bluuebunny/crossref_metadata_2025 huggingface dataset:
Photoredox‐Enabled Self‐(3+2) Cyclization of Vinyldiazo Reagents: Synthesis of Cyclopentenyl α‐Diazo Compounds
Authors: Li Weiyu , Li Sen , Empel Claire , Koenigs Rene M. , Zhou Lei
Published: August 2023

A photocatalytic self‐(3+2) cycloaddition of vinyldiazo compounds is described, which provides cyclopentene derivatives with conservation of one diazo functional group. Experimental insights and density functional theory indicate that the reaction is triggered by an unusual single electron oxidation of vinyldiazo compounds, while the photolysis for the generation of free carbene species is not involved. The synthetic applications of the resulting cyclopentenyl α‐diazo compounds were demonstrated based on the rich chemistry of the diazo functional group.
Spleen SORT LNP Generated in situ CAR T Cells Extend Survival in a Mouse Model of Lymphoreplete B Cell Lymphoma
Authors: Álvarez‐Benedicto Ester , Tian Zeru , Chatterjee Sumanta , Orlando Domenico , Kim Minjeong , Guerrero Erick D. , Wang Xu , Siegwart Daniel J.
Published: August 2023

Chimeric Antigen Receptor (CAR) T cell immunotherapy is revolutionizing treatment for patients suffering from B‐cell lymphoma (BL). However, the current method of CAR T cell production is complicated and expensive, requiring collection of patient blood to enrich the T cell population, ex vivo engineering/activation, and quality assessment before the patient can receive the treatment. Herein we leverage Spleen Selective ORgan Targeted (SORT) Lipid Nanoparticles (LNPs) to produce CAR T cells in situ and bypass the extensive and laborious process currently used. Optimized Spleen SORT LNPs containing 10 % 18 : 1 PA transfected CD3+, CD8+, and CD4+ T cells in wild‐type mice. Spleen SORT LNPs delivered Cre recombinase mRNA and CAR encoding mRNA to T cells in reporter mice and in a lymphoreplete B cell lymphoma model (respectively) after intravenous injection without the need for active targeting ligands. Moreover, in situ CAR T cells increased the overall survival of mice with a less aggressive form of B cell lymphoma. In addition, in situ transfected CAR T cells reduced tumor metastasis to the liver by increasing tumor infiltrating lymphocytes. Overall, these results offer a promising alternative method for CAR T cell production with pre‐clinical potential to treat hematological malignancies.
An Aqueous Redox Flow Battery Using CO2 as an Active Material with a Homogeneous Ir Catalyst**
Authors: Kanega Ryoichi , Ishida Erika , Sakai Takaaki , Onishi Naoya , Yamamoto Akira , Yasumura Hiroki , Yoshida Hisao , Kawanami Hajime , Himeda Yuichiro , Sato Yukari , Ohira Akihiro
Published: August 2023

For the application of CO2 as an energy storage material, a H2 storage system has been proposed based on the interconversion of CO2 and formic acid (or formate). However, energy losses are inevitable in the conversion of electrical energy to H2 as chemical energy (≈70 % electrical efficiency) and H2 to electrical energy (≈40 % electrical efficiency). To overcome these significant energy losses, we developed a system based on the interconversion of CO2 and formate for the direct storage and generation of electricity. In this paper, we report an aqueous redox flow battery system using homogeneous Ir catalysts with CO2‐formate redox pair. The system exhibited a maximum discharge capacity of 10.5 mAh (1.5 Ah L−1), capacity decay of 0.2 % per cycle, and total turnover number of 2550 after 50 cycles. During charging‐discharging, in situ fluorescence X‐ray absorption fine structure spectroscopy based on an online setup indicated that the active species was in a high valence state of IrIV.
Photo‐Responsive Phase‐Separating Fluorescent Molecules for Intracellular Protein Delivery
Authors: Bao Yishu , Chen Hongfei , Xu Zhiyi , Gao Jiayang , Jiang Liwen , Xia Jiang
Published: August 2023

Cellular membranes, including the plasma and endosome membranes, are barriers to outside proteins. Various vehicles have been devised to deliver proteins across the plasma membrane, but in many cases, the payload gets trapped in the endosome. Here we designed a photo‐responsive phase‐separating fluorescent molecule (PPFM) with a molecular weight of 666.8 daltons. The PPFM compound condensates as fluorescent droplets in the aqueous solution by liquid‐liquid phase separation (LLPS), which disintegrate upon photoirradiation with a 405 nm light‐emitting diode (LED) lamp within 20 min or a 405 nm laser within 3 min. The PPFM coacervates recruit a wide range of peptides and proteins and deliver them into mammalian cells. Photolysis disperses the payload from condensates into the cytosolic space. Altogether, a type of small molecules that are photo‐responsive and phase separating are discovered; their coacervates can serve as transmembrane vehicles for intracellular delivery of proteins, whereas photo illumination triggers the cytosolic distribution of the payload.
Analysis of Rhizonin Biosynthesis Reveals Origin of Pharmacophoric Furylalanine Moieties in Diverse Cyclopeptides
Authors: Ehinger Friedrich J. , Niehs Sarah P. , Dose Benjamin , Dell Maria , Krabbe Jana , Pidot Sacha J. , Stinear Timothy P. , Scherlach Kirstin , Ross Claudia , Lackner Gerald , Hertweck Christian
Published: August 2023

