bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment
Authors: Zhao Dan , Kim Donghyun , Ghosh Sarbani , Wang Gang , Huang Wei , Zhu Zonglong , Marks Tobin J. , Zozoulenko Igor , Facchetti Antonio
Published: October 2023

Mechanically deformable polymeric semiconductors are a key material for fabricating flexible organic thin‐film transistors (FOTFTs)—the building block of electronic circuits and wearable electronic devices. However, for many π‐conjugated polymers achieving mechanical deformability and efficient charge transport remains challenging. Here the effects of polymer backbone bending stiffness and film microstructure on mechanical flexibility and charge transport are investigated via experimental and computational methods for a series of electron‐transporting naphthalene diimide (NDI) polymers having differing extents of π‐conjugation. The results show that replacing increasing amounts of the π‐conjugated comonomer dithienylvinylene (TVT) with the π‐nonconjugated comonomer dithienylethane (TET) in the backbone of the fully π‐conjugated polymeric semiconductor, PNDI‐TVT100 (yielding polymeric series PNDI‐TVTx, 100 ≥ x ≥ 0), lowers backbone rigidity, degree of texturing, and π–π stacking interactions between NDI moieties. Importantly, this comonomer substitution increases the mechanical robustness of PNDI‐TVTx while retaining efficient charge transport. Thus, reducing the TVT content of PNDI‐TVTx suppresses film crack formation and dramatically stabilizes the field‐effect electron mobility upon bending (e.g., 2 mm over 2000 bending cycles). This work provides a route to tune π–π stacking in π‐conjugated polymers while simultaneously promoting mechanical flexibility and retaining good carrier mobility in FOTFTs.
Real‐Time Tuning Exciton‐Plasmon Coupling with Photosensitive Nanocavity
Authors: Han Xiaobo , He Zijian , Zhao Dong , Hu Huatian , Li Shujin , Yuan Meng , Wang Kai , Lu Peixiang
Published: October 2023

A novel method is proposed to directly characterize the exciton‐plasmon coupling in a photosensitive nanoparticle‐on‐mirror (NPoM) nanocavity. Under the illumination of UV light, the localized surface plasmon resonance (LSPR) peaks of the nanocavity can be continuously tuned over a wide range (≈65 nm), enabling precise determination of the energy dispersion relationship of plexcitons in the nanocavity. The results indicate that the energy of Rabi splitting can be actively tuned from 65 meV (weak coupling) to 170 meV (strong coupling) by adjusting the LSPR peak of a specific nanocavity (particle size L≈55‐92 nm) to the exciton wavelength (the zero detuning). In addition, the criterion of strong coupling is optimized by introducing single‐particle absorption spectroscopy. The work offers an intuitive method for the strong coupling characterization in nanocavity, paving the way for the real‐time tuning of coupling strength over a wide range (100 meV) from weak to strong coupling regimes.
A Room Temperature High‐Performance Visible‐Light‐Assisted NO2 Gas Sensor Based on Ultrathin Zinc Oxysulfide
Authors: Ha Nam , Xu Kai , Cheng Yinfen , Ou Rui , Ma Qijie , Hu Yihong , Trinh Vien , Ren Guanghui , Zhang Jiaru , Ou Jian Zhen
Published: October 2023

Metal oxysulfides are an emerging group of sensitive materials for high‐performance NO2 sensing owing to their room‐temperature operation capacity, excellent selectivity of NO2, the part‐per‐billion‐leveled limit of detection, as well as high stability against the ambient environment. Here, the room‐temperature NO2 sensing performances of zinc oxysulfide 3D micro‐self‐assembly composed of ultrathin nanoflakes are investigated. The combined hydrothermal–annealing approach is applied to first synthesize zinc sulfide micro‐self‐assembly and then transform it into zinc oxysulfide in a controlled environment. As a result, the majority of S atoms in zinc sulfide are replaced with O atoms, leading to the crystal structure variation from cubic/hexagonal to an orthorhombic configuration. Simultaneously, the corresponding optical bandgap is reduced from ≈3.6 – 3.8 eV to ≈1.92 eV, enabling the visible light harvesting capability. The sensor demonstrates a fully reversible and repeatable sensing response toward 1.26 ppm NO2 gas at room temperature with a response magnitude of ≈2.27 under the 460 nm excitation, a limit of detection (LOD) of 294.8 part‐per‐trillion (ppt), and almost an order of magnitude larger compared to other commonly used gas species. This work demonstrates the great potential of the metal oxysulfide framework for developing next‐generation room‐temperature NO2 gas sensors.
Porous 3D Printed System for Synergistic Tandem Water Cleaning‐Energy Generation
Authors: Ghosal Pranjal , Parui Arko , Singh Abhishek K. , Kumbhakar Partha , Gupta Ashok K , Tiwary Chandra S.
Published: October 2023

Non‐availability of fresh water is the dire consequence of rapid industrialization and the unregulated discharge of industrial effluents. In an attempt to recover water from highly contaminated industrial wastewater, researchers have relied on developing various materials that can treat polluted water efficiently and sustainably. 3D printed materials have proved to be an emerging technology in water treatment. 2D materials have recently enhanced filter technology due to their morphological properties. This study focuses on removing salinity and organic dyes utilizing 2D Gadolinium telluride (Gd2Te3 ) coated 3D printed (2D@3DP) complex architecture. The 2D@3DP structure can potentially increase the contact time of adsorbed saline water due to its complex architecture and can remove ≈52% salinity from brackish water. Furthermore, methylene blue (MB) and Methyl Orange (MO) removal efficiencies are ≈69% and 45%, respectively. Spectroscopic and microscopic results confirm the adsorption of negatively charged chlorine ions on a positively charged 2D surface. The removal of bleaching powder is also tested for real‐life applications, and ≈20% of the bleaching powder is adsorbed. Moreover, the 2D@3DP device exhibits an electrical signal due to impinging sodium chloride droplets from different heights, making it a sustainable solution to address water pollution.
Electronic Flat Band in Distorted Colouring Triangle Lattice
Authors: Li Yaqi , Zhai Shuwei , Liu Yani , Zhang Jingwei , Meng Ziyuan , Zhuang Jincheng , Feng Haifeng , Xu Xun , Hao Weichang , Zhou Miao , Lu Guang‐Hong , Dou Shi Xue , Du Yi
Published: October 2023

