bluuebunny/crossref_metadata_2025 huggingface dataset:
Die Ökonomisierung des Sozialen und der Zwang zur Selbstoptimierung – Implikationen für die Einstellungen der Bevölkerung zu Menschen mit Schizophrenie
Authors: Matuschek Ingo , Angermeyer Matthias , Schomerus Georg
Published: November 2022

Die Einstellungen gegenüber Menschen mit Schizophrenie haben sich in den letzten Jahren verschlechtert. Wir argumentieren, dass dies mit einem Prozess der Ökonomisierung des Sozialen zusammenhängt, der insbesondere in der marktradikalen Fassung des Neoliberalismus den Wettbewerbscharakter in der Gesellschaft als prior platziert hat. Der kalkulatorische Umgang mit sich selbst ist individuell wie gesellschaftlich dominant. In den letzten Jahren ist daraus ein anhaltender Trend zur Selbstoptimierung entstanden, der auch inklusive Qualitäten besitzt: Wer mithält, gehört dazu. Auf der anderen Seite beinhaltet er aber auch eine exkludierende Qualität. Menschen mit Schizophrenie werden im Zuge dessen verstärkt als potenziell belastend bilanziert, als Minderung der eigenen Chancen. Dies trägt möglicherweise zu den beobachteten negativen Einstellungsveränderungen bei.
Sparing the Perineal Body: A Modification of the Posterior Sagittal Anorectoplasty for Anorectal Malformations with Rectovestibular Fistulae
Authors: Badillo Andrea , Tiusaba Laura , Jacobs Shimon Eric , Al-Shamaileh Tamador , Feng Christina , Russell Teresa Lynn , Bokova Elizaveta , Sandler Anthony , Levitt Marc A.
Published: November 2022

Background The posterior sagittal anorectoplasty (PSARP) used to repair an anorectal malformation (ARM) with a rectovestibular fistula involves incising the perineal body skin and the sphincter muscles and a posterior sagittal incision to the coccyx. Perineal body dehiscence is the most common and morbid complication post-PSARP which can have a negative impact on future bowel control. With consideration of all the other approaches described to repair this anomaly, we developed a perineal body sparing modification of the standard PSARP technique.

Methods Four patients with ARM with a rectovestibular fistula were repaired with a perineal body sparing modified PSARP at a single institution between 2020 and 2021. The incision used was limited, involving only the length of the anal sphincter, with no incision anterior or posterior to the planned anoplasty. Dissection of the distal rectum and fistula was performed without cutting the perineal body. Once the distal rectum was mobilized off the posterior vaginal wall and out of the vestibule, the perineal body muscles, where the fistula had been, were reinforced and an anoplasty was then performed.

Results Operative time was the same as for a standard PSARP. There were no intraoperative or postoperative complications. No postoperative dilations were performed. All patients healed well with an excellent cosmetic result. All are too young to assess for bowel control.

Conclusion We present a new technique, a modification of the traditional PSARP for rectovestibular fistula, which spares the perineal body. This approach could eliminate the potential complication of perineal body dehiscence.
Prevalence of synchronous neoplasia in patients with large pedunculated colorectal polyps
Authors: El Rahyel Ahmed , Lahr Rachel E. , Rex Douglas K.
Published: November 2022

Background Large (≥ 20 mm) nonpedunculated colorectal lesions have high rates of synchronous neoplasia and advanced neoplasia. Synchronous neoplasia prevalence in patients with large pedunculated lesions is uncertain. We describe synchronous neoplasia in patients with large pedunculated colorectal polyps, using a cohort of patients with large nonpedunculated lesions as controls.

Methods This study was a retrospective assessment of a prospectively recorded database listing synchronous findings in patients with ≥ 20 mm colorectal lesions referred to a tertiary center for endoscopic resection.

Results At least one synchronous precancerous lesion was identified in 66/78 patients with large pedunculated index lesions (84.6 %, 95 %CI 74.9–91.1) and 726/814 patients with large nonpedunculated index lesions (89.2 %, 95 %CI 87.1–91.3). Patients with a large pedunculated index lesion had mean of 4.8 synchronous conventional adenomas, 56.4 % had ≥ 1 synchronous high risk lesion (advanced adenoma or advanced serrated lesion), 48.7 % had ≥ 1 synchronous advanced conventional adenoma, and 19.2 % had a synchronous neoplastic lesion ≥ 20 mm. Compared with patients with nonpedunculated index lesions, patients with large pedunculated index lesions had comparable rates of synchronous polyps, adenomas, and sessile serrated lesions, and higher rates of synchronous adenomas with villous elements (15.6 % [95 %CI 13.3–18.3] vs. 26.9 % [95 %CI 18.3–37.7]; P = 0.01) and synchronous pedunculated polyps (9.5 % [95 %CI 7.6–11.7] vs. 33.3 % [95 %CI 23.8–44.4]; P < 0.001).