Rhizonin A and B are hepatotoxic cyclopeptides produced by bacterial endosymbionts (Mycetohabitans endofungorum) of the fungus Rhizopus microsporus. Their toxicity critically depends on the presence of 3‐furylalanine (Fua) residues, which also occur in pharmaceutically relevant cyclopeptides of the endolide and bingchamide families. The biosynthesis and incorporation of Fua by non‐ribosomal peptide synthetases (NRPS), however, has remained elusive. By genome sequencing and gene inactivation we elucidated the gene cluster responsible for rhizonin biosynthesis. A suite of isotope labeling experiments identified tyrosine and l‐DOPA as Fua precursors and provided the first mechanistic insight. Bioinformatics, mutational analysis and heterologous reconstitution identified dioxygenase RhzB as necessary and sufficient for Fua formation. RhzB is a novel type of heme‐dependent aromatic oxygenases (HDAO) that enabled the discovery of the bingchamide biosynthesis gene cluster through genome mining.
Novel 1,3‐diphenyl‐4‐(N,N‐dimethylimido dicarbonimidic diamide azo)‐5‐pyrazolone and its chelates with manganese, nickel, copper, and zinc divalent metal ions as an antibacterial activity supported by molecular docking studies: Design, synthesis, DFT, and TD‐DFT/PCM calculations
Authors: Abbas Omar A. , El‐Roudi Omar M. , Abdel‐Latif Samir A.
Published: August 2023

A novel 1,3‐diphenyl‐4‐(N,N‐dimethylimidodicarbonimidic diamide azo)‐5‐pyrazolone as a ligand, simplified as DNP, and its chelates were prepared. Characterization of the structures was performed based on several analytical and spectroscopic techniques. To support these studies, density functional theory (DFT) calculations were carried out by using the B3LYP level, B3LYP/6‐311G** level for the free ligand, and B3LYP/6‐311G**‐LANL2DZ functional level for the solid chelates. The acquired results indicated that DFT calculations generally give compatible results with the experimental ones. Hyper conjugative interactions, molecular stability, bond strength, and intramolecular charge transfer were examined by applying natural bond orbital (NBO) analysis. Nonlinear optical properties of the obtained compounds were investigated by determining molecular polarizability (α), and hyperpolarizability (β) parameters provided a hint for the synthesized compounds' intriguing optical characteristics. The electronic structure of the ligand and its complexes were predicted using the time‐dependent DFT (TD‐DFT) method with a polarizable continuum model (PCM) exploiting the B3LYP approach combined with a 6‐31G(d,p) basis set. The prepared compounds' antibacterial activity was experimentally verified utilizing the agar well diffusion method versus selected G + and G‐ bacteria. The molecular docking mechanism between the bacterially resistant chelates and their inhibited bacteria protein pocket receptors was carried out to determine the modes that these compounds bind to the protein's active sites.
Polybenzoxazine modified by phenolphthalein‐based poly(arylene ether nitrile): Better thermal, mechanical, and dielectric properties
Authors: Zhang Shuai , He Pan , Liu Yalin , Chen Gang , Han Rui
Published: August 2023

Polybenzoxazine, as a ring‐opening polymerized thermosetting resin, suffers from poor toughness. Blending with thermoplastic polymers is a convenient and efficient approach to improve the toughness, however, at the cost of thermal and mechanical properties. In this work, a high‐performance thermoplastic polymer poly(arylene ether nitrile) (PEN) with Tg higher than polybenzoxazine's was used to modify the polybenzoxazine poly(BA‐a). It was found that the PEN improved the mechanical properties, with elongation at break value increased from 1.75% to 3.11% and tensile strength increased from 17.99 to 32.19 MPa when 30 wt% of PEN was introduced. Moreover, due to the better thermal resistance and thermal stability of PEN, Tg of the composites increased from 205.6 to 220.5°C, chary yield at 800°C (Yc) increased from 28% to 46.4%. It was also noted that homogeneous blend was formed at low loading of PEN but phase separation occurred at high content of PEN, with PEN forming isolated spheres. Due to the voids formed between continuous phase and the isolated PEN spheres, the dielectric constant decreased from 3.84 to 3.30 at 1 MHz.
Who tweets scientific publications? A large‐scale study of tweeting audiences in all areas of research
Authors: Zhang Lin , Gou Zhenyu , Fang Zhichao , Sivertsen Gunnar , Huang Ying
Published: August 2023

The purpose of this study is to investigate the validity of tweets about scientific publications as an indicator of societal impact by measuring the degree to which the publications are tweeted beyond academia. We introduce methods that allow for using a much larger and broader data set than in previous validation studies. It covers all areas of research and includes almost 40 million tweets by 2.5 million unique tweeters mentioning almost 4 million scientific publications. We find that, although half of the tweeters are external to academia, most of the tweets are from within academia, and most of the external tweets are responses to original tweets within academia. Only half of the tweeted publications are tweeted outside of academia. We conclude that, in general, the tweeting of scientific publications is not a valid indicator of the societal impact of research. However, publications that continue being tweeted after a few days represent recent scientific achievements that catch attention in society. These publications occur more often in the health sciences and in the social sciences and humanities.
Polarographische Reaktionskinetik
Authors: Hans Willi
Published: August 2023

Bei der Behandlung elektrochemischer Vorgänge an metallischen Elektroden ermöglichen die polarographischen Untersuchungen mit der tropfenden Quecksilberelektrode einen vielseitigen Einblick in die Kinetik der Elektrodenvorgänge. Im folgenden soll ein Überblick über den heutigen Stand der theoretischen und experimentellen Arbeiten gegeben werden. Es ist zweckmäßig, hierbei folgende Einteilung zu wählen:
Untersuchungen über die Heterogenität von Elektrodenoberflächen mit radioaktiven Indikatoren
Authors: Haissinsky M.
Published: August 2023

Es wird unter Heterogenität der Elektrodenoberfläche in erster Linie die statistische Uneinheitlichkeit der Bindungsenergie von darauf abgeschiedenen Atomen verstanden. Dieser Heterogenität im atomistischen Bereich kann sich eine weitere im mikroskopischen Bereich überlagern.

