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1.
J Appl Crystallogr ; 57(Pt 4): 1067-1084, 2024 Aug 01.
Article de Anglais | MEDLINE | ID: mdl-39108823

RÉSUMÉ

Portland cements (PCs) and cement blends are multiphase materials of different fineness, and quantitatively analysing their hydration pathways is very challenging. The dissolution (hydration) of the initial crystalline and amorphous phases must be determined, as well as the formation of labile (such as ettringite), reactive (such as portlandite) and amorphous (such as calcium silicate hydrate gel) components. The microstructural changes with hydration time must also be mapped out. To address this robustly and accurately, an innovative approach is being developed based on in situ measurements of pastes without any sample conditioning. Data are sequentially acquired by Mo Kα1 laboratory X-ray powder diffraction (LXRPD) and microtomography (µCT), where the same volume is scanned with time to reduce variability. Wide capillaries (2 mm in diameter) are key to avoid artefacts, e.g. self-desiccation, and to have excellent particle averaging. This methodology is tested in three cement paste samples: (i) a commercial PC 52.5 R, (ii) a blend of 80 wt% of this PC and 20 wt% quartz, to simulate an addition of supplementary cementitious materials, and (iii) a blend of 80 wt% PC and 20 wt% limestone, to simulate a limestone Portland cement. LXRPD data are acquired at 3 h and 1, 3, 7 and 28 days, and µCT data are collected at 12 h and 1, 3, 7 and 28 days. Later age data can also be easily acquired. In this methodology, the amounts of the crystalline phases are directly obtained from Rietveld analysis and the amorphous phase contents are obtained from mass-balance calculations. From the µCT study, and within the attained spatial resolution, three components (porosity, hydrated products and unhydrated cement particles) are determined. The analyses quantitatively demonstrate the filler effect of quartz and limestone in the hydration of alite and the calcium aluminate phases. Further hydration details are discussed.

2.
Sci Total Environ ; 950: 175200, 2024 Aug 06.
Article de Anglais | MEDLINE | ID: mdl-39117196

RÉSUMÉ

Comprehensive studies on the freeze-thaw (F-T) damage mechanism in siliceous slates are lacking. In this study, we investigated the evolutionary characteristics of F-T damage in siliceous slates. To this end, scanning electron microscopy, X-ray diffraction, X-ray fluorescence, and uniaxial compression tests were used to analyze the microstructure, phase composition, porosity, and macroscopic mechanical parameters of siliceous slate with varying initial water content during F-T cycles. The results revealed several insights. (1) The microstructure of siliceous slate undergoes significant change with respect to increasing water content and number of F-T cycles. The rock surface changed from smooth to rough, and the arrangement of the mineral particles changed from tight to loose. (2) More than 80 % of the contents of siliceous slate comprise oxygen, aluminum, silicon, potassium, and iron. In particular, siliceous slate comprises muscovite, quartz, clinochlore, and kaolinite. Both the clinochlore and kaolinite are unstable clay minerals. As clay minerals exhibit strong water absorption and expansion characteristics, kaolinite undergoes strong hydration reactions. Compared to rock samples without F-T cycles in the dry state, the clay mineral content of siliceous slate decreased by nearly 50 %, from 28.8 % to 15.5 %, after 30 F-T cycles in the saturated state. (3) The mechanical parameters of siliceous slates with varying water content decreased exponentially with the number of F-T cycles, while their porosity exhibited a positive correlation with the number of F-T cycles. The degree of deterioration in both increased with increasing water content. Both the number of F-T cycles and the initial water content were observed to wield a significant effect on the deterioration of siliceous slates. (4) The evolution curve of F-T load damage in siliceous slate exhibited characteristics of transitioning from gentle to concave and then to a convex stage of growth. Our results are expected to provide theoretical guidance for the evaluation and prevention of F-T disasters in cold regions.