Conclusion In patients with large (≥ 20 mm) pedunculated colorectal lesions, rates of synchronous neoplasia and advanced synchronous neoplasia were high and comparable to or higher than rates of synchronous neoplasia in patients with large nonpedunculated colorectal lesions.
Cellular Integrative Immune Markers in Elite Athletes
Authors: Zacher Jonas , Wesemann Fabian , Joisten Niklas , Walzik David , Bloch Wilhelm , Predel Georg
Published: November 2022

The integrative immune markers neutrophil-lymphocyte-ratio (NLR),
platelet-lymphocyte-ratio (PLR) and systemic immune inflammation
index (SII) are established markers in clinical patient care. Adoption
of these markers in elite athletics might prove beneficial for monitoring
training and health. Blood samples of 195 healthy national Olympic squad
athletes were collected before a graded bicycle-ergometric exercise test until
complete exhaustion. Measurements included white blood cells, lymphocytes and
platelets, allowing for the calculation of the integrative immune markers.
Correlations between athlete characteristics (sex, age, sporting discipline,
training experience, training volume) and integrative immune marker-values were
assessed. In a subgroup analysis a second blood sample was collected from 25
athletes at 1 minute after exercise test to assess its effect on the
immune marker levels.

An inverse correlation between peak power output and SII-level (Pearson
correlation coefficient=−.270, p<.001) and NLR-level
(Pearson correlation coefficient=−.249, p<.001) was
found. Athletes with higher aerobic fitness had significantly lower values of
SII and PLR compared to athletes with lower aerobic fitness. An elevated SII
(p=.003) and a reduced PLR (p=.001) was documented as acute
response to the exercise test. The integrative immune markers might be a
promising tool for monitoring training and health in elite athletes.
The Essentials about Neonatal Severe Acute Respiratory Syndrome Coronavirus 2 Infection and Coronavirus Disease: A Narrative Review
Authors: De Luca Daniele , Vauloup-Fellous Christelle , Benachi Alexandra , Masturzo Bianca , Manzoni Paolo , Vivanti Alexandre
Published: November 2022

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection can occur in neonates as the virus can be transmitted both horizontally (from the environment) and vertically (during the pregnancy or at the delivery). Compared to the adult outbreak, neonatal infections do not represent a public health problem. Nonetheless, severe and life-threatening cases may rarely occur and both obstetricians and neonatologists should have a good knowledge of perinatal SARS-CoV-2 infection and related consequences. A high suspicion index must be applied and ruling out neonatal SARS-CoV-2 infection must become a part of the routine clinical workout. Moreover, neonates may be affected by the multisystem inflammatory syndrome, due to a dysregulated host response in the absence of any SARS-CoV-2 infection. We performed a narrative review to summarize here the available literature describing the essentials that should be known by every neonatologist and obstetrician, starting from what has been discovered in 2020 and adding what has been learned in the following years. The paper describes the mechanisms of transmission, clinical features, diagnostic tools, and criteria, as well as possible treatment and prevention strategies. The goal is to provide the practical points to be remembered at the bedside while caring for a pregnant woman or a neonate with suspected or proven coronavirus disease 2019 or multisystem inflammatory syndrome.

Key Points
Looking for dark matter with diamonds
Authors: Lim Alane
Published: November 2022

Current methods for quantum-sensing can be adapted to search for dark matter.
Keeping fine particles aloft in a plasma afterglow
Authors: Thompson Avery
Published: November 2022

A carefully applied electric field can keep floating particles from causing defects in semiconductor devices.
Tracing the network of scientific collaboration
Authors: Lim Alane
Published: November 2022

Scholar hyperdegree distribution can be modeled as a power law distribution.
An approach to the Gaussian RBF kernels via Fock spaces
Authors: Alpay Daniel , Colombo Fabrizio , Diki Kamal , Sabadini Irene
Published: November 2022

We use methods from the Fock space and Segal–Bargmann theories to prove several results on the Gaussian RBF kernel in complex analysis. The latter is one of the most used kernels in modern machine learning kernel methods and in support vector machine classification algorithms. Complex analysis techniques allow us to consider several notions linked to the radial basis function (RBF) kernels, such as the feature space and the feature map, using the so-called Segal–Bargmann transform. We also show how the RBF kernels can be related to some of the most used operators in quantum mechanics and time frequency analysis; specifically, we prove the connections of such kernels with creation, annihilation, Fourier, translation, modulation, and Weyl operators. For the Weyl operators, we also study a semigroup property in this case.
Fourth generation cryogenic neutral cluster beam apparatus for studying fundamental properties of metallic clusters
Authors: Miao Lin , Liu Zhaojun , Chen Zeyang , Wang Xiaohan , Zhou Ziwen , Zhao Jinbo , Fang Shaozheng , Yin Guangjia , Jia Zezhao , Liu Jin , Moro Ramiro , deHeer Walt A. , Ma Lei
Published: November 2022

A cryogenic beam apparatus for studying neutral clusters has been built and tested. The lowest beam temperature reaches less than 9 K at a repetition rate of 20 Hz. Mechanical decoupling from the refrigerator avoids misalignment during temperature ramping. Adopting a permanent magnet based magnetic deflector eliminates the hysteresis and electric noise of the traditional electromagnet and offers excellent reproducibility of the applied magnetic field. The mass spectrometer can operate in either Mass Spectroscopy Time-Of-Flight mode or Position-Sensitive Time-Of-Flight mode with spatial resolution better than 7 μm. Its performance is demonstrated with niobium and cobalt clusters.
Hypergraphon mean field games
Authors: Cui Kai , KhudaBukhsh Wasiur R. , Koeppl Heinz
Published: November 2022