Die Struktur der Elektrodenoberflächen ist durch elektrolytische Abscheidung radioaktiver Indikatoren aus extrem verdünnten Lösungen untersucht worden. Es wurden beobachtet: die kritischen Abscheidungspotentiale (Einfluß der Konzentration und des Oberflächenzustandes), die abgeschiedene Menge als Funktion des Elektrodenpotentials (Gleichung von Herzfeld), die Verteilungsgleichgewichte zwischen der Lösung und der Elektrode bei konstantem Potential (Isothermen). Die mikroskopische Heterogenität wird an Hand von Autoradiographien besprochen. Ferner wird über den Einfluß einer vorherigen Polarisation der Elektrode berichtet.
Über das unscharfe Schmelzen der Hochpolymeren unter hohen Drucken
Authors: Jenckel Ernst , Rinkens Heinz
Published: August 2023

Hochmolekulare Stoffe schmelzen, wie eine vielfache Erfahrung zeigt, in einem Temperaturintervall und nicht, wie die niedermolekularen, bei einer bestimmten Temperatur. In einer früheren Arbeit von Jenckel1) wird das Schmelzen bzw. Kristallisieren der Hochpolymeren in Anlehnung an gewisse einphasige Umwandlungen in Kristallen als einphasige Umwandlung aufgefaßt. Zu dem gleichen Ergebnis ist Münster2) gekommen. In der vorliegenden Arbeit wird das Schmelzen mit Hilfe von Volummessungen bei Drucken bis zu 1800 kg/cm2 untersucht, wobei durchweg eine Verbreiterung des Schmelzintervalls beobachtet wird. Weiterhin wurden Polymerisate mit immer kleinerem Molekulargewicht untersucht, um den Übergang zum gewöhnlichen zweiphasigen Schmelzen der niedermolekularen Stoffe zu finden. Es zeigte sich, daß ein Polyester mit dem Molekulargewicht 1000 noch einphasig schmilzt, ein solcher mit dem Molekulargewicht 500 jedoch bereits zweiphasig.

Es folgt eine ausführliche Erörterung des Ehrenfestschen Begriffes einer Umwandlung höherer Ordnung als Beschreibung einer einphasigen Umwandlung. Das obere Ende des Schmelzbereiches ändert sich mit dem Druck wie eine Umwandlung 2. Ordnung, das untere Ende wie eine Umwandlung 3. oder höherer Ordnung.
Untersuchungen an stationären gestörten Flammen
Authors: Krischer Barbara
Published: August 2023

Steigert man bei einer mit normalem Kegel auf einem Düsenbrenner brennenden Benzol‐Luft‐Flamme den Benzolgehalt des Gemisches, so bilden sich auf dem glatten Kegel Grate aus, deren Zahl mit steigender Überfettung des Gemisches zunimmt.

Zur Prüfung, wieweit die Stabilisierung dieser Erscheinung mit Diffusionseffekten zusammenhängt, wurden über den verschiedenen Zonen der Flamme Abgasproben entnommen. Die Probenahme erfolgte mittels eines sehr engen Quarzröhrchens derart, daß 1. die Strömungsverhältnisse in den Abgasen durch die Probenahme möglichst wenig gestört wurden und daß 2. das Gleichgewicht im Gemisch sehr schnell eingefroren wurde. An Flammen von Benzol‐, Cyclohexan‐, n‐Hexan‐Luft sowie von Wasserstoff‐Methan‐Luft‐Gemischen wurde in Abgasproben der verschiedenen Flammenzonen der CO2‐, CO‐, H2‐ und H2O‐Gehalt quantitativ bestimmt. Dabei zeigte sich, daß über den Graten die sauerstoffärmeren, über den Tälern die sauerstoffreicheren Produkte angereichert waren.
Über die Bleidioxydmodifikationen beim Akkumulator
Authors: Bode Hans , Voss Ernst
Published: August 2023

In der positiven Elektrode eines geladenen Akkumulators ist neben der bekannten tetragonalen Modifikation des Bleidioxyds eine rhombische Form aufgefunden worden. Es kann gezeigt werden, daß zwischen der Kristallstruktur dieser Modifikation und der des roten Bleioxyds sowie der des metallischen Bleis ein enger sterischer Zusammenhang besteht.
Das Dipolmoment zwischen gelösten metallorganischen Verbindungen und organischen Lösungsmittelmolekülen mit Elektronendonatoreigenschaften
Authors: Strohmeier W. , Hümpfner Karlheinz
Published: August 2023

Untersucht wurden die Dipolmomente der Diäthyl‐ und Diphenylverbindungen von Beryllium, Magnesium, Zink, Cadmium und Quecksilber in Heptan, Benzol und Dioxan.

Die untersuchten Verbindungen treten als Elektronenakzeptoren in zwischenmolekulare Wechselwirkung mit den Lösungsmitteln Benzol und Dioxan, welche als Elektronendonatoren fungieren.

