and SOD were in a fast binding and dissociation mode. This study revealed the theoretical basis for studying the antioxidant mechanism of dry-cured beef and provided ideas for developing new dry-cured beef products.

Dissociation Mode of the O-H Bond in Betanidin, pKa-Clusterization Prediction, and Molecular Interactions via Shape Theory and DFT Methods.

Betanidin (Bd) is a nitrogenous metabolite with significant bioactive potential influenced by pH. Its free radical scavenging activity and deprotonation pathway are crucial to studying its physicochemical properties. Motivated by the published discrepancies about the best deprotonation routes in Bd, this work explores all possible pathways for proton extractions on that molecule, by using the direct approach method based on pKa. The complete space of exploration is supported by a linear relation with constant slope, where the pKa is written in terms of the associated deprotonated molecule energy. The deprotonation rounds 1, …, 6 define groups of parallel linear models with constant slope. The intercepts of the models just depend on the protonated energy for each round, and then the pKa can be trivially ordered and explained by the energy. We use the direct approximation method to obtain the value of pKa. We predict all possible outcomes based on a linear model of the energy and some related verified assumptions. We also include a new measure of similarity or dissimilarity between the protonated and deprotonated molecules, via a geometric-chemical descriptor called the Riemann-Mulliken distance (RMD). The RMD considers the cartesian coordinates of the atoms, the atomic mass, and the Mulliken charges. After exploring the complete set of permutations, we show that the successive deprotonation process does not inherit the local energy minimum and that the commutativity of the paths does not hold either. The resulting clusterization of pKa can be explained by the local acid and basic groups of the BD, and the successive deprotonation can be predicted by using the chemical explained linear models, which can avoid unnecessary optimizations. Another part of the research uses our own algorithm based on shape theory to determine the protein's active site automatically, and molecular dynamics confirmed the results of the molecular docking of Bd in protonated and anionic form with the enzyme aldose reductase (AR). Also, we calculate the descriptors associated with the SET and SPLET mechanisms.

Comprehensive effects of heat and flow on the methane hydrate dissociation in porous media

The dissociation of methane hydrate in porous media is a heat flow coupling process. In this paper, we established a heat flow coupling algorithm for hydrate dissociation. A core-scale hydrate dissociation model was established and was verified against a laboratory dissociation experiment. The evolutions of the key characteristics, such as the temperature, the energy, and the hydrate/ice saturations, were analyzed. The effects of heat conductivity and permeability on dissociation characteristics and gas production rate were studied. It is found that there are three different modes under the coordinate system of heat conductivity and the permeability of porous media. In the flow-controlling mode, the rate of hydrate dissociation is mainly related to the flow resistance. In the heat-controlling mode, the rate of hydrate dissociation is mainly related to heat supply. In the heat flow-coupling mode, both the increase in the permeability and the heat supply have positive effects on the increase in the hydrate dissociation rate. In addition, there are different hydrate dissociation front expanding characteristics for the different modes. This analysis of the dissociation mode improves the understanding of events associated with the hydrate dissociation process.

Deep Insights into Complicated Superdislocation Dissociation and Core Properties of Dislocation in L1 2 ‐Al 3 RE Compounds: A Comprehensive First‐Principles Study

The complicated superdislocation dissociation, dislocation core properties, and slip mechanism of L12 structural alloys have been controversial. Herein, the generalized stacking-fault energy surfaces (γ-surfaces) of the {001}, {110}, and {111} planes in L12-Al3RE (RE = Er, Tm, Yb, Lu) compounds are first calculated according to ab initio density functional theory. Based on the γ-surfaces, the superdislocation dissociation modes are preliminarily estimated using the unstable and stable stacking-fault energies and their ratio. The result shows that the possible type of dissociations cannot be determined just from these ratios. Then, the 2D Peierls–Nabarro (PN) model is applied to simulate the ⟨110⟩{111} superdislocation dissociation configuration evolution in L12-Al3RE, and the complete dislocation properties, including the dissociation width, the dislocation movement, and the Peierls energy and stress, are also investigated. The present study indicates that the combination of the γ-surface and the 2D PN model can comprehensively elucidate the superdislocation properties and deformation mechanisms of L12 structural alloys.

Novel Real-Time Library Search Driven Data Acquisition Strategy for Identification and Characterization of Metabolites.