We propose an approach to modeling large-scale multi-agent dynamical systems allowing interactions among more than just pairs of agents using the theory of mean field games and the notion of hypergraphons, which are obtained as limits of large hypergraphs. To the best of our knowledge, ours is the first work on mean field games on hypergraphs. Together with an extension to a multi-layer setup, we obtain limiting descriptions for large systems of non-linear, weakly interacting dynamical agents. On the theoretical side, we prove the well-foundedness of the resulting hypergraphon mean field game, showing both existence and approximate Nash properties. On the applied side, we extend numerical and learning algorithms to compute the hypergraphon mean field equilibria. To verify our approach empirically, we consider a social rumor spreading model, where we give agents intrinsic motivation to spread rumors to unaware agents, and an epidemic control problem.
First-principles redox energy estimates under the condition of satisfying the general form of Koopmans’ theorem: An atomistic study of aqueous iron
Authors: Shirani Javad , Farraj Sinan Abi , Yuan Shuaishuai , Bevan Kirk H.
Published: November 2022

In this work, we explore the relative accuracy to which a hybrid functional, in the context of density functional theory, may predict redox properties under the constraint of satisfying the general form of Koopmans’ theorem. Taking aqueous iron as our model system within the framework of first-principles molecular dynamics, direct comparison between computed single-particle energies and experimental ionization data is assessed by both (1) tuning the degree of hybrid exchange, to satisfy the general form of Koopmans’ theorem, and (2) ensuring the application of finite-size corrections. These finite-size corrections are benchmarked through classical molecular dynamics calculations, extended to large atomic ensembles, for which good convergence is obtained in the large supercell limit. Our first-principles findings indicate that while precise quantitative agreement with experimental ionization data cannot always be attained for solvated systems, when satisfying the general form of Koopmans’ theorem via hybrid functionals, theoretically robust estimates of single-particle redox energies are most often arrived at by employing a total energy difference approach. That is, when seeking to employ a value of exact exchange that does not satisfy the general form of Koopmans’ theorem, but some other physical metric, the single-particle energy estimate that would most closely align with the general form of Koopmans’ theorem is obtained from a total energy difference approach. In this respect, these findings provide important guidance for the more general comparison of redox energies computed via hybrid functionals with experimental data.
Design of a multi-detector, single line-of-sight, time-of-flight system to measure time-resolved neutron energy spectra
Authors: Schlossberg D. J. , Moore A. S. , Kallman J. S. , Lowry M. , Eckart M. J. , Hartouni E. P. , Hilsabeck T. J. , Kerr S. M. , Kilkenny J. D.
Published: November 2022

In the dynamic environment of burning, thermonuclear deuterium–tritium plasmas, diagnosing the time-resolved neutron energy spectrum is of critical importance. Strategies exist for this diagnosis in magnetic confinement fusion plasmas, which presently have a lifetime of ∼1012 longer than inertial confinement fusion (ICF) plasmas. Here, we present a novel concept for a simple, precise, and scale-able diagnostic to measure time-resolved neutron spectra in ICF plasmas. The concept leverages general tomographic reconstruction techniques adapted to time-of-flight parameter space, and then employs an updated Monte Carlo algorithm and National Ignition Facility-relevant constraints to reconstruct the time-evolving neutron energy spectrum. Reconstructed spectra of the primary 14.028 MeV nDT peak are in good agreement with the exact synthetic spectra. The technique is also used to reconstruct the time-evolving downscattered spectrum, although the present implementation shows significantly more error.
Supervised learning and the finite-temperature string method for computing committor functions and reaction rates
Authors: Hasyim Muhammad R. , Batton Clay H. , Mandadapu Kranthi K.
Published: November 2022

A central object in the computational studies of rare events is the committor function. Though costly to compute, the committor function encodes complete mechanistic information of the processes involving rare events, including reaction rates and transition-state ensembles. Under the framework of transition path theory, Rotskoff et al. [Proceedings of the 2nd Mathematical and Scientific Machine Learning Conference, Proceedings of Machine Learning Research (PLMR, 2022), Vol. 145, pp. 757–780] proposes an algorithm where a feedback loop couples a neural network that models the committor function with importance sampling, mainly umbrella sampling, which collects data needed for adaptive training. In this work, we show additional modifications are needed to improve the accuracy of the algorithm. The first modification adds elements of supervised learning, which allows the neural network to improve its prediction by fitting to sample-mean estimates of committor values obtained from short molecular dynamics trajectories. The second modification replaces the committor-based umbrella sampling with the finite-temperature string (FTS) method, which enables homogeneous sampling in regions where transition pathways are located. We test our modifications on low-dimensional systems with non-convex potential energy where reference solutions can be found via analytical or finite element methods, and show how combining supervised learning and the FTS method yields accurate computation of committor functions and reaction rates. We also provide an error analysis for algorithms that use the FTS method, using which reaction rates can be accurately estimated during training with a small number of samples. The methods are then applied to a molecular system in which no reference solution is known, where accurate computations of committor functions and reaction rates can still be obtained.
HP-TACO: A high-pressure triaxial compression apparatus for in situ x-ray measurements in geomaterials
Authors: Shahin G. , Hurley R. C.
Published: November 2022

