Axial Positions Research Articles

Electron temperature and ion density distribution on a vertical section in a weakly magnetized inductively coupled plasma

In this study, the distributions of electron temperature and ion density on a vertical section in a weakly magnetized inductively coupled plasma were measured using radially movable floating probes placed at different axial positions. The chamber used in this experiment included two cylindrical parts: a smaller radius top part with a planar antenna on the top quartz window and a larger radius downstream part. A magnet coil around the chamber top part maintained a divergent magnetic field in the discharge region. As the current in the magnet coil increased, the magnetic field also increased. Due to the variations of the radio frequency electric field in the plasma, the increase in electron temperature can be divided into different stages. At the higher magnetic field, the electric field of the electrostatic wave can increase electron temperature at the chamber center axial. Also, since the electron cyclotron resonance (ECR) heating in the chamber downstream part changed with the magnetic field, the maximum ion density was observed when the magnetic field around the bias electrode was slightly larger than the ECR magnetic condition. The reasons for these variations were verified in the plasma numerical simulations. The ion flux distribution measured on the bias electrode can change from a center-high distribution to an M-shape distribution with the increased magnetic field.

Structures and NMR Solution Dynamics of Diorganotin Complexes with Bulky Quadridentate Salen‐ and Salphen‐Type Schiff Bases (N2O2) Incorporating Diazenylpyridyl Side Arms

AbstractA series of six complexes [n‐Bu2Sn(L1)]⋅S (S=Benzene/toluene, mixed/partial) (1), [Ph2Sn(L1)]n⋅S (S=Benzene) (2), [Bz2Sn(L1)] (3), [n‐Bu2Sn(L2)]n (4), [Ph2Sn(L2)] (5) and [Bz2Sn(L2)] (6) were synthesized using diorganotin(IV) oxide precursors and two new bis‐Schiff bases containing N2O2 donor atoms. The Schiff bases, H2L1 and H2L2, were prepared by reacting ethane‐1,2‐diamine or benzene‐1,2‐diamine with 2‐hydroxy‐5‐(pyridin‐3‐yldiazenyl)benzaldehyde in absolute ethanol. Compounds 1–6 were characterized by IR and NMR spectroscopies, as well as by solid‐state single‐crystal X‐ray diffraction (except for 3 and 6). In all the complexes the bis‐Schiff bases occupy the equatorial positions and the R groups are in axial sites. However, while 1 and 5 are discrete molecules where the tin atoms adopt distorted octahedral geometries, 2 and 4 are monoperiodic polymers with the metal cations in pentagonal bipyramidal environments. Although solid state crystallographic results revealed asymmetrical molecular configurations, solution NMR studies proved symmetric arrangements for all the compounds. Tin NMR spectroscopy confirmed that all complexes are six‐coordinate in solution, despite variations in solid‐state coordination. Further analysis using Hirshfeld surface and fingerprint plots provided insights into intermolecular interactions in compounds 1, 2, 4, and 5. This comprehensive study underscores the structural diversity and solution‐state dynamics of organotin(IV) complexes synthesized using novel Schiff bases.

Migration of para-Nitrophenyl Groups in Methyl Pyranosides: Configuration and Conformation Determine the Kinetics.

para-Nitrophenyl (PNP) ethers of glycosides are important building blocks en route to functional carbohydrates. They are stable in neutral media, however, under basic conditions such as during the Zemplén deacylation of sugars, aryl migration is frequently observed. We have employed a library of O-PNP-substituted methyl glycosides of the manno-, galacto-, gluco- and altro-series to study the kinetics of aryl migration in MeOH/sodium methoxide using NMR spectroscopy revealing that migration between cis-oriented OH groups is faster than between trans-oriented ones. The rate constants of migration decrease in the order of Alt>Man>Gal>Glc and are related to the energy barriers of chair conformation inversion. The energy profile of the 3 to 4-PNP migration in methyl mannoside was calculated using DFT methods suggesting the Meisenheimer complex is an intermediate of PNP migration and that coordination of the sodium cation has a major impact on the energy profile.