Das auf Grund dieser Elektronendonator‐Akzeptor‐Wechselwirkung auftretende Dipolmoment μ nimmt in der Reihenfolge μMgR2>μBeR2>μZnR2>μCdR2>μHgR2 ab. Es ist bei den Diphenylverbindungen jeweils größer als bei den entsprechenden Diäthylverbindungen. Soweit aus Gründen der Löslichkeit das Moment in Heptan bestimmt werden konnte, ergab es sich erwartungsgemäß zu μ = 0. da Heptan kein Elektronendonator ist.
Innermolekularer Protonenübergang im angeregten Zustand
Authors: Weller Albert
Published: August 2023

Die Salizylsäure und ihr Methylester zeigen — im Gegensatz zu den entsprechenden Methoxyverbindungen — eine ungewöhnlich große Stokessche Verschiebung der Fluoreszenz. In unpolaren Lösungsmitteln tritt außerdem noch eine kurzwellige Komponente mit normaler Stokesscher Verschiebung auf. Diese Erscheinungen werden durch einen innermolekularen Protonenübergang im angeregten Zustand als Folge der veränderten Elektronenstruktur gedeutet. Die Bedeutung dieses Vorgangs, der auch bei —180 °C noch stattfindet, wird diskutiert.
Widerstandssprung und Schmelzentropie einiger metallischer Elemente
Authors: Knappwost A. , Thieme F.
Published: August 2023

Mit einer neuen Variante der schon früher beschriebenen Druckguß‐Einbettmethode zur Leitfähigkeitsmessung von Metallen im flüssigen und festen Zustand wurden die Widerstandssprünge der Metalle Al, Tl, Cd, Zn und Hg am Schmelzpunkt gemessen, wobei eine aus der Elektronentheorie der Metalle hergeleitete Beziehung zwischen Widerstandssprung und Schmelzentropie hinreichend gut erfüllt gefunden wird. Stärkere Abweichungen weisen auf eine Änderung der Leitfähigkeitselektronenkonzentration beim Phasenübergang fest‐flüssig hin. Eine solche Änderung der Leitfähigkeitselektronenkonzentration beim Schmelzen liegt beim Cd vor und kann ebenso wie der schwache Abfall des Widerstandes im flüssigen Zn durch das Brillouinsche Zonenmodell erklärt werden. Beim Hg scheint eine Abnahme der Leitfähigkeitselektronenkonzentration beim Schmelzen aufzutreten, wofür auch Anomalien der magnetischen Suszeptibilität des Elektronengases sprechen.
Effect of temperature on the passivity of nickel
Authors: Okamoto Go , Kobayashi Haruo , Nagayama Masaichi , Sato Norio
Published: August 2023

Electrochemical behaviors of the passive nickel electrode were investigated in 1 N sulfuric acid. The dissolution current i is constant (i = id) over the potential range + 0.7 ∼ + 0.9 volt (region A) beyond which it increases steeply with the rise of potential (region B). tan δ which is constant in region A also commences to increase in region B. The linear relation exists between log id and 1/T but has a break at about 60°C. The increase of tan δ was also observed above this temperature. This critical temperature is very close to Kramer's “Umwandlungs‐Temperatur” of exoelectron‐emission. It was suggested that the passive film has a pseudomorphic form in region A and it tends to crystallize above the critical temperature or the critical potential. Such crystallization brings about the reduction of the protective capacity of the passive film on metals.
Über den Mechanismus des Elektropolierens
Authors: Epelboin I.
Published: August 2023

Es scheint gesichert zu sein, daß eine passend gelenkte Diffusion durch Elektropolierung die Nivellierung einer Metalloberfläche bewirken kann.

Wir vermuten, daß sich in gewissen Fällen eine wasserfreie Schicht auf der Anode bildet, die viele Ionen enthält, welche an der Metalloberfläche adsorbiert werden können. Eine Berechnung zeigt, daß das dadurch erzeugte elektrische Feld ausreicht, um die Metallionen unmittelbar aus dem Kristallgitter in die Lösung übertreten zu lassen. Die hohe anodische Spannung, die man oft beobachtet, insbesondere in den Lösungen, die ClO4‐Ionen enthalten, wird der gesamten anodischen Schicht zugeschrieben, die stromleitend ist und viele ClO4–Ionen enthält und nicht etwa einem Oxydfilm hohen Ohmschen Widerstandes. Zum Beweis dieser Hypothese werden Messungen mit Wechselstrom, der dem Elektrolysestrom überlagert wurde, angeführt sowie Beobachtungen, die während der Elektrolyse mit polarisiertem Licht oder im Interferenzkontrast an der Anode gemacht wurden.

Ebenso wird die Polierung des Galliums in einem Bad, dessen Temperatur sehr nahe am Schmelzpunkt (29,75°C) liegt, beschrieben. Es wird gezeigt, daß lokale Erhitzung nicht ausreicht, das Metall zu schmelzen. Dies scheint doch zu bedeuten, daß es einen sehr widerstandsfähigen Film nicht gibt und daraus wird geschlossen, daß die lokale Erhitzung kein wesentlicher Faktor im Mechanismus der Elektropolierung ist. Dieser scheint dagegen mit der Bildung einer diffusen halbleitenden Schicht verbunden zu sein, die die Passivierung der Anode bewirkt.
Vorschlag einer neuartigen Deutung des Relaxationsverhaltens, behandelt am Beispiel des 6‐Nylon
Authors: Müller F. H. , Hellmuth E.
Published: August 2023

Mit Hilfe von Überlegungen, die auf der Anwendung einer von Holzmüller gegebenen Darstellung der Relaxation auf der Basis von im Material laufenden Wärmewellen beruhen, läßt sich zeigen, daß im Fall des 6‐Nylon eine geschlossene Darstellung für die drei zu beobachtenden Dispersionsgebiete und deren Veränderungen mit dem Wassergehalt möglich wird.
Dielektrische Relaxation in Polyvinylchlorid unter allseitigem Druck bis 1000 kp/cm2
Authors: Koppelmann Jan , Gielessen Johannes
Published: August 2023