Triaxial compression experiments are commonly used to characterize the elastic and inelastic behavior of geomaterials. In situ measurements of grain kinematics, particle breakage, stresses, and other microscopic phenomena have seldom been made during such experiments, particularly at high pressures relevant to many geologic and man-made processes, limiting our fundamental understanding. To address this issue, we developed a new triaxial compression device called HP-TACO (High-Pressure TriAxial COmpression Apparatus). HP-TACO is a miniaturized, conventional triaxial compression apparatus permitting confining pressures up to 50 MPa and deviatoric straining of materials, while also allowing in situ x-ray measurements of grain-scale kinematics and stresses. Here, we present the design of and first results from HP-TACO during its use in laboratory and synchrotron settings to study grain-scale kinematics and stresses in triaxially compressed sands subjected to 15 and 30 MPa confining pressures. The data highlight the unique capabilities of HP-TACO for studying the high-pressure mechanics of sands, providing new insight into micromechanical processes occurring during geologic and man-made processes.
Investigation of piezoelectric 0.65Pb(Mg1/3Nb2/3)O3–0.35PbTiO3 films in cross section using piezo-response force microscopy
Authors: Ursic Hana , Sadl Matej
Published: November 2022

Interest in the piezoelectric and ferroelectric properties of micro- and nanomaterials is increasing due to the advances being made in nanotechnology. However, there are only a few techniques that can detect functional properties at the nanoscale, and one of them is piezo-response force microscopy (PFM). So far, this technique has been mainly used to study surface properties of piezoelectric films. In this investigation, we develop a procedure to study films in the cross section by PFM and to investigate the relaxor-ferroelectric domain structure of pristine, screen-printed, and aerosol-deposited 0.65Pb(Mg1/3Nb2/3)O3–0.35PbTiO3 films in the cross section. Due to the different preparation methods used for two films, the grain size and, thus, the relaxor-ferroelectric domain structures differ. Micron-scale domains are observed in the screen-printed films, while sub micrometer-scale domains are found in the aerosol-deposited films. However, no change in the ferroelectric domain structures was observed across the thicknesses of the films.
Monitoring non-specific adsorption at solid–liquid interfaces by supercritical angle fluorescence microscopy
Authors: Au Aaron , Ho Man , Wheeler Aaron R. , Yip Christopher M.
Published: November 2022

Supercritical angle fluorescence (SAF) microscopy is a novel imaging tool based on the use of distance-dependent fluorophore emission patterns to provide accurate locations of fluorophores relative to a surface. This technique has been extensively used to construct accurate cellular images and to detect surface phenomena in a static environment. However, the capability of SAF microscopy in monitoring dynamic surface phenomena and changes in millisecond intervals is underexplored in the literature. Here, we report on a hardware add-on for a conventional inverted microscope coupled with a post-processing Python module that extends the capability of SAF microscopy to monitor dynamic surface adsorption in sub-second intervals, thereby greatly expanding the potential of this tool to study surface interactions, such as surface fouling and competitive surface adhesion. The Python module enables researchers to automatically extract SAF profiles from each image. We first assessed the performance of the system by probing the specific binding of biotin-fluorescein conjugates to a neutravidin-coated cover glass in the presence of non-binding fluorescein. The SAF emission was observed to increase with the quantity of bound fluorophore on the cover glass. However, a high concentration of unbound fluorophore also contributed to overall SAF emission, leading to over-estimation in surface-bound fluorescence. To expand the applications of SAF in monitoring surface phenomena, we monitored the non-specific surface adsorption of BSA and non-ionic surfactants on a Teflon-AF surface. Solution mixtures of bovine serum albumin (BSA) and nine Pluronic/Tetronic surfactants were exposed to a Teflon-AF surface. No significant BSA adsorption was observed in all BSA-surfactant solution mixtures with negligible SAF intensity. Finally, we monitored the adsorption dynamics of BSA onto the Teflon-AF surface and observed rapid BSA adsorption on Teflon-AF surface within 10 s of addition. The adsorption rate constant (ka) and half-life of BSA adsorption on Teflon-AF were determined to be 0.419 ± 0.004 s−1 and 1.65 ± 0.016 s, respectively, using a pseudo-first-order adsorption equation.
Synergistic effect of diatomic Mo–B site confined in graphene-like C2N enables electrocatalytic nitrogen reduction via novel mechanism
Authors: Li Yang , An Wei
Published: November 2022

Structural modulation of the active site with atomic-level precision is of great importance to meet the activity and selectivity challenges that electrocatalysts are commonly facing. In this work, we have designed a metal (M)–nonmetal diatomic site embedded in graphene-like C2N (denoted as Mo–B@C2N), where the electrocatalytic N2 reduction reaction (eNRR) was thoroughly explored using density functional theory combined with the computational hydrogen electrode method. Compared to M–M diatomic sites, the Mo–B site can generate a pronounced synergistic effect that led to eNRR proceeding via a novel quasi-dissociative reaction mechanism that has not been reported relative to the conventional enzymatic, consecutive, distal, and alternating associative mechanism. This newly uncovered mechanism in which N–N bond scission takes place immediately after the first proton-coupled electron transfer (PCET) step (i.e., *NH–*N + H+ + e− → *NH2*N) has demonstrated much advantage in the PCET process over the four conventional mechanism in terms of thermodynamic barrier, except that the adsorption of side-on *N2 seemed thermodynamically unfavorable (ΔGads = 0.61 eV). Our results have revealed that the activation of the inert N≡N triple bond is dominated by the π*-backdonation mechanism as a consequence of charge transfers from both the B and Mo sites and, unexpectedly, from the substrate C2N itself as well. Moreover, the hybrid Mo–B diatomic site demonstrated superior performance over either the Mo–Mo or B–B site for driving eNRR. Our study could provide insight into the delicate relationships among atomic site, substrate, and electrocatalytic performance.
Acoustic embedded eigenstates in metasurface-based structures
Authors: Hamzavi Zarghani Zahra , Monti Alessio , Alù Andrea , Bilotti Filiberto , Toscano Alessandro
Published: November 2022