Dispersionless flat bands (FBs) in momentum space, given rise to electron destructive interference in frustrated lattices, offer opportunities to enhance electronic correlations and host exotic many‐body phenomena, such as Wigner crystal, fractional quantum hall state, and superconductivity. Despite successes in theory, great challenges remain in experimentally realizing FBs in frustrated lattices due to thermodynamically structural instability. Here, the observation of electronic FB in a potassium distorted colouring triangle (DCT) lattice is reported, which is supported on a blue phosphorene‐gold network. It is verified that the interaction between potassium and the underlayer dominates and stabilizes the frustrated structures. Two‐dimensional electron gas is modulated by the DCT lattice, and in turn results in a FB dispersion due to destructive quantum interferences. The FB exhibits suppressed bandwidth with high density of states, which is directly observed by scanning tunneling microscopy and confirmed by the first‐principles calculation. This work demonstrates that DCT lattice is a promising platform to study FB physics and explore exotic phenomena of correlation and topological matters.
Design on Formation of Nickel Silicide by a Low‐Temperature Pulsed Laser Annealing Method to Reduce Contact Resistance for CMOS Inverter and 6T‐SRAM on a Wafer‐Scale Flexible Substrate
Authors: Hsu Yu‐Chieh , Chen Yan‐Yu , Shieh Jia‐Min , Huang Wen‐Hsien , Shen Chang‐Hong , Chueh Yu‐Lun
Published: October 2023

A pulsed laser annealing method is utilized to directly synthesize nickel silicide (NiSi) as a contact material to improve the contact of electric devices. Three laser wavelengths, 355 nm (ultraviolet laser), 532 nm (green laser), and 1064 nm (infrared laser), are used for the NiSi synthesis during the pulsed laser annealing process. A NiSi phase with low sheet resistance is formed by an ultraviolet laser annealing (ULA) process without damaging the polyimide (PI) substrate. With the integration of the ULA process‐induced NiSi into p‐nnel MOSFET (PMOS) and n‐channel MOSFET (NMOS) devices, the on/off ratio improves significantly, and the field‐effect mobility increases by 30% because of the reduction in contact resistance from 21 to 8.5 kΩ. In addition to the PMOS and NMOS, the gains of the CMOS inverter at different Vdd values are improved by at least 30%. Moreover, the static noise margin of 6T‐SRAM is elevated from 0.82 to 1 V at Vdd = 4 V. The ability of the ULA process to synthesize a high‐quality NiSi layer on a flexible substrate is demonstrated. The integration of NiSi into electrical devices offers a new pathway for improving the electrical behavior of flexible devices.
Synergistic effects of substrate inoculation with Pseudomonas strains on tomato phenology, yield, and selected human health‐related phytochemical compounds
Authors: Issifu Muazu , Naitchede Labode Hospice Stevenson , Ateka Elijah Miinda , Onguso Justus , Ngumi Victoria Wambui
Published: October 2023

Plant growth‐promoting rhizobacteria enhances nutritional availability during root colonization. Pseudomonas is the most popular bioinoculant due to its synergistic effects on plant development. This study evaluated the impact of four Pseudomonas strain substrate inoculations on tomato phenology, yield, and selected phytochemical components relevant to human health. The bacterial isolates have been characterized morphologically, biochemically, physiologically, and phylogenetically. Tomato plants on cocopeat substrate were inoculated individually with a bacterial suspension (optical density [OD]600 2.0). Controls included nitrogen–phosphate–potassium (NPK) fertilizer and tap water. The greenhouse experiment was laid out in a completely randomized design with five replications. Data were taken 30, 60, 90, and 120 days after inoculation. All four bacterial isolates could fix nitrogen, solubilize phosphate, and potassium and synthesize indole acetic acid in vitro. The 16S rRNA of the strains BF1P2‐6, BF2P1‐2, BF2P5‐1, and BF4P2‐5 were identified as Pseudomonas putida Y22, Pseudomonas taiwanensis GDLB‐32, Pseudomonas monteilii Bil‐NOR3_15, and Pseudomonas fluorescens Y5, respectively. The strains grew best at pH 7, NaCl 0.0%, and 35°C. Inoculated tomato plants tested over a period of 4 months in a greenhouse showed a significant increase in growth, leaf variables, and yield attributes. Pseudomonas‐inoculated plants were the highest in tannins (46.96 mg/100 g), followed by lycopene (45.57 mg/100 g) and Carotenoids (31.87 mg/100 g). The antioxidant activity of tomato fruit extracts showed the potential for free radicals scavenging activity against 2, 2‐diphenyl‐1‐picrylhydrazyl. Conditions such as pH and electrical conductivity for the cocopeat substrate were within acceptable limits. Bacterial strains and NPK increased cocopeat nitrogen, phosphate, and potassium bioavailability. This study reveals that Pseudomonas strains improve plant growth, yield, and health‐related phytochemical substances in tomato fruits, which could broaden their application in fruit and vegetable crops.
Requirements for hospitals in Japan to have low operative mortality and failure‐to‐rescue rates
Authors: Endo Itaru , Takahashi Arata , Tachimori Hisateru , Miyata Hiroaki , Homma Yuki , Kumamoto Takafumi , Matsuyama Ryusei , Kakeji Yoshihiro , Kitagawa Yuko , Seto Yasuyuki
Published: October 2023

Aim

We explored institutional factors in Japan associated with lower operative mortality and failure‐to‐rescue (FTR) rates for eight major gastrointestinal procedures.

Methods

A 22‐item online questionnaire was sent to 2119 institutional departments (IDs) to examine the association between institutional factors and operative mortality and FTR rates. IDs were classified according to the number of annual surgeries, board certification status, and locality. In addition, the top 20% and bottom 20% of IDs were identified based on FTR rates and matched with the results of the questionnaire survey. Factors associated with operative mortality were selected by multivariate analysis.