Point spread function engineering enable resolution enhanced imaging for Interferenceless coded aperture correlation holography

The point spread function (PSF) of an optical system could characterize the resolving ability of the whole optical system for point light sources. Therefore, the imaging performance of the system could be significantly improved by regulating and optimizing the PSF. In this paper, we innovatively propose a single-exposure hologram resolution enhanced cross-correlation (RECC) method for Interferenceless coded aperture holography(I-COACH) system, circumventing the necessity to obtain the point spread hologram (PSH) of an ideal point object. The RECC method firstly acquires an approximate image of a large-size point object by Lucy-Richardson (LR) algorithm in lens imaging mode, and takes it as a PSF to acquire a PSH with ideal size of the I-COACH system by LR algorithm again, and finally acquires a reconstructed image by the single-exposure hologram RECC method. In the RECC method, the approximate ideal PSHs at different axial positions of the system are acquired by offline operation, therefore, it has a high imaging temporal resolution, and the imaging transverse resolution is not affected by the size of the point objects at the time of recording the PSH, which provides a high imaging signal-to-noise ratio and stable resolution. The proposed method provides powerful technical support for further extending the application field of the I-COACH system, and provides technical reference for other incoherent imaging.

Flow, Heat‐Transfer, and Mixing Behaviors of Scrap Steel in a Refining Ladle with Bottom Blowing

The flow, heat‐transfer, and mixing behaviors of steel scraps with different amounts, positions, and sizes added from the top of the bottom‐blown 300 t ladle are numerically investigated and compared through a coupled model. In the results, it is shown that it takes 59 s to mix the temperature of molten steel after adding scrap steel at the position of x = 0 mm, y = 553.5 mm, and z = 3375 mm. The further the addition position is from the axial position of the permeable brick, the shorter the mixing time of the speed and temperature of molten steel. For the scrap amount of 0.5, 1.5, and 2.5 t, the mixing time of molten steel temperature is 44, 78, and 47 s, correspondingly, which exhibits a pattern of initial increase followed by decrease, with an ≈8 K decline in molten steel temperature for every additional 1.0 t of scrap. When considering the scrap size of 10, 30, and 50 mm, the average temperature mixing time of molten steel is 44, 61, and 45 s, respectively. In this research, theoretical guidance can be can be provided for the addition of scrap in ladle during practical production processes.

An Axially CBD‐Containing Novel Pt(IV) Prodrug Designed to Synergistically Enhance Antitumor Activity by Inducing Mitochondrial Dysfunction

ABSTRACTIn recent years, significant attention has been given to the strategy of linking novel active molecules with different biological targets and antitumor mechanisms to the axial positions of Pt(IV) complexes, aiming to synthesize new Pt(IV) antitumor complexes with excellent properties. In this study, Satraplatin analogs and the highly lipophilic bioactive molecule cannabidiol (CBD) were chosen as the main research subjects. By combining these two and introducing other bioactive small molecules, we aimed to enrich the functionalities of Pt(IV) antitumor complexes. Five new multifunctional Pt(IV) antitumor complexes, P1–P5, were prepared. All Pt(IV) prodrugs demonstrated antitumor effects in various tumor cell lines. Notably, compound P1 exhibited significant inhibitory effects, with half‐maximal inhibitory concentration (IC50) values that were 2.1, 1.5, and 1.3 times higher than those of satraplatin in HCT‐116, A549, and HeLa cell lines, respectively, and 2.4, 1.5, and 2.0 times higher than those of the combination of satraplatin and CBD. The cytotoxicity of P1 toward cancer cell lines is significantly higher than that of the combination therapy group, providing preliminary evidence that the strategy of combining CBD and platinum‐based antitumor drugs into a complex is highly effective in simultaneously enhancing the cytotoxicity of both, resulting in a good synergistic antitumor effect. Further research shows that after treating cells with P1, the induced ROS generation increases in a dose‐dependent manner, disrupting the cell's redox homeostasis, leading to oxidative stress, and ultimately causing cell apoptosis. This strategy of introducing the bioactive molecule CBD into platinum‐based drug formation complexes to improve efficacy has been shown to be feasible and deserves further study.