3.
Anal Bioanal Chem ; 416(22): 4961-4971, 2024 Sep.
Article de Anglais | MEDLINE | ID: mdl-39110175

RÉSUMÉ

In atmospheric pressure chemical ionization mass spectrometry (APCI-MS), [M-3H+H2O]+ ions can deliver analyte-specific signals that enable direct analysis of volatile n-alkane mixtures. The underlying ionization mechanisms have been the subject of open debate, and in particular the role of water is insufficiently clarified to allow for reliable process analytics when the humidity level changes over time. This can be a problem, particularly in online monitoring, where analyte accumulation in the ion source can also occur. Here, we investigated the role of water during APCI-MS of volatile n-alkanes by changing the carrier gas for sample injection from a dry to a wetted state as well as by using 18O-labeled water. This allowed for a distinction between gaseous and surface-adsorbed water molecules. While adsorbed water seems to be responsible for the desired [M-3H+H2O]+ signals through surface reactions with the analyte molecules, gaseous water was found to promote the formation of CnH2n+1O+ of different (and analyte-independent) hydrocarbons, revealing a reaction with hydrocarbon species which accumulated in the ion source during continuous operation. At the same time, gaseous water competed with analyte molecules for ionization and thus suppressed the formation of alkyl (CnH2n+1+) and alkenyl (CnH2n-1+) ions. The results reveal a memory effect due to hydrocarbon adsorption, which may cause severe interpretation difficulties when the ionization chamber undergoes sudden humidity changes. The use of [M-3H+H2O]+ for n-alkane analysis in alkane/water mixtures can be facilitated by constantly maintaining high humidity and hence stabilizing the ionization conditions.

4.
Sci Prog ; 107(3): 368504241275414, 2024.
Article de Anglais | MEDLINE | ID: mdl-39150376

RÉSUMÉ

BACKGROUND: The pressure fluctuation in the volute can be effectively reduced when the impeller of the double-suction pump is staggered, but the mechanism of this reduction is still unclear. At the same time, the traditional analysis method cannot realize the visualization of pressure fluctuation. OBJECTIVE: The purpose of this article is to explore the spatial distribution, propagation, and attenuation law of pressure fluctuation, and on this basis, to research the reason why staggered impeller reduce pressure fluctuation. METHODS: A new method called Pulse tracking network (PTN) was used in this article. Compared with the traditional method, which only analyzes the pressure fluctuation at scattered points, this method greatly improves the spatial resolution of the pressure fluctuation. In particular, the phase analysis is a major highlight of the method. RESULTS: Staggered impeller significantly reduced the pressure fluctuation intensity dominated by blade passing frequency. At the same time, the propagation of the pressure fluctuation in the volute changed from radial to circumferential in the volute cross-section. CONCLUSIONS: Staggered impeller can effectively reduce pressure fluctuation, and the circumferential propagation caused by it is considered to be the main reason for it.

5.
J Clin Ultrasound ; 2024 Jun 20.
Article de Anglais | MEDLINE | ID: mdl-39031559

RÉSUMÉ

OBJECTIVE: Left ventricular dyssynchrony (LVD), the loss of coordinated contraction in the left ventricle, is an early sign of heart failure. LVD can be assessed using phase analysis techniques with gated single-photon emission computed tomography (SPECT) myocardial perfusion imaging (MPI). This study aimed to investigate the impact of obesity on LVD through phase analysis. METHODS: We retrospectively enrolled 152 obese patients and 80 age- and sex-matched nonobese patients who showed normal myocardial perfusion and normal left ventricular ejection fraction (LVEF) on MPI. Phase standard deviation (PSD) and phase histogram bandwidth (PBW), as phase analysis parameters, were compared between patients with and without obesity. RESULTS: Although PSD values were within the normal range (cut-off value >23) for both groups, the PSD values of obese patients were higher than those of the nonobese (20.49 ± 8.66 vs. 14.81 ± 4.93; p < 0.05). PBW values of obese patients were statistically significantly higher than those of the nonobese (57.03 ± 23.17 vs. 41.40 ± 9.96; p < 0.05). The PBW values of obese patients exceeded the normal limits (cut-off value >49). A weak positive correlation was observed between body mass index (BMI) and PBW values in obese patients (r = 0.181, p < 0.05). In patients of normal weight, no correlations were found between BMI and phase analysis parameters. CONCLUSION: LVD may develop in obese patients, even when myocardial perfusion and ejection fraction are preserved. The use of phase analysis with gated SPECT could be an additional finding improving the early detection of left ventricular dyssynchrony in obese patients.

