Electron Density Research Articles

Improving the detection of hypo-vascular liver metastases in multiphase contrast-enhanced CT with slice thickness less than 5 mm using DenseNet

IntroductionThinner slices are more susceptible in detecting small lesions but suffer from higher statistical fluctuation. This work aimed to reduce image noise in multiphase contrast-enhanced CT reconstructed with slice thickness thinner than the clinical setting (i.e., 5 mm) using convolutional neural network (CNN) for enabling better detection of hypo-vascular liver metastasis. MethodsA DenseNet model was used to generate noise map for multiphase CT reconstructed with slice thickness of 2.5 mm and 1.25 mm. Image denoising was conducted by subtracting the CNN-generated noise map from CT images with reduced photon flux due to thinner slice thickness. The performance of DenseNet was evaluated on CT scans of electron density phantoms and patients with hypovascular liver metastases less than 1.5 cm in terms of Hounsfield Unit (HU) variation, statistical fluctuation, and contrast-to-noise ratio (CNR). ResultsThe phantom study demonstrated that the CNN-based denoising method was able to reduce statistical fluctuation in CT images reconstructed with slice thickness of 2.5 mm and 1.25 mm without causing significant edge blurring or variation in HU values. With regards to patient study, it was found that the denoised 2.5-mm and 1.25-mm slices had higher CNR than the conventional 5-mm slices for hypo-vascular liver metastases in all 4 phases of multiphase CT. ConclusionOur results demonstrated that the detection of hypo-vascular liver metastases in multiphase contrast-enhanced CT with slice thickness less than 5 mm could be improved by using the CNN-based denoising method. Implications for practiceReconstruction slice thickness has a strong influence on the image quality of CT imaging. A CNN-based denoising method was used in this work to reduce the image noise in multiphase contrast-enhanced CT reconstructed with slice thickness less than 5 mm.

Plasma atomic layer etching of SiO2 with a low global warming potential fluorocarbon precursor (C6F6)

Reducing greenhouse gas emissions from semiconductor manufacturing has been attracting enormous interest in both industry and academia as global warming issues have increased in significance year by year. Among various strategies, the search for etch precursors that have low global warming potential is actively underway worldwide to reduce the use of conventional precursors with high global warming potential. In this paper, we explore the use of C6F6, a promising candidate to replace the widely utilized perfluorocarbon precursor C4F8, for plasma atomic layer etching (ALE) of SiO2. In situ ellipsometry results indicated that acceptable ALE characteristics were obtained with C4F8 and C6F6 each in their own specific ALE window, while C6F6 showed superior ALE performance. Investigation into the ALE performance with different precursors was then conducted based on plasma diagnostics for radical density, electron density, and plasma potential, and the results of which showed that the difference in the radical composition between precursors significantly affected the resulting ALE trends and also that the excellent ALE performance with C6F6 might originate from its significant polymeric characteristics. We expect the present findings to contribute to the wider adoption of low global warming potential precursors in the etching process.

Dithienylethene-Based Photoswitchable Phosphines for the Palladium-Catalyzed Stille Coupling Reaction.

Homogeneous transition metal catalysis is a constantly developing field in chemical sciences. A growing interest in this area is photoswitchable catalysis, which pursues in situ modulation of catalyst activity through noninvasive light irradiation. Phosphorus ligands are excellent targets to accomplish this goal by introducing photoswitchable moieties; however, only a limited number of examples have been reported so far. In this work, we have developed a series of palladium complexes capable of catalyzing the Stille coupling reaction that contain photoisomerizable phosphine ligands based on dithienylethene switches. Incorporation of electron-withdrawing substituents into these dithienylethene moieties allows variation of the electron density on the phosphorus atom of the ligands upon light irradiation, which in turn leads to a modulation of the catalytic properties of the formed complexes and their activity in a model Stille coupling reaction. These results are supported by theoretical computations, which show that the energy barriers for the rate-determining steps of the catalytic cycle decrease when the photoswitchable phosphine ligands are converted to their closed state.

Electron-Rich Ru Supported on N-Doped Coffee Biochar for Selective Reductive Amination of Furfural to Furfurylamine.