MRI genicular nerve mapping: a novel approach to sagittal genicular nerve localization

Background and objectivesChronic knee pain, including postarthroplasty knee pain, is a major cause of morbidity. Radiofrequency ablation of genicular nerve branches is a treatment option. The literature to date has...

Crystal structure of [Ni(OH2)6]Cl2·(18-crown-6)2·2H2O

The crystal structure of the title compound, hexaaquanickel(II) dichloride–1,4,7,10,13,16-hexaoxacyclooctadecane–water (1/2/2), [Ni(H2O)6]Cl2·2C12H24O6·2H2O, is reported. The asymmetric unit contains half of the Ni(OH2)6 moiety with a formula of C12H32ClNi0.50O10 at 105 K and triclinic (P 1) symmetry. The [Ni(OH2)6]2+ cation has close to ideal octahedral geometry with O—Ni—O bond angles that are within 3° of idealized values. The supramolecular structure includes hydrogen bonding between the water ligands, 18-crown-6 molecules, Cl− anions, and co-crystallized water solvent. Two crown ether molecules flank the [Ni(OH2)6]2+ molecule at the axial positions in a sandwich-like structure. The relatively symmetric hydrogen-bonding network is enabled by small Cl− counter-ions and likely influences the more idealized octahedral geometry of [Ni(OH2)6]2+.

Photochemical and Collision-Induced Cross-Linking in Stereochemically Distinct Scaffolds of Peptides and Nitrile Imines in Gas-Phase Ions.

Intramolecular cross-linking between peptides and nitrile-imine intermediates was studied in stereochemically distinct conjugates in which the reacting components were mounted on cis-1,2-cyclohexane and trans-1,4-cyclohexane scaffolds that we call 1,2-s-peptides and 1,4-s-peptides, respectively. The nitrile-imine intermediates were generated by N2 loss from 2,5-diaryltetrazole tags upon UV-photodissociation at 213 and 250 nm or by collision-induced dissociation, and further interrogated by CID and UVPD-MS3. Peptide fragment ion series originating from linear structures and macrocyclic cross-links were distinguished and used to quantify the cross-linking yields. The yields in MS2 varied between 27% for AAAG conjugates to 78% for GAAAK conjugates, depending on the peptide sequence. The CID-MS3 yields were in a 57-97% range, depending on the peptide sequence. Structures of 1,2-s-peptide and 1,4-s-peptide ions as well as several of their nitrile-imine intermediates and cross-links were investigated by high-resolution cyclic ion mobility in combination with Born-Oppenheimer molecular dynamics and density functional theory calculations. Matches between the experimental and calculated collision cross sections and ion relative Gibbs energies were used to assign peptide structures. Peptide conjugates C-terminated with Gly and Lys residues underwent cross-linking by the carboxyl group, as established by MS3 sequencing and corroborated by carboxyl blocking experiments that lowered the cross-linking yields. Peptide conjugates C-terminated with Arg also cross-linked via the side-chain guanidine group. A notable feature of the 1,4-s-peptide ions was the participation of low-energy twist-boat cyclohexane conformers that was enforced by strong hydrogen bonds between the peptide and nitrile imine.

Parameters impact analysis on contact characteristics of intersected beveloid gear and involute cylindrical gear

According to gear geometry and tooth contact analysis (TCA) theory, the TCA model of intersected beveloid gear and involute cylindrical gear pair is built. The formulas for calculating curvature and contact ellipse at contact points are derived, and the shape and region of contact ellipse are determined. Then, the impacts of cone angle, helix angle and installation errors on contact characteristics are studied by numerical examples. The finite element model of gear pair is established to carry out the loaded tooth contact analysis (LTCA) and verify the accuracy of theoretical TCA model. The results show that gear pair with small cone angle or big helix angle has wide contact area, large carrying capacity and high transmission quality. The shaft angle error may cause the edge contact of gear pair, while the axial position error has limited effect. The research can provide input parameters for the study of tooth surface wear mechanism and dynamics in the future work.