6.
Article de Anglais | MEDLINE | ID: mdl-38960945

RÉSUMÉ

This study aimed to assess the diagnostic efficacy of left ventricular synchrony (LVS) for detecting coronary artery disease (CAD). We explored whether the LVS index derived from phase analysis of D-SPECT provides superior diagnostic value compared to conventional perfusion analysis in identifying obstructive CAD. Patients with suspected or confirmed CAD underwent drug-stress/rest gated D-SPECT myocardial perfusion imaging (MPI) and coronary angiography (CAG). A 50% stenosis was set as the threshold for obstructive CAD. 110 participants were enrolled in this analysis. There were significant differences in phase standard deviation (PSD), phase histogram bandwidth (PHB) and entropy among the four groups. Patients without cardiac disease and those with mild-moderate stenosis exhibited no noticeable contraction asynchrony. However, LVS indices demonstrated a gradual increase with the progression of coronary stenosis when compared to NC (P < 0.001). Obstructive CAD was identified in 43 out of 110 participants (39%). Optimal cutoff values for diagnosing obstructive CAD during stress were determined as 7.6° for PSD, 24° for PHB, and 37% for entropy, respectively. Notably, PSD, PHB, and entropy indices exhibited higher sensitivity compared to MPI. The integration of the stress-induced LVS indices into routine MPI analysis resulted in a significantly greater area under the curve (AUC), leading to improved diagnostic performance and enhanced differential capacity. Stress-induced LVS indices increase with the severity of coronary artery stenosis by D-SPECT phase analysis. Further, the indices-derived phase analysis exhibits superior sensitivity and discriminatory ability compared to MPI in detecting obstructive CAD.

7.
Appl Spectrosc ; : 37028241258109, 2024 Jul 25.
Article de Anglais | MEDLINE | ID: mdl-38881172

RÉSUMÉ

Ongoing technological advancements in the field of mid-infrared (MIR) spectroscopy continuously yield novel sensing modalities, offering capabilities beyond traditional techniques like Fourier transform infrared spectroscopy (FT-IR). One such advancement is MIR dispersion spectroscopy, utilizing a tunable quantum cascade laser and Mach-Zehnder interferometer for liquid-phase analysis. Our study assesses the performance of a custom MIR dispersion spectrometer at its current development stage, benchmarks its performance against FT-IR, and validates its potential for time-resolved chemical reaction monitoring. Unlike conventional methods of IR spectroscopy measuring molecular absorptions using intensity attenuation, our method detects refractive index changes (phase shifts) down to a level of 6.1 × 10-7 refractive index units (RIU). This results in 1.5 times better sensitivity with a sevenfold increase in analytical path length, yielding heightened robustness for the analysis of liquids compared to FT-IR. As a case study, we monitor the catalytic activity of invertase with sucrose, observing the formation of resultant monosaccharides and their progression toward thermodynamic equilibrium. Anomalous refractive index spectra of reaction mixtures, with substrate concentrations ranging from 2.5 to 25 g/L, are recorded, and analyzed at various temperatures, yielding Michaelis-Menten kinetics findings comparable to the literature. Additionally, the first-time application of two-dimensional correlation spectroscopy on the recorded dynamic dispersion spectra correctly identifies the mutarotation of reaction products (glucose and fructose). The results demonstrate high precision and sensitivity in investigating complex time-dependent chemical reactions via broadband refractive index changes.

8.
Auris Nasus Larynx ; 51(4): 738-746, 2024 Aug.
Article de Anglais | MEDLINE | ID: mdl-38850719

RÉSUMÉ

OBJECTIVE: The present study aimed to observe and analyze the ocular movements induced by Coriolis stimulation (eccentric pitch while rotating: PWR) that induces Coriolis forces on the vestibular apparatus of healthy human individuals. METHODS: A total of 31 healthy subjects participated in the study. Eccentric PWR was performed on 27 subjects, by pitching the participants' heads forward and backward at an angle of 30° each on an axis parallel and 7 cm below inter-aural axis, at a frequency of 0.5 Hz while on a chair rotating at a constant angular velocity of 97.2°/s on the earth-vertical axis. Ocular movements during stimulation were recorded using three-dimensional video-oculography. As a subsidiary analysis, 0.5 Hz head roll tilt was used as another stimulus that also induced torsional ocular movements. The forces induced on the vestibular apparatus, and phases of ocular torsion against the stimulus were calculated from the observed data. RESULTS: In the Coriolis stimulation during rightward yaw rotation, a rightward ocular torsion of 4.8° on average, was observed when the head pitched forward, and the direction of ocular torsion reversed when the head pitched backward. During leftward yaw rotation, these relationships were reversed with an average amplitude of 4.7° The phase of ocular torsion preceded that of Coriolis force by 0.2 s during rightward rotation and 0.14 s during leftward rotation. There were no significant differences in amplitude or phase between the directions of rotation. The phase lead of 0.5 Hz roll-tilt was significantly smaller than that of Coriolis stimulation (p < 0.01). CONCLUSION: Coriolis stimulation induced a specific pattern of ocular torsion, where its direction and phase suggested that the mechanism likely involved both the otolith and semicircular canals. Further studies may provide a clue to the magnitude of the otolith and semicircular canal contributions.