Structural characterization of novel metabolites in drug discovery or metabolomics is one of the most challenging tasks. Multilevel fragmentation (MSn) based approaches combined with various dissociation modes are frequently utilized for facilitating structure assignment of unknown compounds. As each of the MS precursors undergoes MSn, the instrument cycle time can limit the total number of precursors analyzed in a single LC run for complex samples. This necessitates splitting data acquisition into several analyses to target lower concentration analytes in successive experiments. Here we present a new LC/MS data acquisition strategy, termed Met-IQ, where the decision to perform an MSn acquisition is automatically made in real time based on the similarity between the experimental MS2 spectrum and a spectrum in a reference spectral library for the known compounds of interest. If similarity to a spectrum in the library is found, the instrument performs a decision-dependent event, such as an MS3 spectrum. Compared to an intensity-based, data-dependent MSn experiment, only a limited number of MS3 are triggered using Met-IQ, increasing the overall MS2 instrument sampling rate. We applied this strategy to an Amprenavir sample incubated with human liver microsomes. The number of MS2 spectra increased 2-fold compared to a data dependent experiment where MS3 was triggered for each precursor, resulting in identification of 14-34% more unique potential metabolites. Furthermore, the MS2 fragments were selected to focus likely sources of useful structural information, specifically higher mass fragments to maximize acquisition of MS3 data relevant for structure assignment. The described Met-IQ strategy is not limited to metabolism experiments and can be applied to analytical samples where the detection of unknown compounds structurally related to a known compound(s) is sought.

Recent Progress in Pd-Based Nanocatalysts for Selective Hydrogenation.

Selective hydrogenation plays an important role in the chemical industry and has a wide range of applications, including the production of fine chemicals and petrochemicals, pharmaceutical synthesis, healthcare product development, and the synthesis of agrochemicals. Pd-based catalysts have been widely applied for selective hydrogenation due to their unique electronic structure and ability to adsorb and activate hydrogen and unsaturated substrates. However, the exclusive and comprehensive summarization of the size, composition, and surface and interface effect of metal Pd on the performance for selective hydrogenation is still lacking. In this perspective, the research progress on selective hydrogenation using Pd-based catalysts is summarized. The strategies for improving the catalytic hydrogenation performance over Pd-based catalysts are investigated. Specifically, the effects of the size, composition, and surface and interfacial structure of Pd-based catalysts, which could influence the dissociation mode of hydrogen, the adsorption, and the reaction mode of the catalytic substrate, on the performance have been systemically reviewed. Then, the progress on Pd-based catalysts for selective hydrogenation of unsaturated alkynes, aldehydes, ketones, and nitroaromatic hydrocarbons is revealed based on the fundamental principles of selective hydrogenation. Finally, perspectives on the further development of strategies for chemical selective hydrogenation are provided. It is hoped that this perspective would provide an instructive guideline for constructing efficient heterogeneous Pd-based catalysts for various selective hydrogenation reactions.

Development of a quantitative screening method for pesticide multiresidues in orange, chili pepper, and brown rice using gas chromatography-quadrupole time of flight mass spectrometry with dopant-assisted atmospheric pressure chemical ionization

A rapid screening method for the quantitative analysis of pesticide multiresidues using a high-resolution accurate mass (HRAM) quadrupole time-of-flight (Q-TOF) with a dopant-assisted gas chromatography-atmospheric pressure chemical ionization (GC-APCI) technique were developed. For convenient and constant supply of APCI dopant, a large-volume dopant bottle with a bypass valve was newly designed, and the developed method was tested with 415 pesticide mixtures for representative produce (orange, chili pepper, and brown rice). Methanol-enriched nitrogen gas was used to produce protonated molecular [M + H]+ ions, and fragment ions were produced by broad-band collision-induced dissociation mode. Twenty representative pesticides were selected and validated for analytical performance. The methanol dopant-assisted GC-APCI-Q-TOF technique is very promising for target and non-target screening and sensitive quantification for hundreds of pesticides in a single run.

Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers.