Highly selective synthesis of primary amines from renewable biomass has attracted increasing attention, but it still faces great challenges in chemical industry applications. In this study, an electron-rich Ru catalyst was constructed by doping N into coffee biochar using a one-pot carbonization method (Ru/NCB-600). Ru/NCB-600 showed high catalytic activity and yield for the reductive amination of furfural with green and cheap NH3 and H2. The excellent catalytic performance of Ru/NCB-600 was closely correlated to the formation of electron-rich Ruδ- species (Ruδ--Nxδ+), which endowed Ru/NCB-600 with an enhanced H2 adsorption and activation ability. Ru/NCB-600 showed a high formation rate of 95.6 gfurfurylamine·gRu-1·h-1 and a high yield of furfurylamine (98.6%) at 50 °C. Ru/NCB-600 can also be used for the reductive amination of various carbonyl compounds in good to excellent yield (95.4-99%). This study thus provides a potential pathway for the highly selective reductive amination of carbonyl compounds by regulating the electron density of Ru.

Precisely Engineering Asymmetric Atomic CoN4 by Electron Donating and Extracting for Oxygen Reduction Reaction

AbstractThe development of nonpyrolytic catalysts featuring precisely defined active sites represents an effective strategy for investigating the fundamental relationship between the catalytic activity of oxygen reduction reaction (ORR) catalysts and their local coordination environments. In this study, we have synthesized a series of model electrocatalysts with well‐defined CoN4 centers and nonplanar symmetric coordination structures. These catalysts were prepared by a sequential process involving the chelation of cobalt salts and 1,10‐phenanthroline‐based ligands with various substituent groups (phen(X), where X=OH, CH3, H, Br, Cl) onto covalent triazine frameworks (CTFs). By modulating the electron‐donating or electron‐withdrawing properties of the substituent groups on the phen‐based ligands, the electron density surrounding the CoN4 centers was effectively controlled. Our results demonstrated a direct correlation between the catalytic activity of the CoN4 centers and the electron‐donating ability of the substituent group on the phenanthroline ligands. Notably, the catalyst denoted as BCTF−Co‐phen(OH), featuring the electron‐donating OH group, exhibited the highest ORR catalytic activity. This custom‐crafted catalyst achieved a remarkable half‐wave potential of up to 0.80 V vs. RHE and an impressive turnover frequency (TOF) value of 47.4×10−3 Hz at 0.80 V vs. RHE in an alkaline environment.

Precisely Engineering Asymmetric Atomic CoN4 by Electron Donating and Extracting for Oxygen Reduction Reaction.

The development of nonpyrolytic catalysts featuring precisely defined active sites represents an effective strategy for investigating the fundamental relationship between the catalytic activity of oxygen reduction reaction (ORR) catalysts and their local coordination environments. In this study, we have synthesized a series of model electrocatalysts with well-defined CoN4 centers and nonplanar symmetric coordination structures. These catalysts were prepared by a sequential process involving the chelation of cobalt salts and 1,10-phenanthroline-based ligands with various substituent groups (phen(X), where X=OH, CH3, H, Br, Cl) onto covalent triazine frameworks (CTFs). By modulating the electron-donating or electron-withdrawing properties of the substituent groups on the phen-based ligands, the electron density surrounding the CoN4 centers was effectively controlled. Our results demonstrated a direct correlation between the catalytic activity of the CoN4 centers and the electron-donating ability of the substituent group on the phenanthroline ligands. Notably, the catalyst denoted as BCTF-Co-phen(OH), featuring the electron-donating OH group, exhibited the highest ORR catalytic activity. This custom-crafted catalyst achieved a remarkable half-wave potential of up to 0.80 V vs. RHE and an impressive turnover frequency (TOF) value of 47.4×10-3 Hz at 0.80 V vs. RHE in an alkaline environment.

In Silico Design and Characterization of a New Molecular Electride: Li@Calix[3]Pyrrole.