Sujet(s)
Mouvements oculaires , Humains , Mâle , Adulte , Femelle , Mouvements oculaires/physiologie , Jeune adulte , Force de Coriolis , Rotation , Volontaires sains , Mouvements de la tête/physiologie
9.
Article de Anglais | MEDLINE | ID: mdl-38917028

RÉSUMÉ

A small ionization needle with an ultrasharp, ultrafine tip is introduced. It is lab-fabricated from tungsten wire and serves as a corona discharge emitter in nanoelectrode atmospheric pressure chemical ionization mass spectrometry (nAPCI-MS). Tip radii ranged from 8 to 44 nm, up to 44× smaller than the sharpest previously reported corona needle. Because of this, nAPCI was able to operate at +1.0 kV with no auxiliary counter electrode. Alternatively, at +1.2 kV, nAPCI could be enclosed in a small plastic assembly for headspace analysis with a sampling tube attachment as long as 15 m. No added heat or gas flow was necessary. The efficacy of nAPCI-MS was demonstrated through needle durability studies and direct analysis of vapors from real-world samples. Provisional identifications include ibuprofen from a pharmaceutical tablet, albuterol aerosol sprayed from a medical inhaler, cocaine from paper currency, caffeine from a fingertip, and bisphenol E from a paper receipt.

10.
Pest Manag Sci ; 80(9): 4650-4664, 2024 Sep.
Article de Anglais | MEDLINE | ID: mdl-38775404

RÉSUMÉ

BACKGROUND: The beet webworm, Loxostege sticticalis, a worldwide pest of many crops, performs a seasonal migration, causing periodic outbreaks in Asia, Europe and North America. Although long-distance migration is well documented in China, patterns of transboundary migration among China, Russia and Mongolia are largely unknown. We performed a phase analysis of L. sticticalis periodic outbreaks among three countries based on 30 years of historical population data, analyzed the wind systems during migration over boundary regions, and traced the migratory routes in a case study of outbreaks in 2008 by trajectory simulation. RESULTS: Highly synchronized outbreak years of L. sticticalis were observed between China and Mongolia, China and eastern Siberia, China and western Siberia, Mongolia and eastern Siberia, eastern Siberia and western Siberia from 1978 to 2008, indicating possible transboundary migration between these regions. Winds at 300-600 m altitude, where adult migration usually occurs, also showed a high probability of northwestern winds in Haila'er (China), Chita (Russia) and Choybalsan (Mongolia), favoring successful adult migration from these areas to northern and northeastern China. Back trajectory analysis further showed that the first-generation adults that caused the severe outbreak of second-generation larvae in 2008 originated from eastern Siberia, eastern Mongolia, and the boundary regions of China-Russia and China-Mongolia. CONCLUSION: Our findings demonstrated that the source of L. sticticalis outbreaks in northern China was closely related to the outbreaks in Siberia and Mongolia via long-distance transboundary windborne migration. This information will help guide international monitoring and management strategies against this notorious pest. © 2024 Society of Chemical Industry.


Sujet(s)
Migration animale , Papillons de nuit , Animaux , Papillons de nuit/physiologie , Mongolie , Russie , Chine , Larve/croissance et développement
11.
Sci Rep ; 14(1): 12286, 2024 May 29.
Article de Anglais | MEDLINE | ID: mdl-38811716

RÉSUMÉ

Magnetic skyrmions are quasi-particles with a swirling spin texture that form two-dimensional lattices. Skyrmion lattices can exhibit defects in response to geometric constraints, variations of temperature or applied magnetic fields. Measuring deformations in skyrmion lattices is important to understand the interplay between the lattice structure and external influences. Geometric phase analysis (GPA) is a Fourier-based image processing method that is used to measure deformation fields in high resolution transmission electron microscopy (TEM) images of crystalline materials. Here, we show that GPA can be applied quantitatively to Lorentz TEM images of two-dimensional skyrmion lattices obtained from a chiral magnet of FeGe. First, GPA is used to map deformation fields around a 5-7 dislocation and the results are compared with the linear theory of elasticity. Second, rotation angles between skyrmion crystal grains are measured and compared with angles calculated from the density of dislocations. Third, an orientational order parameter and the corresponding correlation function are calculated to describe the evolution of the disorder as a function of applied magnetic field. The influence of sources of artifacts such as geometric distortions and large defoci are also discussed.