Peptide modification by a quaternary ammonium group containing a permanent positive charge is a promising method of increasing the ionization efficiency of the analyzed compounds, making ultra-sensitive detection even at the attomolar level possible. Charge-derivatized peptides may undergo both charge remote (ChR) and charge-directed (ChD) fragmentation. A series of model peptide conjugates derivatized with N,N,N-triethyloammonium (TEA), 1-azoniabicyclo[2.2.2]octane (ABCO), 2,4,6-triphenylopyridinium (TPP) and tris(2,4,6-trimetoxyphenylo)phosphonium (TMPP) groups were analyzed by their fragmentation pathways both in collision-induced dissociation (CID) and electron-capture dissociation (ECD) mode. The effect of the fixed-charge tag type and peptide sequence on the fragmentation pathways was investigated. We found that the aspartic acid effect plays a crucial role in the CID fragmentation of TPP and TEA peptide conjugates whereas it was not resolved for the peptides derivatized with the phosphonium group. ECD spectra are mostly dominated by cn ions. ECD fragmentation of TMPP-modified peptides results in the formation of intense fragments derived from this fixed-charge tag, which may serve as reporter ion.

Betrayed by the nervous system: a comparison group study to investigate the \u2018unsafe world\u2019 model of selective mutism

The study presented in the following verifies some assumptions of the novel ‘unsafe world’ model of selective mutism (SM). According to this model, SM is a stress reaction to situations erroneously experienced via cognition without awareness as ‘unsafe’. It assumes a high sensitivity to unsafety, whereby the nervous system triggers dissociation or freeze mode at relatively low thresholds. We examine whether there is a correlation between SM, sensory-processing sensitivity and dissociation. We compared a sample of 28 children and adolescents with SM (mean age 12.66 years; 18 females) to 33 controls without SM (mean age 12.45 years; 21 females). Both groups were compared using a medical history sheet, the ‘Selective Mutism Questionnaire’ (SMQ), a ‘Checklist for Speaking Behaviour’ (CheckS), the ‘Highly Sensitive Person Scale’ (HSPS), the ‘Child Dissociative Checklist’ (CDC), the ‘Adolescent Dissociative Experience Scale’ (A-DES) and the ‘Social Phobia and Anxiety Inventory for Children’ (SPAIK). Appropriate parametric and non-parametric tests were conducted to examine differences between groups. The results indicate that sensory-processing sensitivity was significantly higher in the group of children and adolescents with SM [X2(1) = 7.224, p = 0.0007; d = 1.092]. Furthermore, dissociative symptoms were more common in children and adolescents with SM than in controls [F(1, 33) = 13.004, p = 0.001; d = 0.986]. The results indicate that sensory-processing sensitivity and dissociation are important factors of SM that may hold important implications for the treatment.Trial Registration This study is registered with the ClinicalTrials.gov number NCT04233905.

Identification of New Psychoactive Tryptamines 4-OH-MET and 4-AcO-DMT Using High Resolution Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy

Objective To detect the uncontrolled new psychoactive tryptamines involved in drug-related cases with high resolution mass spectrometry and nuclear magnetic resonance spectroscopy. Methods White and brown powder obtained in actual cases were extracted and analyzed by gas chromatography-quadrupole time-of-flight mass spectrometry （GC-QTOF-MS）, ultra-high performance liquid chromatography-linear ion trap quadrupole-orbitrap mass spectrometry （UPLC-LTQ-Orbitrap MS） and 1H-nuclear magnetic resonance spectroscopy （1H-NMR）. Results After detection by GC-QTOF-MS, the components of white powder showed main characteristic fragment ion peaks at m/z 218.141 0 （molecular ion peak）, 72.080 6 （base peak）, etc. After detection by UPLC-LTQ-Orbitrap MS, its protonated molecular ion was m/z 219.149 4. The main ions in the secondary mass spectrum under the collision-induced dissociation （CID） mode were m/z 160.076 3 and 72.080 8. After detection by GC-QTOF-MS, the components of brown powder showed main characteristic fragment ion peaks at m/z 246.135 7 （molecular ion peak）, 58.065 1 （base peak）, etc. After detection by UPLC-LTQ-Orbitrap MS, its protonated molecular ion was m/z 247.145 0. The main ions in the secondary mass spectrum under CID mode were m/z 202.087 1, 160.076 3 and 134.060 5. NIST 17 library retrieval and 1H-NMR confirmed that the white powder and brown powder contained new psychoactive tryptamines 4-OH-MET and 4-AcO-DMT, respectively. Conclusion GC-QTOF-MS, UPLC-LTQ-Orbitrap MS and 1H-NMR can be used together to identify unknown new psychoactive substances.

Dissociation Strategies to Maximize Coverage of α-Helical Domains in Top-Down Mass Spectrometry of Integral Membrane Proteins.