Electrides, in which anionic electrons are localized independentof the atoms in the compound, have shown promise especially as catalysts and optoelectronic materials. Here, we present a new computationally designed molecular electride, Li@calix[3]pyrrole (Li@C3P). Electron density and electron localization function analyses unequivocally confirm the existence of localized electride electron density,independent of any specific atoms. Non-covalent interaction plots further validate the character of the isolated localized electron, suggesting that the system can be accurately represented by Li+@calix[3]pyrrole⋅e-, denoting its distinct charge separation. The remarkable non-linear optical properties of Li@C3P, including average polarizability= 412.4 au, first hyperpolarizability= 4.46 × 104 au, and second hyperpolarizability= 18.40 × 106 au, are unparalleled in the previously reported and similar Li@C4P molecular electride. Furthermore, energy decomposition analysisin combination with natural orbital for chemical valencetheory sheds light on the mechanism of electron density transfer from Li to the C3P cage, yielding the charge-separated Li@C3P complex.In addition to the electron transfer, a key factor to its electride nature is the electronic structure of the CnP cage, which has its lowest unoccupied molecular orbitallocated in the void adjacent to the N-H groups at the back of the bowl-shaped CnP cage.

Mechanism of plasma chemistry in CO2 hydrogenation using a dielectric barrier discharge reactor

AbstractPlasma‐induced CO2 hydrogenation process has received much attention, while the related plasma chemistry has not been profoundly explored. Herein, electron‐induced and thermochemical effects on CO2 hydrogenation in a dielectric barrier discharge reactor were investigated. The temperatures for the discharge pattern transition for CO2/H2, CO2/H2/N2, CO2/H2/Ar, and CO2/H2/He mixtures were 623, 623, 600, and 600 K, respectively. CO2 conversion was controlled by electron‐induced reactions and was sensitive to discharge pattern and electron density but not electron energy. In contrast, product formation was governed by the thermo‐induced chemistry. These results are useful for a better understanding of plasma‐induced CO2 hydrogenation.

Fast exact algorithm for neutrino oscillation in constant matter density

A recently published method [1,2] for solving the neutrino evolution equation with constant matter density is further refined and used to lay out an exact algorithm for computing oscillation probabilities, which is moderately faster than previous methods when looping through neutrinos of different energies. In particular, the three examples of ν(−)e survival, ν(−)μ survival and ν(−)e appearance probabilities are written in terms of mixing angles, mass differences and matter electron density. A program based on this new method is found to be roughly twice as fast as, and in agreement with, the leading GLoBES package. Furthermore, the behaviour of all relevant effective parameters is sketched out in terms of a range of neutrino energies, or matter electron densities. For instance, the ν(−)e survival probability in constant matter density is found to have no dependence on the mixing angle θ23 or the CP-violating phase δ13.

How electrons still guard the space: Electron number distribution functions based on QTAIM∩ELF intersections.

Despite the importance of the one-particle picture provided by the orbital paradigm, a rigorous understanding of the spatial distribution of electrons in molecules is still of paramount importance to chemistry. Considerable progress has been made following the introduction of topological approaches, capable of partitioning space into chemically meaningful regions. They usually provide atomic partitions, for example, through the attraction basins of the electron density in the quantum theory of atoms in molecules (QTAIM) or electron-pair decompositions, as in the case of the electron localization function (ELF). In both cases, the so-called electron distribution functions (EDFs) provide a rich statistical description of the electron distribution in these spatial domains. Here, we take the EDF concept to a new fine-grained limit by calculating EDFs in the QTAIM ∩ ELF intersection domains. As shown in AHn systems based on main group elements, as well as in the CO, NO, and BeO molecules, this approach provides an exquisitely detailed picture of the electron distribution in molecules, allowing for an insightful combination of the distribution of electrons between Lewis entities (such as bonds and lone pairs) and atoms at the same time. Besides mean-field calculations, we also explore the impact of electron correlation through Hartree-Fock (HF), density functional theory (DFT) (B3LYP), and CASSCF calculations.

Synergistic Strain Suppressing and Interface Engineering in Na4MnV(PO4)3/C for Wide-Temperature and Long-Calendar-Life Sodium-Ion Storage.