Results

Of the 1083 IDs that responded to the questionnaire, 568 (213 382 patients) were included in the analysis. Operative morbidity, operative mortality, and FTR rates in the top 20% and bottom 20% of IDs were 13.1% and 8.4% (p < 0.001), 0.52% and 4.3% (p < 0.001), and 4.0% and 51.2% (p < 0.001), respectively. Based on the patients' background characteristics, the top 20% of IDs handled more advanced cases. No significant difference in locality was seen between better or worse hospital FTR rates, but fewer esophagectomies, hepatectomies, and pancreatoduodenectomies were performed in depopulated areas. Six items were found to be associated with operative mortality by multivariate logistic analysis. Only 50 (8.8%) IDs met all five factors related to better FTR rates.

Conclusions

The present findings indicate that several hospital factors surrounding surgical treatment, characterized by abundant human resources, are closely related to better postoperative recovery from severe complications.
Modular Customization and Regulation of Metal–Organic Frameworks for Efficient Membrane Separations
Authors: Shu Lun , Peng Yuan , Song Hongling , Zhu Chenyu , Yang Weishen
Published: October 2023

Metal–organic frameworks (MOFs) are considered ideal membrane candidates for energy‐efficient separations. However, the MOF membrane amount to date is only a drop in the bucket compared to the material collections. The fabrication of an arbitrary MOF membrane exhibiting inherent separation capacity of the material remains a long‐standing challenge. Herein, we report a MOF modular customization strategy by employing four MOFs with diverse structures and physicochemical properties and achieving innovative defect‐free membranes for efficient separation validation. Each membrane fully displays the separation potential according to the MOF pore/channel microenvironment, and consequently, an intriguing H2/CO2 separation performance sequence is achieved (separation factor of 1656–5.4, H2 permeance of 964–2745 gas permeation unit). Taking advantage of this strategy, separation performance can be manipulated by a non‐destructive modification separately towards the MOF module. This work establishes a universal full‐chain demonstration for membrane fabrication‐separation validation‐microstructure modification and opens an avenue for exclusive customization of membranes for important separations.
Structural and Catalytic Insight into the Unique Pentacyclic Triterpene Synthase TwOSC
Authors: Luo Yunfeng , Ma Xiaoli , Qiu Yufan , Lu Yun , Shen Siyu , Li Yang , Gao Haiyun , Chen Kang , Zhou Jiawei , Hu Tianyuan , Tu Lichan , Zhao Huan , Li Dan , Leng Faqiang , Gao Wei , Jiang Tao , Liu Changli , Huang Luqi , Wu Ruibo , Tong Yuru
Published: October 2023

The oxidosqualene cyclase (OSC) catalyzed cyclization of the linear substrate (3S)‐2,3‐oxidosqualene to form diverse pentacyclic triterpenoid (PT) skeletons is one of the most complex reactions in nature. Friedelin has a unique PT skeleton involving a fascinating nine‐step cation shuttle run (CSR) cascade rearrangement reaction, in which the carbocation formed at C2 moves to the other side of the skeleton, runs back to C3 to yield a friedelin cation, which is finally deprotonated. However, as crystal structure data of plant OSCs are lacking, it remains unknown why the CSR cascade reactions occur in friedelin biosynthesis, as does the exact catalytic mechanism of the CSR. In this study, we determined the first cryogenic electron microscopy structure of a plant OSC, friedelin synthase, from Tripterygium wilfordii Hook. f (TwOSC). We also performed quantum mechanics/molecular mechanics simulations to reveal the energy profile for the CSR cascade reaction and identify key residues crucial for PT skeleton formation. Furthermore, we semirationally designed two TwOSC mutants, which significantly improved the yields of friedelin and β‐amyrin, respectively.
Urea‐catalyzed N‐Glycosylation of Amides/Azacycles with Glycosyl Halides
Authors: Wei Meng‐Man , Ma Yu‐Feng , Zhang Gao‐Lan , Li Qin , Xiong De‐Cai , Ye Xin‐Shan
Published: October 2023

The efficient synthesis of N‐glycosides via direct N‐glycosylation of amides/azacycles has been reported. The glycosylation of amides/azacycles with glycosyl halides in the presence of a catalytic amount of urea proceeded smoothly to provide the corresponding N‐glycosylated amides or nucleosides in good to excellent yields with 1,2‐trans‐stereoselectivity. Moreover, by the addition of terpyridine, the 1,2‐cis‐stereoselectivity was achieved.
Untersuchung der Polarisationserscheinungen an Elektroden aus glattem Platin mit Hilfe von Ladekurven
Authors: Giner J.
Published: October 2023

Mit Hilfe von Ruhespannungs(ϵR) Messungen, Ladekurven [ϵ(t)J‐Kurven] und Nachpolarisationskurven [ϵ(t)J=0‐Kurven] wird das elektrochemische Verhalten der Pt‐Elektrode hauptsächlich in 1n H2SO4‐Lösung in stromlosem Zustand (Ruhezustand) sowie bei anodischer bzw. kathodischer Belastung untersucht.

Die genannten Meßmethoden zeigen übereinstimmend, daß keine definierten Oxyde sondern Chemisorptionsschichten von Sauerstoff das Verhalten der Elektrode bestimmen.

Aus der Form der Ladekurven kann man auf den Bedeckungsgrad von chemisorbiertem Sauerstoff schließen. Die Ruhespannung ist um so positiver, je größer der Bedeckungsgrad ist. Diese Bedeckung kann entweder durch anodische Belastung oder durch chemische Oxydation (Vorbehandlung mit Chromschwefelsäure) erzeugt werden. Die Bedeckung wird kleiner durch kathodische Belastung.

Bei der Aufnahme anodischer Ladekurven an einer Elektrode, die bereits im Ruhezustand eine starke Sauerstoff‐Belegung aufweist, treten charakteristische Doppelstufen auf, die wahrscheinlich zwei Teilschritten in der Chemisorption entsprechen.

Die Ladekurven zeigen ferner, daß vor der H2‐Entwicklung eine Chemisorption von atomarem Wasserstoff auftritt. Insbesondere lassen die intermittierten Ladekurven darauf schließen, daß bei 1 n H2SO4 die Reaktion:

keine merkliche Überspannung besitzt. Dagegen ist die Reaktion:

sehr gehemmt.