Im Frequenzbereich von 50 Hz bis 600 kHz und im Temperaturbereich zwischen 20°C und 120°C wurde bei allseitigen Drucken zwischen 1 at und 1000 at der dielektrische Verlustfaktor von Polyvinylchlorid gemessen. Die Ergebnisse zeigen den großen Einfluß des freien Volumens auf die innere Beweglichkeit dieses hochpolymeren Stoffes.
Die Ultraschalldispersion in Gasgemischen
Authors: Correia P.
Published: August 2023

Die Theorie von Tanczos [2] über die Schalldispersion in reinen mehratomigen Gasen in dem Frequenzgebiet, in welchem Schwingungsrelaxation auftritt, wird auf Gasgemische übertragen.

Um die übergangswahrscheinlichkeit von Schwingungsquanten in Translationsenergie zu berechnen, wird ein vom Tanczosschen abweichendes Modell für die Abhängigkeit der zwischenmolekularen Kräfte von den Normalkoordinaten aufgestellt.

Es wird weiter ein Ausdruck für die Schallgeschwindigkeit als Funktion des Quotienten (Frequenz/Druck) abgeleitet, der für die quantenmechanische Behandlung der Schwingungsrelaxation eine exaktere und zweckmäßigere Form besitzt.

Die Berechnungen für die Schalidispersion von Gemischen aus mehratomigen Gasen mit Edelgasen sind qualitativ in Einklang mit Meßwerten der Euckenschen Schule [14].
Bestimmung der reaktionskinetischen Parameter aus nichtisothermen Messungen
Authors: van Heek K. H. , Jüntgen H.
Published: August 2023

Es wird ein Überblick gegeben über die Auswertung von nichtisotherm durchgeführten Messungen der Reaktionsgeschwindigkeit physikalischer und chemischer Prozesse. Zur Berechnung von Reaktionsordnung, Aktivierungsenergie und Frequenzfaktor bestehen verschiedene Rechenverfahren, die erläutert und miteinander verglichen werden. Die Anwendbarkeit der einzelnen Methoden wird an fünf unterschiedlichen Reaktionen kritisch untersucht.
Electrochemical Reactions of Blood Coagulation Factors — Their Role in Thrombosis
Authors: Srinivasan S. , Duic L. , Ramasamy N. , Sawyer P. N. , Stoner G. E.
Published: August 2023

Thrombosis is a reaction at a solid (blood vessel wall or prosthetic material)‐electrolyte (blood) interface. It is initiated by a series of reactions of blood coagulation factors at this interface. Conducting materials, used for vascular and heart valve prostheses, which register potentials in blood more positive than +100 to +200 mv versus the normal hydrogen electrode (NHE) trigger this reaction. The same is true with positively charged insulator materials. These observations suggest an electrochemical mechanism for blood coagulation. Using electrochemical (electrocapillary, differential capacity, potentiodynamic and potentiostatic) ellipsometric, electron microscopic and hematological methods, the adsorption and charge transfer reactions, as well as where possible, their role in blood coagulation, were investigated at solid (mostly metal)‐solution interfaces. These studies reveal that: (1) adsorption of amino‐acids, peptides and proteins on metals is a potential dependent phenomenon; (2) blood coagulation factors (fibrinogen, prothrombin, thrombin, Factors V, VIII and IX) take part in electron transfer reactions; (3) fibrinogen is electropolymerised on electrodes maintained at anodic potentials; (4) fibrinogen clotting times are increased by its prior exposure to an electrode maintained at a potential of —800 mv; (5) electrochemical activation of prothrombin at positive potentials yields a product with thrombin activity; (6) heparin inhibits the adsorption of fibrinogen on freshly cleaved mica surfaces. These results are most valuable in the elucidation of the electrochemical mechanism of thrombosis. Several of the enzyme reactions in blood coagulation appear to occur by electrochemical pathways.
Rate Constants for Electron Transfer from Organic Crystals to Redox Ions in Solution
Authors: Willig F. , Scherer G. , Rothämel W.
Published: August 2023

The time dependence of saturation currents in organic crystals is governed quantitatively by the consumption of charge injecting redox ions in the electron transfer reaction at the crystal surface. Rate constants for electron transfer have been derived from the absolute magnitude of the saturation currents and indepently from their time dependence. These rate constants have been determined in the absence of a voltage drop in the Helmholtz‐layer i.e. for an ideal non‐equilibrium situation. In dependence on the sign and magnitude of the standard free energy of reaction, saturation currents in organic crystals are larger, equal to or smaller than the exchange current of the same redox ion at a metal electrode. If one can assume the applicability of current electron transfer theory as developed by Marcus and others, a quantitative comparison between theory and experimental results yields proof for non‐adiabatic electron transfer reactions between organic crystals and redox ions in solution.
The Role of Proton‐Proton Interactions in Proton Transfer Processes in Ice and Water
Authors: Fang J. K. , Godzik K. , Hofacker G. L.
Published: August 2023