Energy confinement plays an important role in improving wave–matter interactions, enabling applications such as sensing, lasing, and filtering. One convenient solution for achieving large energy-confinement is based on embedded eigenstates, i.e., non-radiating eigenmodes supported by open structures. While the analysis of these modes is quite consolidated in electromagnetics and optics, their relevance in acoustics has been less explored, despite their wide application potential. In this work, we explore acoustic embedded scattering eigenstates within the radiation continuum enabled by resonant metasurface pairs. At resonance, each metasurface strongly reflects the input wave, but as their surface resonances interfere with each other through coupling with a longitudinal resonance, an embedded eigenstate emerges. Through both theoretical and numerical analysis, we show the conditions for such an exotic resonant state to emerge and its implication for acoustic systems.
Partial-ionization deconfinement effect in magnetized plasma
Authors: Mlodik M. E. , Kolmes E. J. , Ochs I. E. , Rubin T. , Fisch N. J.
Published: November 2022

In partially ionized plasma, where ions can be in different ionization states, each charge state can be described as a different fluid for the purpose of multi-ion collisional transport. In the case of two charge states, transport pushes plasma toward equilibrium, which is found to be a combination of local charge-state equilibrium and generalized pinch relations between ion fluids representing different charge states. Combined, these conditions lead to a dramatic deconfinement of ions. This deconfinement happens on the timescale similar but not identical to the multi-ion cross-field transport timescale, as opposed to electron–ion transport timescale in fully ionized plasma. Deconfinement occurs because local charge-state equilibration enforces the disparity in diamagnetic drift velocities of ion fluid components, which in turn leads to the cross-field transport due to ion–ion friction.
Photophysics of β-Ga2O3: Phonon polaritons, exciton polaritons, free-carrier absorption, and band-edge absorption
Authors: Cheng Lu , Wu Yanlin , Zhong Wenbin , Chen Duanyang , Qi Hongji , Zheng Wei
Published: November 2022

Monoclinic gallium oxide (β-Ga2O3) has attracted much attention from the fields of optoelectronic and electronic devices owing to the properties of wide bandgap, great breakdown field strength, as well as the economic advantages of low-cost growth of large-size single crystals. Here, the basic photophysical properties including absorption (free-carrier absorption and band-edge absorption) and reflection (phonon polaritons and exciton polaritons) of differently doped β-Ga2O3 with diverse carrier concentrations are studied in detail. The unpolarized reflection spectra of differently doped β-Ga2O3 crystals are well fitted based on the non-polarized reflection model. Besides, according to analysis, the longitudinal–transverse splitting energy of β-Ga2O3 direct excitons is estimated to be as high as 100 meV, reflecting the strong interaction between light and excitons. It is hoped that this work can provide beneficial reference for a comprehensive understanding on the spectral physical characteristics of β-Ga2O3, so as to deepen and expand the basic recognition of this material in the aspect of photophysical properties.
The millimeter-wave spectrum of the SiP radical (X2Πi): Rotational perturbations and hyperfine structure
Authors: Burton M. A. , Sheridan P. M. , Ziurys L. M.
Published: November 2022

The millimeter/submillimeter-wave spectrum of the SiP radical (X2Πi) has been recorded using direct absorption spectroscopy in the frequency range of 151–532 GHz. SiP was synthesized in an AC discharge from the reaction of SiH4 and gas-phase phosphorus, in argon carrier gas. Both spin–orbit ladders were observed. Fifteen rotational transitions were measured originating in the Ω = 3/2 ladder, and twelve in the Ω = 1/2 substate, each exhibiting lambda doubling and, at lower frequencies, hyperfine interactions from the phosphorus nuclear spin of I = 1/2. The lambda-doublets in the Ω = 1/2 levels appeared to be perturbed at higher J, with the f component deviating from the predicted pattern, likely due to interactions with the nearby excited A2Σ+ electronic state, where ΔEΠ-Σ ∼ 430 cm−1. The data were analyzed using a Hund’s case aβ Hamiltonian and rotational, spin–orbit, lambda-doubling, and hyperfine parameters were determined. A 2Π/2Σ deperturbation analysis was also performed, considering spin–orbit, spin-electronic, and L-uncoupling interactions. Although SiP is clearly not a hydride, the deperturbed parameters derived suggest that the pure precession hypothesis may be useful in assessing the 2Π/2Σ interaction. Interpretation of the Fermi contact term, bF, the spin-dipolar constant, c, and the nuclear spin-orbital parameter, a, indicates that the orbital of the unpaired electron is chiefly pπ in character. The bond length in the v = 0 level was found to be r0 = 2.076 Å, suggestive of a double bond between the silicon and phosphorus atoms.
Orthorhombic distortion-induced anatase-like optoelectronic properties of rutile TiO2
Authors: Chen Binjie , Kang Kungwan , Jeen Hyoungjeen , Zhang Yuqiao , Lin Jinghuang , Feng Bin , Ikuhara Yuichi , Hoshino Sena , Matsunaga Katsuyuki , Ohta Hiromichi
Published: November 2022