In neutralen und alkalischen Lösungen zeigt auch die erstgenannte Elektrodenreaktion eine gewisse Überspannung.

Auch der Einfluß einer vorgegebenen O2‐Atmosphäre auf das Verhalten der Pt‐Elektrode im Ruhezustand und bei Belastung wird untersucht.
Die Mischungswärmen des Antimons mit B‐Metallen. I. Die Systeme mit Zink und Cadmium
Authors: Wittig Franz Eberhard , Gehring Eckard
Published: October 2023

Zur weiteren Prüfung des Verhaltens der Mischungswärmen der B‐Metalle wurden die Systeme des Antimons mit B‐Metallen untersucht. In den Systemen mit Zink und Cadmium ergeben sich gewisse Abweichungen aus dem zusätzlichen Einfluß einer heteropolaren Bindung. Diese äußert sich in einem Minimum der ξ‐Kurve und einem stufenförmigen Verlauf der partiellen Mischungswärmen im Bereich der stöchiometrischen Zintl‐Phase und wird nach Wagner durch einen Elektronenübergang auf das Antimon gedeutet. Es treten aber Abweichungen vom idealen Verlauf auf. Der zusätzliche Einfluß der heteropolaren Bindung führt zu Abweichungen von der sonst bei Systemen der B‐Metalle gültigen Gruppenregel.
Molecular Beam Investigations of Bimolecular Reactions
Authors: Toennien J. P.
Published: October 2023

In the present review the attempt has been made to relate the molecular beam results on chemical reactions to the macroscopic reaction rate constants. The review starts with a summary of the phenomenological description of bimolecular reactions. The advantages and disadvantages of this simple description are pointed out. In the second section the collision theory of rate constants is derived and the Boltzmann equation for calculating the rate of a macroscopic reaction under extreme conditions is introduced. The connection between reactive cross sections and chemical forces is emphasized. In the third section the crossed molecular beam method is decribed. Recent measurements of the following properties of reactive collisions are then reviewed: angular distribution of products, integral reactive cross sections, internal excitation of the products and, finally, orientation dependence of reactive cross sections. The review ends with a brief interpretation of the beam data in terms of chemical forces.
Schwefelkohlenstoff‐Oxydation, Geschwindigkeit von Elementarreaktionen Teil I
Authors: Homann K. H. , Krome G. , Gg. Wagner H.
Published: October 2023

Die bei der Oxydation von CS2 stattfindenden Elementarreaktionen wurden bei vermindertem Druck bis zu Temperaturen von 1450 °K bei starker Inertgasverdünnung im isothermen Strömungssystem untersucht. In dem angegebenen Temperaturbereich ergaben sich für die Reaktionsgeschwindigkeiten in Arrhenius‐Darstellung folgende Ausdrücke:

magnified image

Für die folgenden Reaktionen ließen sich die Geschwindigkeitskonstanten größenordnungsmäßig bestimmen: T ∼ 1100 °K.

magnified image
Die Geschwindigkeit der Reaktion von atomarem Wasserstoff mit Azetylen. (I)
Authors: Hoyermann K. , Gg. Wagner H. , Wolfrum J.
Published: October 2023

Die Reaktion H + C2H2 wurde in einem Strömungssystem untersucht, das an ein ESR‐ und ein Massenspektrometer angeschlossen war. Dabei wurde das Reaktionsschema durch Isotopenaustausch mit D‐Atomen geklärt, und die Messung der Reaktionsgeschwindigkeit erfolgte über einen weiten Bereich von Druck (0,5–30 Torr) und Temperatur (243–463 °K). Aus den Messungen kann man mit Hilfe der Theorien unimolekularer Reaktionen die Geschwindigkeitskonstante des ersten Schrittes bestimmen.
Verteilung der Geschwindigkeitskonstanten für den monomolekularen Zerfall feldionisierter Moleküle
Authors: Tenschert G. , Beckey H. D.
Published: October 2023

The kinetics of unimolecular decomposition of field ionized organic molecules was studied over a continuous range of life times from several times 10−11 sec to several times 10−6 sec. A retarding potential technique was developed for this purpose. The electric field was low enough in that range for drawing some general conclusions on the unimolecular decomposition of large organic ions in the field free case: There exists a continuous range of average velocity constants k̄(t) = − d N(t)/N(t) · dt in the time interval from several times 10−11 to several times 10−6 sec, for ions such as n‐heptane and tert. butyl benzene.
Berechnung der Aktivierungsenergie für den Ligandenaustausch an übergangsmetallionen in Lösung
Authors: Breitschwerdt K.
Published: October 2023

Für den Fall schwacher Ligandenfelder, wie er für Ionen der ersten übergangsmetallreihe und Wassermoleküle als Liganden vorliegt, wurden die Energien der Konfigurationen d1 bis d9 als Funktion von Eigenschaften und Position der Liganden in den Symmetrien C4ν, D3b und D5b in Einheiten der Ligandenfeldtermaufspaltung Dq bestimmt. Die Matrixelemente der betreffenden Ligandenpotentiale wurden mit Hilfe der Methode der Äquivalenzoperatoren berechnet. Für die Radialverteilung der Ladungsdichte der 3d‐Elektronen wurden Ergebnisse von SCF‐Rechnungen zugrunde gelegt.

Die Aktivierungsenergien für den Ligandenaustausch, die sich als Differenz der Energien im Übergangszustand und im Gleichgewichtszustand ergeben, zeigen dieselbe doppelte Periodizität innerhalb der Übergangsmetallreihe wie die experimentell bestimmten Geschwindigkeitskonstanten für den Ligandenaustausch. Darüber hinaus sind für einen Übergangszustand mit Symmetrie C4ν, bei dem sich der zu substituierende Ligand gerade so weit vom Zentralion entfernt hat, daß der neue Ligand seinen Platz einnehmen kann, die berechneten Aktivierungsenergien in guter quantitativer Übereinstimmung mit den experimentellen Werten. Daraus ergibt sich, daß der Ligandenaustausch über einen SN1‐Mechanismus erfolgt.
The hydrolysis of 1‐chloro 2‐nitro ethane, chloro diphenyl methane and benzoyl chloride in dioxane‐water mixtures at 1–1000 at
Authors: Büttner D. , Heydtmann H.
Published: October 2023