The dynamics of the hydrated proton complex is studied by means of a semiempirical model involving effective one‐proton potentials and two‐body repulsions for protons in neighboring H‐bonds. Protonic Hartree states are calculated for the H21O+10 complex in an ice‐like conformation. Proton‐proton correlation is studied by a selective CI treatment giving rise to low lying proton transfer states which may play a key role in the proton transfer processes in water and ice. The couplings of the collective protonic states to local modes are discussed and a new mechanism for proton mobility in water is described in detail.
Integration of artificial neural network and physiologically based biopharmaceutic models in the development of sustained‐release formulations
Authors: Severino Martins Frederico , Borges Luiza , Oliveira do Couto Rene , Schaller Stephan , de Freitas Osvaldo
Published: August 2023

Model‐informed drug development is an important area recognized by regulatory authorities and is gaining increasing interest from the generic drug industry. Physiologically based biopharmaceutics modeling (PBBM) is a valuable tool to support drug development and bioequivalence assessments. This study aimed to utilize an artificial neural network (ANN) with a multilayer perceptron (MLP) model to develop a sustained‐release matrix tablet of metformin HCl 500 mg, and to test the likelihood of the prototype formulation being bioequivalent to Glucophage® XR, using PBBM modeling and virtual bioequivalence (vBE). The ANN with MLP model was used to simultaneously optimize 735 formulations to determine the optimal formulation for Glucophage® XR release. The optimized formulation was evaluated and compared to Glucophage® XR using PBBM modeling and vBE. The optimized formulation consisted of 228 mg of hydroxypropyl methylcellulose (HPMC) and 151 mg of PVP, and exhibited an observed release rate of 42% at 1 h, 47% at 2 h, 55% at 4 h, and 58% at 8 h. The PBBM modeling was effective in assessing the bioequivalence of two formulations of metformin, and the vBE evaluation demonstrated the utility and relevance of translational modeling for bioequivalence assessments. The study demonstrated the effectiveness of using PBBM modeling and model‐informed drug development methodologies, such as ANN and MLP, to optimize drug formulations and evaluate bioequivalence. These tools can be utilized by the generic drug industry to support drug development and biopharmaceutics assessments.
Microwave‐assisted solvent‐free synthesis of some novel thiazole‐substituted thiosemicarbazone analogues: antimicrobial and anticancer studies
Authors: Hossan Aisha
Published: August 2023

The increased resistance to antibiotics has compelled researchers to devise novel active compounds targeting multidrug‐resistant pathogenic microorganisms. A series of thiosemicarbazone derivatives was synthesized by reacting thiosemicarbazide with 2‐aryl‐4‐formylthiazole, 2‐aryl‐5‐formyl‐4‐methylthiazole, and/or 5‐acetyl‐2‐aryl‐4‐methylthiazole compounds. These thiosemicarbazone‐based thiazole adducts were evaluated for their inhibitory activities against tuberculosis H37Ra and Bovis BCG mycobacteria. Their cytotoxicity was assessed against two cancer cell lines: colonic carcinoma (HCT‐116) and cervical cancer (HeLa). Notably, these thiosemicarbazones exhibited minimal cytotoxic effects on these cell lines even at their highest concentrations. Furthermore, the prepared thiosemicarbazone derivatives demonstrated significant antimicrobial efficacy against Bacillus subtilis and Staphylococcus aureus (Gram‐positive bacterial pathogens) as well as Escherichia coli and Pseudomonas fluorescens (Gram‐negative bacterial pathogens). While most of the prepared thiosemicarbazone derivatives exhibited moderate activity against Candida albicans (a fungal strain), their performance was notable. The thiosemicarbazone‐based thiazole adducts were also successfully synthesized using a solvent‐free approach under microwave irradiation. Compared with conventional reflux methods, the microwave‐assisted technique yielded high thiazole yields within just 5 min, obviating the need for catalysis. This study signifies significant strides toward the rational design of more potent antimycobacterial agents.
Enhancement of the substrate specificity of D‐amino acid oxidase based on tunnel‐pocket engineering
Authors: Wang Liuyu , Tang Heng , Zhu Hongli , Xue Yaping , Zheng Yuguo
Published: August 2023

D‐Amino acid oxidase (DAAO) selectively catalyzes the oxidative deamination of 
D‐amino acids, making it one of the most promising routes for synthesizing optically pure 
L‐amino acids, including 
L‐phosphinothricin (
L‐PPT), a chiral herbicide with significant market potential. However, the native DAAOs that have been reported have low activity against unnatural acid substrate 
D‐PPT. Herein, we designed and screened a DAAO from Rhodotorula taiwanensis (RtwDAAO), and improved its catalytic potential toward 
D‐PPT through protein engineering. A semirational design approach was employed to create a mutation library based on the tunnel‐pocket engineering. After three rounds of iterative saturation mutagenesis, the optimal variant M3rd‐SHVG was obtained, exhibiting a >2000‐fold increase in relative activity. The kinetic parameters showed that M3rd‐SHVG improved the substrate binding affinity and turnover number. This is the optimal parameter reported so far. Further, molecular dynamics simulation revealed that the M3rd‐SHVG reshapes the tunnel‐pocket and corrects the direction of enzyme–substrate binding, allowing efficiently catalyze unnatural substrates. Our strategy demonstrates that the redesign of tunnel‐pockets is effective in improving the activity and kinetic efficiency of DAAO, which provides a valuable reference for enzymatic catalysis. With the M3rd‐SHVG as biocatalyst, 500 mM D,
L‐PPT was completely converted and the yield reached 98%. The results laid the foundation for further industrial production.
Optimization of a HPLC–UV bioanalytical method using Box–Behnken design to determine the oral pharmacokinetics of neratinib maleate in Wistar rats
Authors: Mahajan Radhika , Ravi Punna Rao , Khan Md Shareef
Published: August 2023