12.
Data Brief ; 54: 110507, 2024 Jun.
Article de Anglais | MEDLINE | ID: mdl-38799709

RÉSUMÉ

Plants emit a range of volatile organic compounds (VOCs) as a way of interacting with their biotic and abiotic surroundings. These VOCs can have various ecological functions, such as attracting pollinators, repelling herbivores, or may be emitted in response to abiotic stress. For the present dataset, we used gas chromatography coupled ion mobility spectrometry (GC-IMS) to analyse the VOCs emitted by different plant species under controlled conditions. GC-IMS is a rapid and sensitive technique for gas phase analysis, that separates VOCs based on their retention time and drift time, resulting in characteristic heatmaps where the xy-position of a signal corresponds to compound identity, while signal intensity reflects its abundance. In this dataset, rapid analysis by GC-IMS was used to record emission pattern of 140 plant species from different taxonomic groups. This includes both floral volatiles and emission from leaves after induced damage. The data was pre-evaluated and listed in one table, containing information on the plant material used, as well as information on the respective emission patterns (including already identified compounds). Thus, this dataset provides a broad overview over plant VOC emissions. These can be used to either check the distribution of knowns substances, or the specific emissions of plants for functional, ecological or physiological studies or as the starting point for chemotaxonomic studies. The extraordinary ease with which these data can be generated - with the suitable set-up - lends itself to larger scale systematic or ecological studies across plant (or animal) groups and even ecosystems.

13.
Materials (Basel) ; 17(3)2024 Jan 29.
Article de Anglais | MEDLINE | ID: mdl-38591501

RÉSUMÉ

The growing demand for composite materials capable of enduring prolonged loads in high-temperature and aggressive environments presents pressing challenges for materials scientists. Ceramic materials composed of silicon carbide largely possess high mechanical strength at a relatively low density, even at elevated temperatures. However, they are inherently brittle in nature, leading to concerns about their ability to fracture. The primary objective of this study was to develop a novel technique for fabricating layered composite materials by incorporating SiC-based ceramics, refractory metals, and their silicides as integral constituents. These layered composites were produced through the liquid-phase siliconization method applied to metal-carbon blanks. Analysis of the microstructure of the resultant materials revealed that when a metal element interacts with molten silicon, it leads to the formation of a layer of metal silicide on the metal's surface. Furthermore, three-point bending tests exhibited an enhancement in the bending strength of the layered composite in comparison to the base silicon carbide ceramics. Additionally, the samples demonstrated a quasi-plastic nature during the process of destruction.

14.
Ann Nucl Med ; 38(6): 441-449, 2024 Jun.
Article de Anglais | MEDLINE | ID: mdl-38498236

RÉSUMÉ

PURPOSE: Left ventricular mechanical dyssynchrony (LVMD) is an important prognostic factor in coronary artery disease. A growing body of evidence indicates that LVMD parameters derived from phase analysis of gated myocardial SPECT may allow risk stratification for future cardiac events. We performed a systematic review and meta-analysis on the prognostic value of LVMD on gated SPECT in patients with coronary artery disease. METHODS: PubMed, Embase, and the Cochrane library were searched until August 25, 2022, for studies reporting the prognostic value of LVMD on gated SPECT for outcomes of all-cause death, cardiac death, or major adverse cardiovascular event (MACE) in patients with coronary artery disease. Hazard ratios (HRs) and their 95% confidence intervals (CIs) were meta-analytically pooled using a random-effects model. RESULTS: Nine studies (26,750 patients) were included in a qualitative synthesis. Among the SPECT LVMD parameters used in various studies, high phase standard deviation, phase bandwidth, and phase entropy were widely evaluated and reported to be associated with high rates of all-cause death, cardiac death, or MACE. For five studies (23,973 patients) in the quantitative synthesis, the pooled HR of LVMD for predicting MACE was 2.81 (95% CI 2.03-3.88). Studies using combined phase parameters to define LVMD showed higher HRs than a study using phase entropy (p = 0.0180). CONCLUSION: LVMD from gated myocardial SPECT is a significant prognostic factor for coronary artery disease. Phase analysis of gated SPECT may be useful for accurate risk stratification and could be applied for clinical decision-making in such patients.