The rate constants for the hydrolysis reactions of 1‐chloro 2‐nitro ethane, chloro diphenyl methane and benzoyl chloride in dioxane‐water mixtures were determined between 1 and 1000 at. The reaction of water with 1‐chloro 2‐nitro ethane, which is of the SN2 type, was studied at 70 °C in the solvent range of 9.8–49.3 weigth‐% water. The reaction of water with chloro diphenyl methane, which is of the SN1 type, was studied at 25 and 50 °C in the solvent range of 9.8–36.0 weight‐% water. The hydrolysis of benzoyl chloride, for which different mechanisms have been proposed, was studied at 25 °C in the solvent range of 4.3–29.3 weight‐% water. The volumes of activation for the total pressure range and the apparent molar volumes of the reactants for 1 at were determined and an interpretation of the volumes as functions of the solvent composition was attempted.
Indirekte Kernspinkopplung in den Methyl‐, Silyl‐ und Hydridverbindungen der VI. Hauptgruppe
Authors: Pfisterer G. , Dreeskamp H.
Published: October 2023

Die Konstanten der indirekten Kernspinkopplung wurden durch Doppelresonanz in den Verbindungen der VI. Hauptgruppe O(CH3)2, S(CH3)2, Se(CH3)2, Te(CH3)2, Se2(CH3)2, Te2(CH3)2, (CH3)SeTe(CH3), O(SiH3)2, S(SiH3)2, Se(SiH3)2, CH3OH, CH3SH, CH3SeH und SeHD mit Vorzeichen relativ zu 1J′CH > 0 bestimmt. Die normierten Konstanten 1J′XC und 1J′XSi sind negativ (X = 77Se und 125Te), während 1J′SeH und 1J′SeTe positiv sind (1J′SeTe = – 169 Hz). Der Anstieg von | 1J′| mit der Ordnungszahl der koppelnden Kerne wird durch die Zunahme des Kernspin‐Elektronenspin‐Kontaktterms interpretiert. 2JHD in SeHD ist negativ wie auch 2JCH in den CH3XH‐Verbindungen, während 2J′XH in allen Fällen positiv ist. Die vicinalen Konstanten 3JHH, 3JCH und 3J′SiH sind alle positiv, wobei 3JCH mit steigender Ordnungszahl des Zentralatoms regelmäßig abnimmt. Für 4JHH wurden Werte im Bereich von 0 bis + 0,7 Hz gefunden. Die Absolutwerte der Konstanten 2JCC nehmen von 2,4 Hz in O(CH3)2 bis 0,2 Hz in Te(CH3)2 ab. 1JSeH ist relativ stark abhängig von Temperatur, Konzentration und Isotopensubstitution. Mit diesen experimentellen Daten wird der Mechanismus der indirekten Spinkopplung diskutiert. In einigen Fällen wurde ein positiver sekundärer Isotopeneffekt auf die chemische Verschiebung von 1H, 77Se und 125Te durch 2H und 13C‐Substitution beobachtet.
Kernresonanzuntersuchungen am 1.10‐Phenanthrolin und seinen Komplexverbindungen. Teil III. H1‐Messungen zur Protonenanlagerung am 1.10‐Phenanthrolin
Authors: Rosenberger H. , Pettig M. , Madeja K. , Engelhardt G. , Radeglia R.
Published: October 2023

Es werden H1‐Kernresonanzmessungen zur Protonenanlagerung am 1.10‐Phenanthrolin mit unterschiedlichen Säuren (HCl und CF3COOH) in verschiedenen Lösungsmitteln (CH3OH, CH3CN, DMSO) beschrieben. In allen Fällen wird ein schneller Protonenaustausch der NH+‐Protonen festgestellt, der auch bei −80 °C nicht „eingefroren”︁ werden kann. Bei Protonierung werden alle H1‐Resonanzen zu tiefen Feldern in der Reihenfolge Δ δ4 > Δ δ3 > Δ δ5 > Δ δ2 verschoben. Für das freie, mono‐und diprotonierte 1.10‐Phenanthrolin wurden EHT‐Gesamtelektronenrechnungen ausgeführt. Die beste Übereinstimmung zwischen experimentell und theoretisch bestimmten Elektronendichten für das protonierte 1.10‐Phenanthrolin besteht bei Annahme kleiner formaler Ladungen am Stickstoff (Δ = 0,0 bis + 0,3).
Die Überführungswärme von Frenkel‐Defekten in AgBr
Authors: Weiss K.
Published: October 2023

An der Zelle (–)(Pt)(T′,Ag)/AgBr/(Pt,T″)(Pt)(+) sind die anisothermen Polarisationsströme bei Temperaturen zwischen 325 und 370 °C gemessen worden. Weiterhin wurde die Thermokraft von Elektronen in silbergesättigtem AgBr bei 370 °C bestimmt. Aus den Messungen kann die Summe der Überführungswärmen der ionischen und elektronischen Defekte berechnet werden. Auf Grund einfacher Modellvorstellungen für die Elektronen im Leitungsband schätzt man die Überführungswärme der Elektronen zu RT/2 ab; damit kann man aus den Messungen Zahlenwerte für die Überführungswärme der fehlgeordneten Kationen und das chemische Potential der Elektronen angeben.
Gasdiffusionsmessungen zwischen 273 und 1300 °K
Authors: Schneider Manfred , Schäfer Klaus
Published: October 2023

Eine neue Apparatur zur Messung des Diffusionskoeffizienten von Gasen wird beschrieben. Sie kann in einem sehr weiten Bereich der Temperatur eingesetzt werden.