Performance evaluation of an automatically controlled transcutaneous energy transfer system powering left ventricular assist device.

The survival rate of LVAD recipients may be improved by eliminating the infection failure mode at the percutaneous lead entry site. Wireless powering through a Transcutaneous Energy Transfer System (TETS) is a promising solution for achieving this. However, automatic controls need to be employed to compensate for the variations in efficiency and power transfer due to changes in load and coil-to-coil gaps. This article discusses the results of invitro and animal models performance evaluation of an automatically controlled TETS for powering a Left Ventricular Assist Device. It was found that power up to 20 W could be transferred at an axial gap of 30 mm. A 5% variation in speed and a 2% change in flow rate are observed with the change in tissue thickness, in porcine carcass model. The LVAD could be operated at the required RPM irrespective of the change in axial positions.

Vertically oriented low-dimensional perovskites for high-efficiency wide band gap perovskite solar cells.

Controlling crystal growth alignment in low-dimensional perovskites (LDPs) for solar cells has been a persistent challenge, especially for low-n LDPs (n < 3, n is the number of octahedral sheets) with wide band gaps (>1.7 eV) impeding charge flow. Here we overcome such transport limits by inducing vertical crystal growth through the addition of chlorine to the precursor solution. In contrast to 3D halide perovskites (APbX3), we find that Cl substitutes I in the equatorial position of the unit cell, inducing a vertical strain in the perovskite octahedra, and is critical for initiating vertical growth. Atomistic modelling demonstrates the thermodynamic stability and miscibility of Cl/I structures indicating the preferential arrangement for Cl-incorporation at I-sites. Vertical alignment persists at the solar cell level, giving rise to a record 9.4% power conversion efficiency with a 1.4 V open circuit voltage, the highest reported for a 2 eV wide band gap device. This study demonstrates an atomic-level understanding of crystal tunability in low-n LDPs and unlocks new device possibilities for smart solar facades and indoor energy generation.

Fiber Bragg Grating-based sensor for measuring supersonic inlet terminal shock at different angles of attack

This study presents a multipoint pressure measurement system using fiber Bragg grating sensors to detect terminal shock positions. The system consisted of a fiber optic string encapsulated with multiple diaphragm-based fiber Bragg grating sensors, capable of detecting flow field characteristics at fourteen different axial positions of the inlet. The calibration results indicated a sensitivity of 46.47 pm/kPa, a linear correlation coefficient of 0.9997, and a maximum repeatability error below 1.44%. In supersonic wind tunnel tests, the system effectively measured pressure and located the terminal shock across varying angles of attack and throttling degrees. The maximum difference compared to conventional pressure sensors was 4.7%, and the terminal shock positioning error was limited to 1.2%. Overall, the system has robust multipoint measurement capabilities and is priced at only one-tenth of traditional sensors, showing great potential in the field of inlet measurements.

Synthesis of the cis‐ and trans‐3‐Fluoro Analogues of Febrifugine and Halofuginone