Sujet(s)
Tomographie d'émission monophotonique cardiaque synchronisée à l'ECG , Maladie des artères coronaires , Imagerie de perfusion myocardique , Dysfonction ventriculaire gauche , Humains , Maladie des artères coronaires/imagerie diagnostique , Pronostic , Dysfonction ventriculaire gauche/imagerie diagnostique , Dysfonction ventriculaire gauche/physiopathologie
15.
Magn Reson Imaging ; 109: 271-285, 2024 Jun.
Article de Anglais | MEDLINE | ID: mdl-38537891

RÉSUMÉ

Functional magnetic resonance imaging (fMRI) plays a crucial role in neuroimaging, enabling the exploration of brain activity through complex-valued signals. These signals, composed of magnitude and phase, offer a rich source of information for understanding brain functions. Traditional fMRI analyses have largely focused on magnitude information, often overlooking the potential insights offered by phase data. In this paper, we propose a novel fully Bayesian model designed for analyzing single-subject complex-valued fMRI (cv-fMRI) data. Our model, which we refer to as the CV-M&P model, is distinctive in its comprehensive utilization of both magnitude and phase information in fMRI signals, allowing for independent prediction of different types of activation maps. We incorporate Gaussian Markov random fields (GMRFs) to capture spatial correlations within the data, and employ image partitioning and parallel computation to enhance computational efficiency. Our model is rigorously tested through simulation studies, and then applied to a real dataset from a unilateral finger-tapping experiment. The results demonstrate the model's effectiveness in accurately identifying brain regions activated in response to specific tasks, distinguishing between magnitude and phase activation.


Sujet(s)
Encéphale , Imagerie par résonance magnétique , Théorème de Bayes , Imagerie par résonance magnétique/méthodes , Encéphale/imagerie diagnostique , Encéphale/physiologie , Cartographie cérébrale/méthodes , Simulation numérique
16.
Angew Chem Int Ed Engl ; 63(16): e202317695, 2024 04 15.
Article de Anglais | MEDLINE | ID: mdl-38380831

RÉSUMÉ

3D electron diffraction (3D ED) has shown great potential in crystal structure determination in materials, small organic molecules, and macromolecules. In this work, an automated, low-dose and low-bias 3D ED protocol has been implemented to identify six phases from a multiple-phase melt-crystallisation product of an active pharmaceutical ingredient, griseofulvin (GSF). Batch data collection under low-dose conditions using a widely available commercial software was combined with automated data analysis to collect and process over 230 datasets in three days. Accurate unit cell parameters obtained from 3D ED data allowed direct phase identification of GSF Forms III, I and the known GSF inclusion complex (IC) with polyethylene glycol (PEG) (GSF-PEG IC-I), as well as three minor phases, namely GSF Forms II, V and an elusive new phase, GSF-PEG IC-II. Their structures were then directly determined by 3D ED. Furthermore, we reveal how the stabilities of the two GSF-PEG IC polymorphs are closely related to their crystal structures. These results demonstrate the power of automated 3D ED for accurate phase identification and direct structure determination of complex, beam-sensitive crystallisation products, which is significant for drug development where solid form screening is crucial for the overall efficacy of the drug product.


Sujet(s)
Électrons , Polymères , Polymères/composition chimique , Griséofulvine/composition chimique , Polyéthylène glycols/composition chimique , Cristallisation/méthodes
17.
Anal Bioanal Chem ; 416(8): 1843-1855, 2024 Mar.
Article de Anglais | MEDLINE | ID: mdl-38355845