The current research work reports the development and validation of a sensitive, robust and reproducible bioanalytical method for quantifying neratinib maleate in rat plasma. More than 85% of the drug was extracted from the plasma samples by protein precipitation. The method was optimized using Box–Behnken design, a response surface method. The effect of three critical factors, viz., the pH of the buffer (X1), the aqueous phase proportion in the mobile phase (X2) and the mobile phase flow rate (X3), was studied on two response variables, retention time (Y1) and United States Pharmacopoeia (USP) width (Y2). With the highest overall desirability function value of 0.943, the obtained optimized method conditions were: X1 = 2.4 ± 0.1; X2 = 66.7 ml, and X3 = 0.85 ml/min. Under the optimized conditions, the values of Y1 and Y2 for a sample containing 1 ppm of the drug were found to be 14.1 min and 0.50 ± 0.003, respectively. Single‐dose intravenous bolus (7.5 mg/kg) and oral (15 mg/kg) pharmacokinetic studies were performed to determine the absolute bioavailability of the drug. The optimized bioanalytical method was sensitive enough to capture 95% of the drug eliminated from the body. The absolute oral bioavailability of the drug was 49.30%.
Predicting consumer purchase intention on electric cars in India: Mediating role of attitude
Authors: Mukesh  , Narwal Mahabir
Published: August 2023

To reduce emission of greenhouse gases, electric vehicle is a good option. During recent time in India, there is emergence of electric vehicle start‐ups. This paper predicts purchase intention of the consumer on electric cars with mediation role of attitude. A questionnaire was framed to collect the data from all ages with 173 valid samples. SmartPLS 4 and SPSS were used to test hypotheses and research model. The secondary data helped in understanding the concept of electric vehicles and consumer preferences for them. The findings showed that price perception, government support and environmental concern significantly influence consumer attitude on electric cars except relative product advantage and range anxiety. Result shows mediating role of attitude between independent variables (Price perception and environmental concern) and purchase intention. Study highlights the role of relative product advantage, range anxiety, government support, environmental concern, and price perception in electric vehicle (car) adoption but it has limitations that the study were conducted in Haryana state (India). The opinions and perceptions of the respondents may also limit the study. In practical, the market of EVs is continuously growing in India. The present study encourages the different stakeholders to go with plan that actually work. At present, driving electric cars in India is luxury for people due to its high prices. There were very less discussion on consumer perception toward EVs in previous literatures.
An auxiliary development framework for lightweight RPG games based on Unity3D
Authors: Zhang Bo , Shi Huiping , Wang Xinyu
Published: August 2023

With the growing prevalence of virtual reality technology across industries like cinema, video animation, and gaming, game developers must cater to a wider range of players. Game engines serve as middleware, reducing the time spent on coding and improving productivity for creating video games. While mainstream game engines offer a plethora of customization options, certain developers may find themselves limited when it comes to controlling specific aspects of the game. Due to the lack of built‐in functionality in current game engines like Unity and Unreal, the author developed TRPGFramework, a lightweight framework based on Unity3D, to address some of these problems. The game framework consists of two main parts: ZGamework (overall framework) and BGamework (game‐specific framework). To enhance performance, scalability, and code reusability in the game development process, the entity‐component‐system structure is implemented. This approach increases maintainability and makes the code clearer, easier to expand, and debuggable. By creating a simple 2D RPG game for performance testing, we confirmed that the framework significantly improves code reusability and modularity, resulting in faster development time and increased efficiency for interactive applications and games. This framework is particularly useful for creating real‐time combat role‐playing games, which are some of the most complex games available today. Using entity‐component‐system principles, we developed a buff system and unit controller optimized to allow hundreds of intelligent units to fight on the same screen or thousands of non‐intelligent units to fight simultaneously.
Symbiotic Antimicrobial Effects of Cellulose‐Based Bio‐Nanocomposite for Disease Management of Agricultural Crops
Authors: Sharma Chhavi , Singh Dinesh , Srivastava Ritu , Narain Sharma Shailesh
Published: August 2023

In the present work, a bionanocomposite for plant crop protection was prepared by non‐toxic biocompatible & biodegradable nanomaterials (Cellulose & TiO2) to utilize its synergistic effects against antimicrobial pathogens. The commercially available microcrystalline cellulose has been reduced to a nanometric scale regime using acid hydrolysis, while the standard TiO2 nano‐powder of particle size ~20 nm has been used to prepare their nanocomposite (NC). The antibacterial studies via agar well diffusion method demonstrated that after 72 h of incubation, parent nanomaterials Ncell and TiO2 were not showing any activity against phytopathogens X. campestris pv. campestris, and Clavibacter while the nanocomposite's NC's were still effective depicting both bacteriostatic and bactericidal actions. However, the bacterial growth of biocontrol P. fluorescence was not affected by Ncell, TiO2 NPs and NC after 72 h of incubation. The antifungal testing results via poison food agar assay method suggest that the nanocomposite, along with Ncell and TiO2 NPs, exhibited strong inhibition of fungal growth of Phytophthora Spp at 0.125 mg/ml concentration while for F. graminearum, similar effect was observed at 0.25 mg/ml concentration. The nanocomposite has proved its potential by exhibiting longer & stronger synergistic effects against plant pathogens as a good antimicrobial agent for protection of agricultural crops.
Platelet‐derived microvesicles induce intracellular calcium mobilization in human platelets
Authors: Yadav Pooja , Panigrahi Abhishek R. , Beura Samir K. , Singh Sunil K.
Published: August 2023