Titanium dioxide (TiO2) is an excellent photocatalyst and transparent conducting oxide. It has two major crystal structures: rutile and anatase. Anatase TiO2 is valuable from an industrial point of view because it typically displays better photocatalytic and electronic transport properties than rutile TiO2. To further extract the functional properties of TiO2, understanding the correlation between the electronic structure and the crystal structure is essential. Because the electronic structure strongly depends on the crystal structure, introducing lattice distortion to rutile TiO2 should effectively modulate its electronic structure. Here, we show that Nb-doped rutile TiO2 epitaxial films on (11¯00) α-Al2O3 substrates exhibit anatase-like optoelectronic properties due to orthorhombic lattice distortions and experimentally observe the change in the electronic structure. Reducing the film thickness increases the orthorhombic distortion ratio (b/a) up to 3.4%. As b/a increases, the carrier effective mass decreases from 35 to 3 m0 (m0: electron mass) and the optical bandgap significantly increases. The present observations provide insight into regulating the TiO2 physical properties and should be beneficial for designing TiO2-based photocatalysts and transparent conducting electrodes.
Geometric defects induced by strain relaxation in thin film oxide superlattices
Authors: Webb Matthew , Ma Tao , Hunter Allen H. , McSherry Sean , Kaufman Jonathan , Deng Zihao , Carter William B. , Kioupakis Emmanouil , Esfarjani Keivan , Lenert Andrej , Heron John T.
Published: November 2022

Functional thin film superlattices with stability in extreme environments can lead to transformative performance in optical and thermal applications such as thermophotovoltaics. In this work, key issues associated with defects that prevent layer-by-layer growth in epitaxial, low-miscibility oxide superlattices are investigated. Layer protrusions, approximately 8 nm wide and 3 nm thick, arise from a strain relaxation mechanism in 8 nm bilayer superlattices of Ba(Zr0.5Hf0.5)O3/MgO and propagate through the subsequent superlattice layers forming an inverted pyramid structure that is spatially phase offset from the matrix. The density and size of these defects scales with the number of interfaces in the sample, indicating that surface roughness during growth is a significant factor in the formation of these defects. In situ high temperature transmission electron microscopy (1000 °C, in vacuo) measurement reveals that phase decomposition of Ba(Zr0.5Hf0.5)O3 and decoherence of the superlattice is nucleated by these defects. This work highlights that achieving optimum growth conditions is imperative to the synthesis of single-crystalline superlattices with sharp interfaces for optimized performance in extreme environments.
Effect of thermal oxidation on helium implanted 316L stainless steel
Authors: Hong Minsung , Morales Angelica Lopez , Chan Ho Lun , Macdonald Digby D. , Balooch Mehdi , Xie Yujun , Romanovskaia Elena , Scully John R. , Kaoumi Djamel , Hosemann Peter
Published: November 2022

The effect of thermal oxide layer on He implanted 316L stainless steel was studied to evaluate experimentally how thermal oxidation affects the diffusion and distribution of He in the material. In the case of thermal oxidation of a He implanted sample, with an increase in oxidation time, the max swelling height increases logarithmically as a function of time and finally saturates for all samples except for the lowest dose of implanted He. Concerning TEM results, two void regions are identified. Similar to the calculation, the total irradiated depth was around 250 nm and the large void region was formed around 100–150 nm depth. On the other hand, the small void region was observed immediately under oxide layer from the thermal oxidation. In contrast, there were no voids in the altered zone near the metal/oxide interface in the non-thermal oxidized/He implanted sample. This description of the phenomena was justified using the Kirkendall effect and the Point Defect Model.
On fault-mode phenomenon in no-insulation superconducting magnets: A preventive approach
Authors: Dong Fangliang , Park Dongkeun , Lee Wooseung , Hao Luning , Huang Zhen , Bascuñán Juan , Jin Zhijian , Iwasa Yukikazu
Published: November 2022

Here, we present experimental and analytical results of a preventive approach applied to a fault-mode phenomenon caused by electrodes or power-source failure in a no-insulation (NI) high-temperature superconducting REBa2Cu3O7−x (REBCO, RE = rare earth) magnet. It is generally agreed that the NI magnets, at least those of laboratory scale, are self-protected from overheating and, therefore, from quenching, chiefly because of turn-to-turn current bypassing unique to NI. However, these NI magnets do experience unexpected quenches, e.g., when the current through the magnet suddenly drops due to the aforementioned fault-mode phenomenon. Here, we report this phenomenon of a sudden-discharging-triggered quench of an NI REBCO coil, conduction-cooled, and operated at 4.2 K. We also present our preventive approach for this phenomenon that relies on an appropriately designed resistor shunted across the coil terminals. With this shunt resistor, a quench was prevented by suppressing the quench initiating turn-to-turn heat and induced overcurrent within the NI winding, and the coil current decayed safely.
A pragmatic protocol for determining charge transfer states of molecules at metal surfaces by constrained density functional theory
Authors: Meng Gang , Jiang Bin
Published: November 2022