RÉSUMÉ

Online monitoring of dynamic chemical processes involving a wide volatility range of hydrocarbon species is challenging due to long chromatographic measurement times. Mass spectrometry (MS) overcomes chromatographic delays. However, the analysis of n-alkane mixtures by MS is difficult because many fragment ions are formed, which leads to overlapping signals of the homologous series. Atmospheric pressure chemical ionization (APCI) is suitable for the analysis of saturated hydrocarbons and is the subject of current research. Still, although APCI is a "soft ionization" technique, fragmentation is typically inevitable. Moreover, it is usually applied for liquid samples, while an application for online gas-phase monitoring is widely unexplored. Here, we present an automated APCI-MS method for an online gas-phase analysis of volatile and semi-volatile n-alkanes. Mass spectra for n-heptane and n-decane reveal [M-H]+, [M-3H]+ and [M-3H+H2O]+ as abundant ions. While [M-H]+ and [M-3H]+ show an excessive fragmentation pattern to smaller CnH2n+1+ and CnH2n-1+ cations, [M-3H+H2O]+ is the only relevant signal within the CnH2n+1O+ ion group, i.e., no chain cleavage is observed. This makes [M-3H+H2O]+ an analyte-specific ion that is suitable for the quantification of n-alkane mixtures. A calibration confirms the linearity of C7 and C10 signals up to concentrations of ~1000-1500 ppm. Moreover, validated concentration profiles are measured for a binary C7/C10 mixture and a five-alkane C7/C10/C12/C14/C20 mixture. Compared to the 40-min sampling interval of the reference gas chromatograph, MS sampling is performed within 5 min and allows dynamic changes to be monitored.

19.
Heliyon ; 10(3): e25506, 2024 Feb 15.
Article de Anglais | MEDLINE | ID: mdl-38352740

RÉSUMÉ

IN939 is a modern class of nickel-based superalloys designed for continuous operational sustenance at elevated temperatures owing to their excellent combination of fatigue, creep, and corrosion resistance. This unique performance of IN939 is associated with the composition of this alloy, along with specific post-processing treatments such as solution treatment and aging, giving rise to features such as the presence of γ' residues, as well as the presence of MC and M23C6 carbides. This also includes the absence of the eutectic and incipient melting phases. For this alloy, the primary part development is by the powder bed fusion process using a laser powder bed fusion machine. At the same time, a solo study highlights the use of an EB-PBF machine for the synthesis. The AM development process of these alloys is hindered by machine parameters, which have been found ineffective in isolation to obtain a fully dense structure with desired properties. The purpose of these parameters is to improve their core properties while minimizing defects associated with powder metallurgy routes, such as porosity, detrimental precipitates, grain anisotropy, etc. This study aims to provide an overview of the advancements in research related to IN939, explicitly focusing on the benchmarks achieved through additive manufacturing techniques. We have discussed the work performed in this area, compared the results of different studies, and identified the gaps in current research. By doing so, we aim to provide a comprehensive understanding of the potential of IN939 and its applications in extreme environments.

20.
J Fluoresc ; 34(1): 381-395, 2024 Jan.
Article de Anglais | MEDLINE | ID: mdl-37273030

RÉSUMÉ

While some studies inferred that valid information can be retrieved for the refolding of proteins and consequent identification of folding intermediates in the stopped-flow spectrometry collapse phase, other studies report that these burst phase folding intermediates can be questioned, implying a solvent-dependent modification of the still unfolded polypeptide chain. We therefore decided to investigate the burst phase occurring for the α-synuclein (Syn) amyloid protein by stopped-flow spectrometry. Solvent-dependent modification effects indeed occurred for the Nα-acetyl-L-tyrosinamide (NAYA) parent small compound and for the folded monomeric ubiquitin protein. More complex was the burst phase analysis of the disordered Syn amyloid protein. While this amyloid protein was determined to be aggregated at pH 7 and pH 2, in particular, this protein at pH 3 appears to be in a monomeric state in the burst phase analysis performed. In addition, the protein at pH 3 appears to suffer a hydrophobic collapse with the formation of a possible folded intermediate. This folded intermediate seems to result from a fast contraction of the disordered amyloid polypeptide chain, which is proceeded by an expansion of the protein, due to the occurrence of solvent-dependent modification effects in a milliseconds time scale of the burst phase. Generally, it can be argued that both literature criteria of solvent-dependent modifications of the disordered Syn amyloid protein and of the formation of its possible folded intermediate are very likely to occur in the burst phase.


Sujet(s)
Pliage des protéines , alpha-Synucléine , alpha-Synucléine/composition chimique , Protéines amyloïdogènes , Solvants , Peptides , Amyloïde/composition chimique , Amyloïde/métabolisme , Cinétique
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