A Na4MnV(PO4)3 (NMVP) cathode is regarded as a promising cathode candidate for sodium-ion batteries (SIBs). However, issues such as low electronic conductivity and partial cation dissolution contribute to high polarization and structure distortion. Herein, we engineered the local electron density and reaction kinetic properties of NMVP cathodes with varying oxygen vacancies by introducing varying amounts of Zr doping and carbon coating. The optimized sample exhibited a high-rate capacity of 71.8 mAh g-1 at 30 C (83.1% capacity retention after 1000 cycles) and excellent performance over a wide temperature range (84.1 mAh g-1 at 60 °C and 61.4 mAh g-1 at -30 °C). In situ X-ray diffraction technology confirmed a redox solid solution and a two-phase reaction mechanism, revealing minor changes in cell volume and slight strain variations after Zr doping, effectively suppressing the structural distortion. Theoretical calculations illustrated that Zr doping largely shrinks the band gap of NMVP, enriches local electron density, and slightly alters the local element distribution and bond lengths. Moreover, full-cells have shown high energy density (259.9 Wh kg-1) and outstanding cycling stability (200 cycles). The work provides fresh insights into the synergistic effect of strain suppressing and interface engineering in promoting the development of wide temperature range and long-calendar-life SIBs.

Weak Bonding and Anharmonicity in Thermoelectric ZnSb

AbstractThe Zn─Sb binary system contains two high‐performing thermoelectric materials, namely the ordered ZnSb and the disordered Zn13Sb10. Both systems exhibit low thermal conductivity, which is speculated to originate from multicentre bonding within Zn2Sb2‐rhombi. Here, the electron density of ZnSb is reported based on multipole modelling of accurate X‐ray diffraction data measured at 20 K. Topological analysis reveals that the bond paths in the rhombus are endocyclically strained and that electron density is concentrated within the rhombus rather than along its geometric bonds consistent with a multicentre bond description. However, the electron density is not equally shared between the geometric bonds of the rhombus. Electron density analysis and modelling of low‐temperature anharmonicity reveal that one Zn–Sb interaction is weaker than the other. Taken together with the orientation of bonds external to the rhombus structure, an alternative description emerges wherein the multicentre bond is more partially localised along one set of the opposite legs of the rhombus. In this description, the stronger bond can be considered a traditional 2‐centre‐2‐electron bond, while the weaker interaction is coordinative to the covalent bond. The anharmonicity and low thermal conductivity may consequently be understood as Zn rattling along the coordinative interaction.

Pt on Atomic-Layered WO3 Islands: Electronic Tuning of Platinum-Tungsten Heterostructures for Highly Efficient Low-Temperature VOC Combustion.

Adjusting the electronic state of noble metal catalysts on a nanoscale is crucial for optimizing the performance of nanocatalysts in many important environmental catalytic reactions, particularly in volatile organic compound (VOC) combustion. This study reports a novel strategy for optimizing Pt catalysts by modifying their electronic structure to enhance the electron density of Pt. The research illustrates the optimal 0.2Pt-0.3W/Fe2O3 heterostructure with atomic-thick WO3 layers as a bulking block to electronically modify supported Pt nanoparticles. Methods such as electron microscopy, X-ray photoelectron spectroscopy, and in situ Fourier transform infrared spectroscopy confirm Pt's electron-enriched state resulting from electron transfer from atomic-thick WO3. Testing for benzene oxidation revealed enhanced low-temperature activity with moderate tungsten incorporation. Kinetic and mechanistic analyses provide insights into how the enriched electron density benefits the activation of oxygen and the adsorption of benzene on Pt sites, thereby facilitating the oxidation reaction. This pioneering work on modifying the electronic structure of supported Pt nanocatalysts establishes an innovative catalyst design approach. The electronic structure-performance-dependent relationships presented in this study assist in the rational design of efficient VOC abatement catalysts, contributing to clean energy and environmental solutions.