Electron transfer from a metal surface to a molecule is very important at the gas–surface interface, which can lead to electron-mediated energy transfer during molecular scattering from the surface, as evidenced by numerous state-to-state molecular beam experiments of NO and CO scattering from noble metal surfaces. However, it remains challenging to determine relevant charge-transfer states and their nonadiabatic couplings from first principles in such systems involving a continuum of metallic electronic states. In this work, we propose a pragmatic protocol for this purpose based on the constrained density functional theory (CDFT) approach. In particular, we discuss the influence of the charge partitioning algorithm used in CDFT to define the constraint property in molecule–metal systems. It is found that the widely used Bader charge analysis is adequate to define the physically sound CDFT diabatic states corresponding to a molecule with or without extra electron transferred from the metal. Numerical tests validate that the proposed CDFT scheme properly describes the electron transfer behaviors in several benchmark systems, namely, NO or CO interacting with Au(111) or Ag(111). The effects of the surface work function and the molecular electron affinity on electron transfer are discussed in detail by comparing the CDFT states of the four systems. This pragmatic CDFT protocol lays the foundation for constructing accurate global diabatic potential energy surfaces for these important systems and can be generalized to study other interfacial electron transfer related problems.
On convective instabilities in a rotating fluid with stably stratified layer and thermally heterogeneous boundary
Authors: Garai Susmita , Sahoo Swarandeep
Published: November 2022

The onset of convection in a rotating plane layer due to a vertical temperature gradient is studied in this paper. The background stratification is modulated by lateral temperature variations and stable stratification aimed at understating the Earth's outer core convection subject to thermal core–mantle interaction. At the top boundary, sinusoidal and Gaussian temperature variations are imposed apart from the reference case of isothermal condition used in the classical Rayleigh–Benard convection. The additional modulating conditions break the top–bottom flow symmetry leading to flow localization and asymmetry that exhibit modified temporal dynamics unlike that of the classical Rayleigh–Benard cells. The threshold for convection is lowered with flows occurring in surplus heat flux regions caused by the imposed conditions. Despite flow suppression in the stable layer, rapid rotation favors the penetration of convection rolls with smaller wavelengths. The lateral variations in temperature imposed at the top boundary enhance such axial penetration with a laterally varying penetrative extent resulting in a modified clustered flow structure unlike the reference case. With both modulating conditions imposed, the onset of overstable modes is favored for low Prandtl numbers, a regime which is relevant to the Earth's core conditions. With rapid rotation, a novel mode of traveling wave instability occurs at the onset of convection, the propagation direction of which is controlled by the lateral temperature gradients at the top boundary. The onset of oscillatory modes is suppressed by the imposition of the modulating conditions indicated by the significant lowering of the transition Prandtl number.
Hydraulic loss analysis in a pump-turbine with special emphasis on local rigid vortex and shear
Authors: Yuan Zhiyi , Zhang Yongxue , Zhou Wenbo , Wang Cong
Published: November 2022

Since the pump as turbine is increasingly employed in energy storage, improving efficiency in both pump and turbine modes is required for economic benefits. This study aims to analyze vortex flow characteristics and vortex control methods in both modes to reduce hydraulic loss. In this paper, a delayed detached eddy simulation was applied in a low specific speed pump-turbine. Based on the entropy production analysis and vorticity binary decomposition in the local vortices, the results show that the local shear is the leading cause of hydraulic loss instead of the existence of vortices. The average wake loss can be 1.6 times higher than the loss in jet regions in pump mode, but there is little difference in the distribution of shear and vortices in the wake flow in turbine mode. The local loss caused by the rotor–stator interaction with a tongue effect at blade passing frequency is up to threefold over the loss without a tongue effect in both modes. Reducing shear and ratio of shear to rigid vorticity of the local vortices via modification in the volute tongue angle to suppress the tongue effect can be an effective way to decrease hydraulic loss in both modes.
Tailoring intersystem crossing of perylenediimide through chalcogen-substitution at bay-position: A theoretical perspective
Authors: Ahmed Raka , Manna Arun K.
Published: November 2022

Molecular-scale design strategies for promoting intersystem crossing (ISC) in small organic molecules are ubiquitous in developing efficient metal-free triplet photosensitizers with high triplet quantum yield (ΦT). Air-stable and highly fluorescent perylenediimide (PDI) in its pristine form displays very small ISC compared to the fluorescence due to the large singlet–triplet gap (ΔES−T) and negligibly small spin–orbit coupling (SOC) between the lowest singlet (S1) and triplet state (T1). However, its ΦT can be tuned by different chemical and mechanical means that are capable of either directly lowering the ΔES−T and increasing SOC or introducing intermediate low-lying triplet states (Tn, n = 2, 3, …) between S1 and T1. To this end, herein, a few chalcogen (X = O, S, Se) bay-substituted PDIs (PDI-X2) are computationally modeled aiming at introducing geometrical-strain at the PDI core and also mixing nπ* orbital character to ππ* in the lowest singlet and triplet excited states, which altogether may reduce ΔES−T and also improve the SOC. Our quantum-chemical calculations based on optimally tuned range-separated hybrid reveal the presence of intermediate triplet states (Tn, n = 2, 3) in between S1 and T1 for all three PDI-X2 studied in dichloromethane. More importantly, PDI-X2 shows a significantly improved ISC rate than the pristine PDI due to the combined effects stemming from the smaller ΔES−T and the larger SOC. The calculated ISC rates follow the order as PDI-O2 < PDI-S2 < PDI-Se2. These research findings will be helpful in designing PDI based triplet photosensitizers for biomedical, sensing, and photonic applications.
Novel nano-ZnO/alginate films with potential antibacterial properties
Authors: Zhang Shuping , Gao Yue , Li Yankai , Li Li , Wu Huiling
Published: November 2022