Die bei den Gaspaaren H2–N2, H2–CO2, He–Ar und N2–CO2 zwischen 273 und 1300 °K gemessenen Diffusionskoeffizienten sowie die aus diesen ermittelten Parameter für Lennard‐Jones‐(6‐n)‐Potentiale werden mitgeteilt.
Kraftkonstantenberechnung nach dem Frequenzgangverfahren
Authors: Fadini A.
Published: October 2023

Zur Berechnung einer beliebigen reellen Kraftkonstantenmatrix aus der mathematisch möglichen Lösungsmannigfaltigkeit von F wird ein Iterationsverfahren dargestellt. Zur Aufstellung einer Ausgangsmatrix werden reduzierte Lineargleichungen der Isotopenreduktionsmethode und der Gruppentheorie verwendet. Diese reduzierten Lineargleichungen stellen zugleich exakte Auswahlregeln zur Auffindung der physikalischen Kraftkonstantenmatrix Fphys aus F dar.
Die säurekatalysierte Isomerisierungsreaktion des trans‐Diaquo‐dioxalato‐chrom‐(III)‐Anions in wäßriger Lösung
Authors: Kelm H. , Stieger H. , Harris G. M.
Published: October 2023

Die Geschwindigkeit der Isomerisierungsreaktion des trans‐[Cr(C2 O4)2(H2O)2]−‐Ions wurde in Abhängigkeit von der Säure‐konzentration gemessen. Während die Geschwindigkeitskonstante der Reaktion bis in den Bereich von 0,6 molarer Säure eine Proportionalität zur titrimetrisch bestimmten Wasserstoffionenkonzentration zeigt, steigt sie bei höherer Säurekonzentration mehr als proportional an. Mit Hilfe der modifizierten Hammettschen Aciditätsfunktion konnte die Starke Beschleunigung der Reaktion als Säurekatalyse gedeutet werden, wobei das Komplexion in einem dem geschwindigkeitsbestimmenden Schritt vorgelagerten Gleichgewicht protoniert wird. Sowohl der ermittelte Deuteriumisotopieeffekt der Reaktion und seine Abhängigkeit von der Säurekonzentration als auch die Ergebnisse in D2 O‐H2O‐Mischungen und ihre Deutung durch die Gross‐Butler‐Gleichung stützen den angenommenen Mechanismus der Säurekatalyse.
Ultraviolettspektrum und Reaktionen des HO2‐Radikals im thermischen Zerfall von H2O2
Authors: Troe J.
Published: October 2023

Im thermischen Zerfall von H2O2 tritt unter geeigneten Bedingungen das HO2‐Radikal als Zwischenprodukt in vergleichsweise hohen Konzentrationen auf. Aus diesem Grunde eignet sich das System besonders zu einer Suche nach einem Elektronenspektrum des Radikals. Dazu wurde der thermische Zerfall von H2O2 hinter reflektierten Stoßwellen in Argon als Trägergas im Bereich 950 < T < 1450 °K untersucht. Neben dem Absorptionskontinuum von H2O2 wurde im Bereich 2200–2800 Å ein weiteres Absorptionskontinuum gefunden. Der zeitliche Verlauf dieser Absorption stimmt bei unterschied‐lichen experimentellen Bedingungen sehr gut mit dem für das HO2‐Radikal zu erwartenden Profil überein. Bei Zuordnung dieses Spektrums zum HO2 läßt sich nach Analyse der Rolle des HO2 im Zerfallsmechanismus von H2O2 der Verlauf des Absorptionskoeffizienten abschätzen.
Zur Reaktion H + H + H2O → H2 + H2O
Authors: Eberius H. , Hoyermann K. , Wagner H. Gg.
Published: October 2023

Die Rekombinationsreaktion von Wasserstoffatomen in Gegenwart von Wasser

Wurde in einem Strömungssystem mit einem ESR‐ und einem Massenspektrometer untersucht. Für die Geschwindigkeitskonstante dieser Reaktion bei T = 303 °K ergab sich der Wert von
Die Abhängigkeit des zweiten Virialkoeffizienten und der Transportphänomene in Gasen von den Exponenten des Lennard‐Jones‐Potentials
Authors: Schramm Bernbard
Published: October 2023

Die zur Berechnung der Transportgrößen in Gasen und Gasmischungen notwendigen Stoßintegrale für mehrere Lennard‐Jones‐n‐ 7‐Potentiale wurden berechnet und in Abhängigkeit von der reduzierten Temperatur T*=kT.ϵ tabelliert. Zusammen mit den schon früher veröffentlichten Tabellen für die Stoßintegrale einiger n‐6‐Potentiale [8] ist damit die Möglichkeit gegeben, den Einfluß einer Änderung der Exponenten n und m der Lennard‐Jones‐n‐m‐Potentiale auf die Transportgrößen systematisch zu untersuchen. Eine solche Untersuchung wird hier vorgelegt. Sie schließt den zweiten Virialkoeffizienten in die Überlegungen mit ein. Durch die Einfühmng geeigneter reduzierter Größen gelingt es, die Unterschiede der einzelnen n‐m‐Potentiale zu erfassen, ohne auf Meßdaten zurückzugreifen.
über die 1H‐NMR‐Spektren linearer Di‐Aza‐Acene und ihrer N‐Oxyde
Authors: Limbach Hans‐Heinrich , Seiffert Wolfgang , Ohmes Ernst , Zimmermann Herbert
Published: October 2023

Die 1H‐NMR‐Spektren von Chinoxalin I, Chinoxalin‐N‐monooxyd II, Chinoxalin‐N,N‐dioxyd III, Phenazin IV, Phenazin‐N‐monooxyd V, Phenazin‐N,N‐dioxyd VI, Benzo[g]chinoxalin VII, Benzo[b]phenazin VIII, Benzo[b]phenazin‐N‐monooxyd IX, Benzo[b]phenazin‐N,N‐dioxyd X, Dibenz[b,i]phenazin XI wurden gemessen. Die chemischen Verschiebungen und Kopplungskonstanten wurden auf iterativem Weg durch Angleich von experimentellen und berechneten Spektren bestimmt. Einige Konzentrations‐ und Lösungsmittelabhängigkeiten der chemischen Verschiebungen werden diskutiert.
Die Schwingungsspektren des flüssigen Fluors
Authors: Jacob E. , Goubeau J.
Published: October 2023

IR‐ und Ramanspektren des flüssigen Fluors wurden im Bereich innermolekularer Schwingungen gemessen. Um die sehr schwache IR‐Absorption unbeeinflußt von polaren, stark absorbierenden Verunreinigungen registrieren zu können, mußte besonderes Augenmerk auf Reinigung und Manipulation des F2 gelegt werden. Es wird eine IR‐Tieftemperaturküvette für flüssiges Fluor beschrieben.
Kinetik der Manganat/Permanganat‐Redoxelektrode an Platin und Gold
Authors: Plieth W. J.
Published: October 2023