The evaluation for plasma noise in arbitrary time-delay interferometry combinations

The laser interferometer space antenna (LISA) uses laser interferometry to measure gravitational wave-induced distance changes between freely falling test masses on separate spacecraft. In practice, the space-borne gravitational wave detector operates in a plasma medium, and subsequently, the variations in electron density affect the refractive index and add displacement noise to measurements. Geometric time-delay interferometry (TDI) is the TDI combinations searched by geometric method, which is employed to mitigate overwhelming laser phase noise. This study explores all forty-five second-generation geometric TDI combinations up to sixteen links, analyzing plasma noise effects via power spectral density and cross-spectral density calculations for different optical links. Our findings reveal that plasma noise can exceed the noise floor, which comprises optical metrology system and test mass acceleration noise, in certain low-frequency regions due to different noise transfer behaviors. Further, we establish electron density requirements for various TDI combinations, showing that densities below 100cm−3/Hz @ 10mHz satisfy LISA’s criteria across all forty-five combinations. This allows for optimized TDI selection based on specific plasma densities.

Morphological study of incompetent saphenous veins: apoptosis and ultrastructural changes of smooth muscle cells.

Varicose veins affect approximately 25% of people in industrialized countries. The study aimed at detecting apoptotic cells and histopathological changes in varicose vein walls. Patients (N.=41) with varicose veins and 30 control group patients were divided into two groups according to their age (younger and older than 50 years). Apoptosis was determined by the TUNEL assay, elastin and collagen IV expression by immunohistochemistry and ultrastructural changes by transmission electron microscopy. The results show that the number of apoptotic cells in the layers of varicose veins increased, in particular in a group of patients aged over 50 years. In the varicose veins as compared to control veins the elastic fibers were found to be thinner, more fragmented and disorderly arranged. Elastin and collagen IV expression was found to decline in the intima and the media of varicose veins in both age groups. Electron microscopy demonstrated hypertrophy and degeneration of smooth muscle cells. Furthermore, cells with ultrastructural feature of apoptosis were noted. In the disorganized and expanded extracellular matrix membrane-bound vesicles, ghost bodies with different size and electron density were observed. Ghost bodies seem to bud off from smooth muscle cells and are likely to be involved in extracellular matrix remodeling as they are seen in close contact with collagen fibers. The study demonstrates increase of apoptotic cells in the wall of varicose veins along with vein wall structural abnormalities including alterations of smooth muscle cells and decline of elastin and collagen IV expression.

Analysis and design of fast flow liquid Li divertor for fusion nuclear science facility (FNSF) using coupled plasma boundary and LM MHD/heat transfer codes *

The SOLPS-ITER code is utilized to analyze the boundary plasma associated with a fast-flow lithium (Li) divertor configuration in the fusion nuclear science facility (FNSF) tokamak and identify operational regimes with acceptable divertor and core conditions. Plasma transport from the SOLPS-ITER code has been coupled with a liquid metal (LM) MHD/heat transfer code to model a Li open-surface divertor design and assess its impact on the scrape-off-layer (SOL) and core plasma performance. Simulations with only Neon (Ne) impurity seeding have been conducted to evaluate its impact on meeting FNSF design demands for the divertor and upstream plasma parameters. Simulation results indicate that Ne seeding significantly mitigates divertor heat flux but potentially reduces both upstream electron and main ion density due to fuel dilution. The combined application of Ne seeding and deuterium (D2) puffing is required to satisfy the FNSF design requirements on upstream density ( ne,sepOMP ∼1× 1020 m−3) and divertor energy flux ( q⊥,maxOdiv < 10 MW m−2). D2 puffing plays a role in counteracting upstream density drops and augmenting energy and momentum losses through atomic and molecular processes.The inlet Li flow velocity is systematically varied across a wide range to identify acceptable flows and corresponding LM surface temperatures. This comprehensive analysis identifies the acceptable Li flow parameters, LM surface temperature, and emitted Li fluxes necessary to meet the major design constraints. The emitted Li fluxes exhibit minimal impact on the main plasma at surface temperatures up to approximately ∼525 ∘C, corresponding emitted Li fluxes of up to φ Li ∼2 ×1023 atoms s−1. Uncertainties in the Li emission processes from the surface are also investigated, primarily influencing Li loss in the lower surface temperature range ( <525∘ C), with simulation results indicating a minor impact on the divertor and upstream plasma. Conversely, evaporation predominantly drives the Li loss processes at higher surface temperature ranges ( >525∘ C), contaminating both the divertor and upstream plasma.