This study was conducted to develop nano-ZnO/alginate films with good mechanical properties and potent antibacterial activity as a new kind of wound dressing. The nano-ZnO/alginate films were prepared by a solvent casting method. Meanwhile, the thickness, water absorption and water vapour permeability (WVP) of alginate films with different alginate and glycerol contents were evaluated. Results show a positive influence of alginate and glycerol on the thickness and moisture sorption properties. In addition, the WVP of the films first increased and then decreased as the glycerol content increased, but it was not significantly affected by the concentration of alginate. Finally, the antimicrobial properties of the films were tested against E. coli and S. aureus, the results revealed that when the nano-ZnO content based on the film-forming solution was 0.25% (w/v) the films exhibited strong activity against both pathogens with a reduction in CFU of 99.48% for E. coli and 99.02% for S. aureus. The outcome of this study indicated that the nano-ZnO/alginate films could be used as a new kind of wound dressing.
Facile synthesis of Ti
Authors: Zhu Linyu , Ye Ruihao , Tang Peisong , Xia Pengfei
Published: November 2022

The layered Ti3C2 was successfully fabricated by etching the Al layer of Ti3AlC2 with the assistance of trifluoroacetic acid (TFA). By controlling the reaction time, the residual Ti3AlC2 phase in the Ti3C2 materials can be well removed by the TFA and the thickness of single Ti3C2 layer is ~10 nm. The absorption activity of the samples were also evaluated by adsorbing Congo red (CR) in the aqueous solution. The layered Ti3C2 exhibits much better absorption performance than that of pristine Ti3AlC2 and the maximum adsorption amount of CR is up to 351 mg g−1. This work develops a novel strategy to synthesize layered Ti3C2 without using the corrosive solvent.
My 37 years of working with nitrogen heterocycles and alkaloids
Authors: Pyne Stephen G.
Published: November 2022

This account highlights work from my laboratory at the University of Wollongong (UOW), concerning nitrogen heterocycles and alkaloids, from my appointment as lecturer in Chemistry in February 1985 to the present time as an Emeritus Professor since 2022. I am thankful to the Royal Australian Chemical Institute for the recognition of my work through the recent award of a Distinguished Fellow at the national conference in Brisbane in July 2022.
Structural reassignment of a dibenz[
Authors: Riches Andrew G. , Hart Christopher J. S. , Schmit Matthieu , Debele Emmanuel A. , Tiash Snigdha , Clapper Erin , Skinner-Adams Tina S. , Ryan John H.
Published: November 2022

A screen for compounds with antigiardial activity in the Compounds Australia Scaffolds library identified SN00797640 (supplied structure being 8-acylaminodibenzoxazepinone 1) as a hit compound with potent anti-parasitic activity (concentration for 50% growth inhibition of Giardia duodenalis, IC50 0.18 μM). To further explore the structure–activity relationships in this series, compound 1 and analogues, including its 7-acylaminodibenzoxazepinone regioisomer (2), were synthesized and assessed for anti-Giardia activity. While regioisomer 2 demonstrated antigiardial activity, resynthesized 1 and other 8-acylaminodibenzoxazepinone analogues were inactive. Comparison of spectroscopic and physical properties demonstrated the correct structure of SN00797640 to be 7-acylamino regioisomer 2. These results highlight the importance of independent synthesis in verifying the structure and activity of screening hits.
Ta/Cu transition region in TC4/Inconel718 bimetallic structure fabricated by laser deposition manufacturing
Authors: Chenyang Wang , Fei Xing , Guojian Xu , Xiangyu Liu , Hongyou Bian
Published: November 2022

The bimetallic structure formed by TC4 and Inconel718 has broad potential applications in aerospace. Based on the laser deposition manufacturing technique, a TC4/Inconel718 bimetallic structure was fabricated via the Ta/Cu transition layer. The test results indicated that a Ta/Cu transition region with a width of 475.0 μm was formed. The microstructure of the transition region changed from a reticular to a rod structure, and the corresponding phase compositions were β-Ta + Ti2Cu + TiCu and TiCu+γ-Cu + Cr2Ta. Owing to the formation of Ti–Cu and Cr–Ta phases in the transition region, the Vickers hardness reached 444.0 HV. The ultimate tensile strength was 280 MPa, and the fracture morphology presented a quasi-cleavage fracture, which occurred in the Ta/Cu transition region where Ti–Cu brittle phases exist.
REC drives recombination to repair double-strand breaks in animal mtDNA
Authors: Klucnika Anna , Mu Peiqiang , Jezek Jan , McCormack Matthew , Di Ying , Bradshaw Charles R. , Ma Hansong
Published: November 2022

Mechanisms that safeguard mitochondrial DNA (mtDNA) limit the accumulation of mutations linked to mitochondrial and age-related diseases. Yet, pathways that repair double-strand breaks (DSBs) in animal mitochondria are poorly understood. By performing a candidate screen for mtDNA repair proteins, we identify that REC—an MCM helicase that drives meiotic recombination in the nucleus—also localizes to mitochondria in Drosophila. We show that REC repairs mtDNA DSBs by homologous recombination in somatic and germline tissues. Moreover, REC prevents age-associated mtDNA mutations. We further show that MCM8, the human ortholog of REC, also localizes to mitochondria and limits the accumulation of mtDNA mutations. This study provides mechanistic insight into animal mtDNA recombination and demonstrates its importance in safeguarding mtDNA during ageing and evolution.