The novel synthesis of racemic cis‐ and trans‐3‐fluorofebrifugine and halofuginone is described. This straight‐forward seven‐step process relies on an electrophilic fluorination‐allylation sequence generating a mixture of N‐Cbz protected, diastereomeric 2‐allyl‐3‐fluoropiperidines. On separation, a Wacker oxidation‐methyl functionalisation sequence enabled introduction of the required quinazolinone portion. Finally, removal of the N‐Cbz protecting group lead to isolation of the 3‐fluorofebrifugine dihydrobromide analogues that are of potentially pharmacological use. Analysis of the NMR spectra for each stereoisomer provides information concerning the preferred conformers of the different diastereomers. Evidence indicates that the cis‐diastereomer favours a conformation where the F‐atom occupies an axial orientation. In contrast, for its trans‐stereoisomeric counterpart, the 2‐substituent overrides any F‐atom effect and it preferentially occupies a conformer where both substituents occupy equatorial positions. Finally, interconversion between the cis‐ and trans‐diastereomers was studied. In DMSO‐d6 and as their free‐bases, isomerisation of each diastereomer gave a common 65:35 ratio of trans‐ to cis‐3‐fluorofebrifugine. Determination of the reaction rate constants for the isomerisation process at different temperatures enabled calculation of the activation energy barriers, for each process, using an Arrhenius plot. The activation energy barrier for the isomerisation of the trans‐isomer was 94.3 kJ mol‐1, whereas for the cis‐isomer it was 84.5 kJ mol‐1

Complex-valued scatter compensation in nonlinear microscopy

Nonlinear, i.e., multiphoton microscopy is a powerful technique for imaging deep into biological tissues. Its penetration depth can be increased further using adaptive optics. In this work, we present a fast, feedback-based adaptive-optics algorithm, termed C-DASH, for multiphoton imaging through multiple-scattering media. C-DASH utilizes complex-valued light shaping (i.e., joint shaping of amplitude and phase), which offers several advantages over phase-only techniques: it converges faster, it delivers higher image quality enhancement, it shows a robust performance largely insensitive to the axial position of the correction plane, and it has a higher ability to cope with, on the one hand, scattering media that vary over time and, on the other hand, scattering media that are partially absorbing. Furthermore, our method is practically self-aligning. We also present a simple way to implement C-DASH using a single reflection off a phase-only spatial light modulator. We provide a thorough characterization of our method, presenting results of numerical simulations as well as two-photon excited fluorescence imaging experiments. Published by the American Physical Society 2024

Experimental and theoretical studies of alkyl 2-(2,4,6,8-tetraaryl-3,7-diazabicyclo[3.3.1]nonan-9-ylidene)hydrazine carboxylates: Synthesis, spectroscopic, crystal structure, Hirshfeld surface, and antimicrobial studies

The nine alkyl 2-(2,4,6,8-Tetraaryl-3,7-diazabicyclo[3.3.1]nonan-9-ylidene)hydrazine carboxylates having bicyclic bispidine core were synthesized and characterized using FT-IR, NMR, and mass spectra. Further confirmation of the structure and positioning of the groups was obtained using single crystal XRD investigation. The analysis revealed that one piperidine ring adopts a chair and another a boat form. The aryl groups in the chair conformation are positioned equatorially, whereas those in the boat conformation are orientated axially. The carbazate group (C=N-NH-COOR) aligned the center of the two piperidine rings, with a small deviation towards the boat conformation piperidine ring. The dihedral angle between the chair and boat conformations of the piperidine ring (2f) is 48.51 Å and 45.12 Å, respectively. Hirshfeld and 2D fingerprint analysis show considerable H···H bonding interactions in the crystal. The intermolecular interaction and mechanical stability of crystals were investigated using interaction energy and crystal void analysis. Reduced density gradient and localized orbital locator analyses were used to investigate intramolecular interactions and electron delocalization. The molecule's higher and lower electron densities were investigated utilizing frontier molecular orbital analysis and Molecular Electrostatic Potential. The antimicrobial activity of the compounds was investigated using four bacterial and two fungus strains.

Design Issues and Solutions for Improving the Comfort of Neo-Ming Style Chair

This paper explores the design issues and solutions for improving the comfort of new Ming-style chairs. It first analyzes the historical origins, traditional aesthetics, and modern users' new demands for comfort in these chairs. Then, it highlights the comfort-related challenges in terms of chair form, materials, structure, and usage scenarios. The study proposes design principles from the perspectives of ergonomics, material innovation, structural optimization, and modern usage scenarios. Specific strategies to enhance comfort are provided, such as optimizing the angle between the chair back and chair surface, improving cushion materials, optimizing the chair's supporting structure, and incorporating intelligent design. This paper also discusses the challenges of integrating technology with traditional design, the application of eco-friendly materials, and the diverse demands of consumer groups. Finally, it summarizes the future trends and challenges in the comfort-focused design of Neo-Ming style chair.