Im Redoxsystem Manganat/Permanganat in In NaOH wurden an Platin‐ und Goldelektroden potentiostatische Einschaltmessungen durchgeführt. Aus den Strom‐Zeitkurven können durch Extrapolation auf t = 0 Anfangsstromdichten bestimmt werden. Die Anfangsstromdichte‐Potentialkurven ergeben bei kleinen Überspannungen den Durchtrittswiderstand und die Austauschstromdichte i0. Bei größeren Überspannungen besteht zwischen dem Logarithmus der Anfangsstromdichte und dem Potential eine lineare Tafel‐Beziehung. Die Tafel‐Geraden zeigen charakteristische Besonderheiten. Die Durchtrittsfaktoren α+ und α− ergänzen sich nicht zu eins. Die elektrochemischen Reaktionsordnungen sind nicht ganzzahlig, zum Teil ergeben sich negative Werte. Die Schnittpunkte der anodischen und kathodischen Tafel‐Geraden mil der Ordinate bei ϵ = ϵ0 ergeben Austauschstromdichten i0,+i0,‐ ≠ i0. Das beobachtete Verhalten kann quantitativ beschrieben werden mit einem Durchtrittsmechanismus aus zwei konsekutiven Teilreaktionen. Die Teilreaktionen sind die Adsorptions/Desorptionsreaktionen der Redoxkomponenten.
Economic simulation of batch and continuous aqueous two‐phase purification for viral products
Authors: Nold Natalie M. , Pearson Eric , Heldt Caryn L.
Published: October 2023

Vaccine manufacturing strategies that lower capital and production costs could improve vaccine access by reducing the cost per dose and encouraging localized manufacturing. Continuous processing is increasingly utilized to drive lower costs in biological manufacturing by requiring fewer capital and operating resources. Aqueous two‐phase systems (ATPS) are a liquid–liquid extraction technique that enables continuous processing for viral vectors. To date, no economic comparison between viral vector purifications using traditional methods and ATPS has been published. In this work, economic simulations of traditional chromatography‐based virus purification were compared to ATPS‐based virus purification for the same product output in both batch and continuous modes. First, the modeling strategy was validated by re‐creating a viral subunit manufacturing economic simulation. Then, ATPS capital and operating costs were compared to that of a traditional chromatography purification at multiple scales. At all scales, ATPS purification required less than 10% of the capital expenditure compared to chromatography‐based purification. At an 11 kg per year production scale, the ATPS production costs were 50% less than purification with chromatography. Other chromatography configurations were explored, and may provide a production cost benefit to ATPS, but the purity and recovery were not experimentally verified. Batch and continuous ATPS were similar in capital and production costs. However, manual price adjustments suggest that continuous ATPS plant‐building costs could be less than half that of batch ATPS at the 11 kg per year production scale. These simulations show the significant reduction in manufacturing costs that ATPS‐based purification could deliver to the vaccine industry.
The Challenge and Obstacles of Becoming an iSchool: The Case of Zadar, Croatia
Authors: Aparac‐Jelušić Tatjana
Published: October 2023

EDITOR'S SUMMARY

The journey of the University of Zadar's Department of Information Sciences to iSchool recognition reflects the challenging requirements for an academic institution to attain that status. The department was accredited in 2014, with undergraduate and graduate programs evolving from the Department of Librarianship, accredited since 2005. The department co‐publishes a scientific journal, organizes professional conferences, operates a joint graduate program with other universities, promotes active involvement in international professional organizations and encourages collaboration with universities around the world to promote student exchange studies. Admission requirements, curricula and professional competencies follow recommendations for all levels of study, with special focus at the doctoral level on supporting Croatia's written heritage. Having demonstrated institutional dedication to the field of information sciences and support of robust academic study, the department's sole remaining obstacle for full recognition as an iSchool is stable research funding.
Second Chance Pell sets stage for rapid expansion of prison college programs
Authors: D’Orio Wayne
Published: October 2023

WASHINGTON, D.C. — Higher education is in need of some good news. Polls constantly show the public's faith in the importance of higher education is sliding, and to top it off, an enrollment cliff is imminent.
The tumor suppressive effect and apoptotic mechanism of TRAIL gene‐containing recombinant NDV in TRAIL‐resistant colorectal cancer HT‐29 cells and TRAIL‐nonresistant HCT116 cells, with each cell bearing a mouse model
Authors: Jung Bo‐Kyoung , An Yong Hee , Jang Sung Hoon , Ryu Gyoungah , Jung Saet‐byel , Kim Seonhee , Kim Cuk‐Seong , Jang Hyun
Published: October 2023

Background

TRAIL is an anticancer drug that induces cancer cell apoptosis by interacting with death receptors (DRs). However, owing to low cell‐surface expression of DRs, certain colorectal cancer (CRC) cells resist TRAIL‐induced apoptosis. Newcastle disease virus (NDV) infection can elevate DR protein expression in cancer cells, potentially influencing their TRAIL sensitivity. However, the precise mechanism by which NDV infection modulates DR expression and impacts TRAIL sensitivity in cancer cells remains unknown.

Methods

Herein, we developed nonpathogenic NDV VG/GA strain‐based recombinant NDV (rNDV) and TRAIL gene‐containing rNDV (rNDV‐TRAIL). We observed that viral infections lead to increased DR and TRAIL expressions and activate signaling proteins involved in intrinsic and extrinsic apoptosis pathways. Experiments were conducted in vitro using TRAIL‐resistant CRC cells (HT‐29) and nonresistant CRC cells (HCT116) and in vivo using relevant mouse models.

Results

rNDV‐TRAIL was found to exhibit better apoptotic efficacy than rNDV in CRC cells. Notably, rNDV‐TRAIL had the stronger cancer cell‐killing effect in TRAIL‐resistant CRC cells. Western blot analyses showed that both rNDV and rNDV‐TRAIL infections activate signaling proteins involved in the intrinsic and extrinsic apoptotic pathways. Notably, rNDV‐TRAIL promotes concurrent intrinsic and extrinsic signal transduction in both HCT‐116 and HT‐29 cells.