Transmembrane α-helical domains of membrane proteins tend to remain structured in the gas phase, presenting a challenge for efficient electron capture/transfer dissociation during top-down dissociation mass spectrometry (MS) experiments. In this study, we compare results from different dissociation modes on a modern Orbitrap platform applied to a model integral membrane protein containing two transmembrane helices, the c-subunit of the Fo domain of the chloroplast ATP synthase. Using commercially available options, we compare collisionally activated dissociation (CAD) with the related variant higher-energy collisional dissociation (HCD) and with electron transfer dissociation (ETD). HCD performed better than CAD and ETD. A combined method utilizing both ETD and HCD (EThcD) demonstrates significant synergy over HCD or ETD alone, representing a robust option analogous to activated ion electron capture dissociation, whereby an infrared laser was used to heat the protein ion alongside electron bombardment. Ultraviolet photodissociation at 213 nm displays at least three backbone dissociation mechanisms and covered nearly 100% of backbone bonds, suggesting significant potential for this technique.

Structural Characterization of Daunomycin-Peptide Conjugates by Various Tandem Mass Spectrometric Techniques.

The use of peptide-drug conjugates has generated wide interest as targeted antitumor therapeutics. The anthracycline antibiotic, daunomycin, is a widely used anticancer agent and it is often conjugated to different tumor homing peptides. However, comprehensive analytical characterization of these conjugates via tandem mass spectrometry (MS/MS) is challenging due to the lability of the O-glycosidic bond and the appearance of MS/MS fragment ions with little structural information. Therefore, we aimed to investigate the optimal fragmentation conditions that suppress the prevalent dissociation of the anthracycline drug and provide good sequence coverage. In this study, we comprehensively compared the performance of common fragmentation techniques, such as higher energy collisional dissociation (HCD), electron transfer dissociation (ETD), electron-transfer higher energy collisional dissociation (EThcD) and matrix-assisted laser desorption/ionization–tandem time-of-flight (MALDI-TOF/TOF) activation methods for the structural identification of synthetic daunomycin-peptide conjugates by high-resolution tandem mass spectrometry. Our results showed that peptide backbone fragmentation was inhibited by applying electron-based dissociation methods to conjugates, most possibly due to the “electron predator” effect of the daunomycin. We found that efficient HCD fragmentation was largely influenced by several factors, such as amino acid sequences, charge states and HCD energy. High energy HCD and MALDI-TOF/TOF combined with collision induced dissociation (CID) mode are the methods of choice to unambiguously assign the sequence, localize different conjugation sites and differentiate conjugate isomers.

Aberrant RL2 O-GlcNAc antibody reactivity against serum-IgA1 of patients with colorectal cancer.

O-GlcNAcylation, a single attachment of N-acetylglucosamine (GlcNAc) on serine and threonine residues, plays important roles in normal and pathobiological states of many diseases. Aberrant expression of O-GlcNAc modification was found in many types of cancer including colorectal cancer (CRC). This modification mainly occurs in nuclear-cytoplasmic proteins; however, it can exist in some extracellular and secretory proteins. In this study, we investigated whether O-GlcNAc-modified proteins are present in serum of patients with CRC. Serum glycoproteins of CRC patients and healthy controls were enriched by wheat germ agglutinin, a glycan binding protein specifically binds to terminal GlcNAc and sialic acid. Two-dimensional gel electrophoresis, RL2 O-GlcNAc immunoblotting, affinity purification, and mass spectrometry were performed. The results showed that RL2 O-GlcNAc antibody predominantly reacted against serum immunoglobulin A1 (IgA1). The levels of RL2-reacted IgA were significantly increased while total IgA were not different in patients with CRC compared to those of healthy controls. Analyses by ion trap mass spectrometry using collision-induced dissociation and electron-transfer dissociation modes revealed one O-linked N-acetylhexosamine modification site at Ser268 located in the heavy constant region of IgA1; unfortunately, it cannot be discriminated whether it was N-acetylglucosamine or N-acetylgalactosamine because of their identical molecular mass. Although failed to demonstrate unequivocally it was O-GlcNAc, these data indicated that serum-IgA had an aberrantly increased reactivity against RL2 O-GlcNAc antibody in CRC patients. This specific glycosylated form of serum-IgA1 will expand the spectrum of aberrant glycosylation which provides valuable information to cancer glycobiology.