Molecular Simulation of Cyclohexane in Nanoporous Materials: Adsorption of Conformers and Coadsorption with Water and Carbon Dioxide.

Molecular simulation is used to investigate the adsorption of an organic molecule and its different conformers into various nanoporous adsorbents. In more detail, we perform grand canonical Monte Carlo simulations to determine the adsorption isotherms for cyclohexane with its three conformers (chair, boat, and twisted boat) at three different temperatures into a molecular model of active carbons and two metal-organic frameworks (MOFs) (Cu-BTC and Al-Fum). By considering the adsorption of each conformer separately, we show that the adsorption isotherms are weakly dependent on the molecular conformation. When considering the concomitant adsorption of the three conformers under realistic conditions (to verify the population of each conformer in bulk mixtures), we show that the chair conformer is predominantly adsorbed in each material. However, such favorable adsorption mostly reflects the fact that this conformer has the largest population in the bulk mixture under the same thermodynamic conditions. On the contrary, with an increase in the cyclohexane gas pressure, the adsorption of boat and twisted boat conformers increases, while that of the chair conformer decreases as packing (entropy) effects become predominant during confinement. The adsorption of cyclohexane in the active carbon and MOF materials is also considered in the presence of water and CO2 atmospheres. In the case of the Al-fumarate material, the material is found to be strongly organophilic so that water and CO2 adsorption are negligible, and cyclohexane adsorption is not affected by competitive adsorption under any considered thermodynamic condition. On the contrary, for the active carbon and Cu-BTC material, competitive adsorption between cyclohexane and water or CO2 is observed even if cyclohexane adsorption remains preferred. While the different molecules coexist in the adsorbed phase at low pressures, increasing the cyclohexane pressure beyond 103 Pa promotes cyclohexane adsorption concomitantly with water and/or CO2 desorption.

Triptycene-Based Tripodal Molecular Platforms.

Molecular platforms are essential components of various surface-mounted molecular devices. Here, we document the synthesis of two universal triptycene-based tripodal pedestals featuring terminal alkynes in the axial position. We showcase their versatility by incorporating them into the structures of diverse functional molecules such as unidirectional light-driven molecular motors, photoswitches, and Brownian molecular rotors using standard cross-coupling reactions. We also present their fundamental physical properties, including acidity constants, data from differential scanning calorimetry, and crystallographic analysis of two parent and five derived structures. Finally, and importantly, we demonstrate that the photochemical properties of selected photoswitch representatives remain uncompromised when fused with tripods.

Linear‐ and Cyclo‐Hexa(amino)hexaboranes: New Routes to Synthesis of B6 Chain and B6 Ring

In this work, a linear‐hexaborane(8) B6(NMe2)6(CH2SiMe3)2 was synthesized using a new method. By replacing one chlorine atom of Cl2B3(NMe2)3 with CH2SiMe3 group, compound ClB3(NMe2)3CH2SiMe3 was prepared. Reductive dehalogenative coupling of ClB3(NMe2)3CH2SiMe3 led to linear‐hexaborane(8). Moreover, the six‐membered boron ring, cyclo‐hexaborane B6(NEt2)6 was synthesized by reductive dehalogenation of Br2BNEt2. The first linear‐hexaborane(8) and cyclo‐hexaborane B6(NEt2)6 crystal structures were fully characterized by X‐ray structural analysis and 11B, 1H, and 13C NMR spectroscopy. While the B1⋅⋅⋅⋅B6 chain in linear‐hexaborane(8) is strongly twisted at all B ̶ B bonds, the B6 ring cyclo‐hexaborane B6(NEt2)6 has a chair conformation similar to cyclohexane.