Conclusions

Therefore, rNDV‐TRAIL infection effectively enhances DR expression in DR‐depressed HT‐29 cells. Moreover, the TRAIL protein expressed by rNDV‐TRAIL effectively interacts with DR, leading to enhanced apoptosis in TRAIL‐resistant HT‐29 cells. Therefore, rNDV‐TRAIL has potential as a promising therapeutic approach for treating TRAIL‐resistant cancers.
Colitis cystica profunda: A report of two cases
Authors: Jiang Qingling , Qin Si , Zhang Han , Liu Guangjian
Published: October 2023

Key Clinical Message

Colitis cystica profunda (CCP) is a rare benign disease characterized by mucus‐filled cysts in the submucosa. Endoscopic, radiological and histological examinations are not highly specific, which can lead to misdiagnosis, resulting in unnecessary radical surgical resection. This report presents two cases of CCP with their clinical and imaging features.
Rheumatic mitral valve disease with left atrial myxoma: Unexpected encounter
Authors: Yang Jiaqi , Huang Kun , Li Xuejie
Published: October 2023

Key Clinical Message

Rheumatic mitral stenosis associated with left atrial myxoma has been reported previously. We reported an admitted rare case of rheumatic mitral regurgitation with left atrial myxoma. The discrimination between left atrial myxoma and thrombi presents a diagnostic challenge in the presence of rheumatic mitral valve disease.
Facial pyoderma gangrenosum associated with fallopian tube carcinosarcoma
Authors: Mardani Ghazal , Shahidi Dadras Mohammad , Abdollahimajd Fahimeh , Safari Giv Toktam , Pourgholi Elnaz , Rakhshan Azadeh , Ghalamkarpour Fariba
Published: October 2023

Key Clinical Message

Pyoderma gangrenosum (PG) is a neutrophilic dermatosis associated with underlying disorders. The association between PG and solid organ tumors (SM), including gynecologic cancers, has been previously reported. Here, we report a case of a 61‐year‐old woman with pyoderma gangrenosum on the posterior auricular region associated with an underlying fallopian tube carcinosarcoma: a rare and aggressive gynecologic malignancy. The patient's ulcer responded favorably to treatment, and surgical resection of the tumor was performed. The patient was then referred for further cancer management. No new lesions or recurrences were found over the 18 months of routine follow‐up.
Fine‐needle aspiration biopsy of axillary lymph nodes: A reliable diagnostic tool for breast cancer staging
Authors: Sallout Luai , Tashkandi Mohamed , Moqnas Amani , AlMajed Hebah , Al‐Naeem Abdulrhman , Alwelaie Yazeed
Published: October 2023

Background

Pathologic evaluation of sentinel lymph node biopsy (SLNB) samples is crucial for axillary staging in patients newly diagnosed with breast cancer. Patients with pathologic evidence of nodal metastasis scheduled for upfront surgery typically also undergo axillary lymph node dissection (ALND). Although SLNB is the gold standard method for detecting nodal metastasis, axillary lymph node fine‐needle aspiration biopsy (FNAB) utility has not been thoroughly explored.

Methods

Ultrasound‐guided axillary lymph node FNAB samples along with concurrent ipsilateral breast tissue samples were searched and reviewed. The control group included histologic findings of axillary dissection or intraoperative SLNB results.

Results

A total of 354 axillary lymph node FNAB samples with matched histology were included. Of these, 187 (52.8%) were positive for metastatic carcinoma of breast origin; 143 (40.4%) were negative for metastasis; 12 (3.4%) showed atypical cells; six (1.7%) were suspicious for metastasis; and six (1.7%) were nondiagnostic because of a lack of lymphoid tissue and malignant cells. Of the 143 negative FNAB samples, 22 (15.4%) were positive on either intraoperative SLNB or ALND. When only the positive and negative FNAB samples were accounted for (n = 330; 93.2%), overall diagnostic sensitivity and specificity were 89.4% and 99.2%, respectively.

Conclusions

Although axillary SLNB is the standard procedure for detecting nodal metastasis of breast origin, axillary lymph node FNAB appears to be a suitable alternative in a significant proportion of patients. A standard SLNB should be performed in cases of negative axillary lymph node FNAB findings, particularly nodes with abnormal imaging findings.
Wnt1 induces osteoblastic changes in a well‐established osteolytic skeletal metastatic model derived from breast cancer
Authors: Sugyo Aya , Tsuji Atsushi B. , Sudo Hitomi , Sugiura Yoshiya , Koizumi Mitsuru , Higashi Tatsuya
Published: October 2023

Background

Osteoblastic skeletal metastasis is frequently observed in prostate cancer. An effective therapy has not been developed due to the unclear molecular mechanism. The Wnt family is involved in various biological phenomena including bone metabolism. There is no direct evidence that the family causes osteoblastic skeletal metastasis.

Aims

The present study aims to evaluate whether overexpressed Wnt induces osteoblastic bone metastasis in a well‐established osteolytic bone metastatic model.

Methods and Results

The breast cancer‐derived 5a‐D‐Luc‐ZsGreen cells were transfected with Wnt1, Wnt3A, and Wnt5A expression vectors, producing stably highly expressing cells. These cells were intracardially transplanted in nude mice. Bone metastasis development was confirmed by fluorescence imaging. Hind‐limb bones including metastasis were dissected and visualized through micro‐CT imaging. After imaging, sections were stained with hematoxylin and eosin (H&E), and immunohistochemically stained with an anti‐SATB2 antibody. Luminescent imaging confirmed mice with bone metastases in the hind limbs. Micro‐CT imaging found an osteoblastic change only in bone metastasis of mice transplanted with Wnt1‐expressing cells. This was confirmed on H&E‐stained sections. SATB2 immunostaining showed differentiated osteoblasts were at the site of bone metastases in the diaphysis. SATB2 in the Wnt/β‐catenin pathway activated by overexpressed Wnt1 could induce osteoblastic change.

Conclusion

Our findings provided direct evidence Wnt1 is involved in osteoblastic bone metastasis development. Our model would be a powerful tool for further elucidating molecular mechanisms underlying the disease and developing effective therapies.