The enhancement effect of water-gas two-phase flow on depressurization process: Important for gas hydrate production

Depressurization is one of the most efficient methods in the production testing of natural gas hydrates. However, problems such as hydrate reformation, ice generation and insufficient dissociation driving force in the later period of depressurization adversely affect the gas production. It has been confirmed that controlling the flowrate ratio of a water-gas two-phase flow can help enhance the hydrate dissociation. However, the effect of the water-gas flowrate ratio on the hydrate dissociation behaviors during depressurization is unclear. In this study, three dissociation modes involving a combination of water-gas flow and depressurization were examined: mode 1 (concurrent start of depressurization and water-gas flow), mode 2 (depressurization is first used to dissociate the hydrate, and the water-gas flow is initiated after 15 min), and mode 3 (depressurization is first used, and the water-gas flow is initiated after 30 min). The feasibility of water-gas flow to accelerate hydrate dissociation and mitigate ice generation was confirmed during the depressurization process. In all the modes, the higher water-gas flowrate ratio and lower dissociation pressure significantly increased the energy recovery rate and decreased the energy input. Additionally, the water-gas flow, especially that with a higher flowrate ratio, effectively accelerated the elimination of the dark-zone (mixture of ice and hydrate) by providing continuous heat transfer. Mode 1 corresponded to the highest energy recovery rate, lowest energy input and most rapid disappearance of the dark-zone under the same experimental conditions. Therefore, mode 1 was regarded as the most efficient mode to dissociate hydrate in an actual hydrate production.

Electric-Field Mediated Chemistry: Uncovering and Exploiting the Potential of (Oriented) Electric Fields to Exert Chemical Catalysis and Reaction Control.

This Perspective discusses oriented external-electric-fields (OEEF), and other electric-field types, as "smart reagents", which enable in principle control over wide-ranging aspects of reactivity and structure. We discuss the potential of OEEFs to control nonredox reactions and impart rate-enhancement and selectivity. An OEEF along the "reaction axis", which is the direction whereby electronic reorganization converts reactants' to products' bonding, will accelerate reactions, control regioselectivity, induce spin-state selectivity, and elicit mechanistic crossovers. Simply flipping the direction of the OEEF will lead to inhibition. Orienting the OEEF off the reaction axis enables control over stereoselectivity, enantioselectivity, and product selectivity. For polar/polarizable reactants, the OEEF itself will act as tweezers, which orient the reactants and drive their reaction. OEEFs also affect bond-dissociation energies and dissociation modes (covalent vs ionic), as well as alteration of molecular geometries and supramolecular aggregation. The "key" to gaining access to this toolbox provided by OEEFs is microscopic control over the alignment between the molecule and the applied field. We discuss the elegant experimental methods which have been used to verify the theoretical predictions and describe various alternative EEF sources and prospects for upscaling OEEF catalysis in solvents. We also demonstrate the numerous ways in which the OEEF effects can be mimicked by use of (designed) local-electric fields (LEFs), i.e., by embedding charges or dipoles into molecules. LEFs and OEEFs are shown to be equivalent and to obey the same ground rules. Outcomes are exemplified for Diels-Alder cycloadditions, oxidative addition of bonds by transition-metal complexes, H-abstractions by oxo-metal species, ionic cleavage of halogen bonds, methane activation, etc.

Sequential amidation of peptide C-termini for improving fragmentation efficiency.

Owing to the poor fragmentation efficiency caused by the lack of a positively charged basic group at the C-termini of peptides, the identification of nontryptic peptides in classical proteomics is known to be less efficient. Particularly, attaching positively charged basic groups to C-termini via chemical derivatizations is known to be able to enhance their fragmentation efficiency. In this study, we introduced a novel strategy, C-termini sequential amidation reaction (CSAR), to improve peptide fragmentation efficiency. By this strategy, C-terminal and side-chain carboxyl groups were firstly amidated by neutral methylamine (MA), and then C-terminal amide bonds were selectively deamidated through peptide amidase while side-chain amide bonds remained unchanged, followed by the secondary amidation of C-termini via basic agmatine (AG). We optimized the amidation reaction conditions to achieve the MA derivatization efficiency of >99% for side-chain carboxyl groups and AG derivatization efficiency of 80% for the hydrolytic C-termini. We applied CSAR strategy to identify bovine serum albumin (BSA) chymotryptic digests, resulting in the increased fragmentation efficiencies (improvement by 9-32%) and charge states (improvement by 39-52%) under single or multiple dissociation modes. The strategy described here might be a promising approach for the identification of peptides that suffered from poor fragmentation efficiency.