The behavior of low-symmetry penta(chloro)cyclotriphosphazene-substituted monophthalocyanines in the oriented external electric fields

Electric field-mediated chemistry provides fertile ground for interdisciplinary research, where theoretical ideas and experimental data converge to unravel the complexities of molecular behavior under the influence of electric fields, offering unprecedented opportunities for scientific research and technological innovation. Thus, this work is devoted to the study underscoring the importance of oriented external electric fields (OEEFs) in modulating the structural and electronic properties of low-symmetry monophthalocyanines, which is crucial for enhancing their reactivity and nonlinear optical response. The highlight of this article is that the OEEFs lead to molecular conductivity due to reduced energy gap and electron density shifting towards the phosphazene ring. Additionally, there is a tendency for the elimination of chlorine atoms in the trans- position relative to the phthalocyanine macrocycle. Also, the use of the previously created CORRELATO algorithm has allowed the demonstration of the relationship between structural changes and microscopic parameters responsible for the appearance of NLO properties of final dye materials.

Surface engineering by rogue wave induced by energetic carbon clusters

Abstract Swift heavy ions are effective in nanostructuring of materials surfaces. The irradiation of lanthanum fluoride with 30 MeV C60 leads to the creation of surface nanohillocks of size larger than the ones produced by monoatomic heavy ions. The generation of the observed nano-sized hillocks are described here by a new approach, which is based on ion-induced intensive electronic excitations that create localised rogue waves. Consequently, the induced nonlinear ion-acoustic rogue waves are considered as a hallmark of nanohillocks formation. Plasma hydrodynamic equations produce a relationship between normalised electron number density and crystal lattice spacing. Similarities to the hillock profile suggest the crucial primary role of electron density in the fabrication of surface nanostructures.

An in-depth investigation of nonlinear optical properties of self-assembled borophene doped with P7Ba2NO3: a computational simulating study

Density functional theory was used to conduct a theoretical analysis of super salt doped on borophene. With the LanL2DZ basis set, which is appropriate for metal atoms, the B3LYP technique was used. Numerous analyses were used to characterize the structural properties, such as molecular geometry, frontier molecular orbital, non-covalent interaction, electron density difference map, molecular electrostatic potential, Density of States (DOS), UV–vis spectroscopy and infrared vibrational spectra analysis. The nonlinear optical characteristics were investigated through polarizability as well as hyperpolarizability calculations theoretically. The values were noticeably greater than those of borophene in all the above results. Compared to borophene, which has a hardness value of 0.905 eV, all the complexes exhibited small values of hardness, ranging from 0.41 eV to 0.795 eV. In addition, it was found that all the complexes had lower excitation energies as opposed to the greater excitation energy of borophene. Due to its lowest excitation energy (E), Boro@SS4 showed a striking increase in average polarizability ( αo = 847.13 au) in addition average first hyperpolarizability ( β0 = 540007.60 au) in comparison to borophene ( αo = 593.75 au and β0 = 383.76 au).

Scaling and merging macromolecular diffuse scattering with mdx2.

Diffuse scattering is a promising method to gain additional insight into protein dynamics from macromolecular crystallography experiments. Bragg intensities yield the average electron density, while the diffuse scattering can be processed to obtain a three-dimensional reciprocal-space map that is further analyzed todetermine correlated motion. To make diffuse scattering techniques more accessible, software for data processing called mdx2 has been created that is both convenient to use and simple to extend and modify. mdx2 is written in Python, and it interfaces with DIALS to implement self-contained data-reduction workflows. Data are stored in NeXus format for software interchange and convenient visualization. mdx2 can be run on the command line or imported as a package, for instance to encapsulate a complete workflow in a Jupyter notebook for reproducible computing and education. Here, mdx2 version 1.0 is described, a new release incorporating state-of-the-art techniques for data reduction. The implementation of a complete multi-crystal scaling and merging workflow is described, and the methods are tested using a high-redundancy data set from cubic insulin. It is shown that redundancy can be leveraged during scaling to correct systematic errors and obtain accurate and reproducible measurements of weak diffuse signals.