Platelet‐derived microvesicles (PMVs) represent a significant proportion of microvesicles in circulation and have been linked to various pathophysiological complications. Recent research suggests that PMVs carry significant amounts of cargo that can affect cellular functions by influencing calcium oscillations in target cells. As calcium is involved in multiple cellular processes, including hemostasis and thrombosis, this study aimed to investigate the impact of PMVs on platelet calcium mobilization. The study found that PMVs increase platelet intracellular calcium levels via both intracellular storage and extracellular space in a dose‐dependent manner. The study highlighted the critical role of the dense tubular system, acidic vacuoles, mitochondrial stores, and store‐operated calcium entry (SOCE) in PMV‐mediated calcium release in human platelets. Moreover, the study revealed that PMV‐induced calcium rise in platelets does not occur via sarcoendoplasmic reticulum calcium ATPase, and extracellular calcium addition further increases the calcium level in platelets, demonstrating the involvement of SOCE. These findings provide insights into the platelet stimulation signaling mechanisms and contributes to our understanding of platelet and cell behavior when exposed to PMV‐rich environments.
Enhanced Laccase Activity and Stability as Crosslinked Enzyme Aggregates on Magnetic Copper Ferrite Nanoparticles for Biotechnological Processes
Authors: Escalante Morales Laura Karina , Sengar Prakhar , Dorado Baeza Andrea , Vazquez‐Duhalt Rafael , Chauhan Kanchan
Published: August 2023

Highly stable and reusable magnetic crosslinked enzyme aggregates (m‐CLEAS) of laccase are synthesized with simultaneous improved enzymatic activity. Magnetic copper ferrite nanoparticles (CFNPs) were synthesized by solvothermal procedure with an average size of ~8 nm. The nanometric m‐CLEAS were formed by co‐aggregation of enzyme with CFNPs and crosslinked using glutaraldehyde. Different mass ratios of CFNPs:Laccase were assayed (1 : 2, 1 : 3, and 1 : 6), where 1 : 6 resulted in the highest activity recovery (97 %). The m‐CLEAS showed an average size of ~239 nm, ~24 % enzyme immobilization efficiency, and loading as high as 1.75 g of protein per g of support. As expected, m‐CLEAS oxidized the substrate with a higher transformation rate (kcat) and catalytic efficiency (kcat/Km) than the free enzyme. m‐CLEAS showed superior storage and thermostability compared to free enzyme and non‐magnetic CLEAS. In particular, the m‐CLEAS showed ~150 % and ~100 % residual activity after 30 days of storage at 4 °C and room temperature, respectively. Furthermore, m‐CLEAS showed good recyclability, retaining ~78 % and ~54 % laccase activity after 5 and 10 cycles of reuse, respectively. This work highlights the facile and cost‐effective synthesis of nanometric m‐CLEAS with exceptional storage stability and simultaneously improved laccase activity, making them suitable for a range of green industrial processes.
Resource Utilization of Waste Medicine: A Case of Furazolidone Used for Oilfield Water Treatment
Authors: Xu Zhongying , Wang Yefei , Cao Xuewen , Zhu Shidong , Tang Ying
Published: August 2023

As a case study in the practical problem of how to solve the issue of waste medicine more reasonably, furazolidone (FZD) was investigated as an acidizing corrosion inhibitor and bactericide for oilfield water treatment. Gravimetric results indicate that FZD exhibits high inhibitory efficiency under acidic conditions. In addition, the corrosion inhibition performance decreases as the temperature increases. The adsorption of FZD on the surface of steel has been studied, and the experimental results indicate that the material exhibits the characteristics of a Langmuir‐type adsorption isotherm. The thermodynamic results demonstrate that the adsorption behavior of FZD on the steel surface is that of an exothermic, spontaneous, entropy‐decreasing process. Finally, the bactericidal activity of FZD was investigated. This work provides a simple and beneficial way to utilize a particular waste drug.
Mechanistic Investigations of Electrochemical Ethanol Oxidation Reaction by In Situ Raman Spectroscopy
Authors: Xu Jinchang , Wang Zhenyou
Published: August 2023

The Electrochemical Ethanol Oxidation Reaction (EOR) plays a pivotal role in next‐generation energy conversion devices. A clear understanding of the EOR reaction mechanism is critical for rational catalyst design, a task complicated by the numerous reaction intermediates and pathways involved. To this end, in situ Raman spectroscopy has proven invaluable in identifying many such intermediates at the electrode/electrolyte interface under varying applied potentials. Therefore, this technique allows for inference of the reaction mechanism based on the detected Raman signals of intermediates and observed structural changes, positioning in situ Raman spectroscopy as one of the most suitable methods for studying the EOR reaction mechanism. In this short review, with an eye towards future applications, we concentrate on the essential fundamentals of EOR and highlight recent advancements in understanding the EOR mechanism by in situ Raman spectroscopy.
“Click” Chemistry for the Functionalization of Graphene Oxide with Phosphorus Dendrons: Synthesis, Characterization and Preliminary Biological Properties
Authors: Alami Omar , Laurent Régis , Tassé Marine , Coppel Yannick , Bignon Jérôme , El Kazzouli Saïd , Majoral Jean‐Pierre , El Brahmi Nabil , Caminade Anne‐Marie
Published: August 2023

Two families of phosphorhydrazone dendrons having either an azide or an alkyne linked to the core and diverse types of pyridine derivatives as terminal functions have been synthesized and characterized. These dendrons were grafted via click reaction to graphene oxide (GO) functionalized with either alkyne or azide functions, respectively. The resulting modified‐GO and GO‐dendrons materials have been characterized by Fourier Transform Infrared (FTIR), Raman spectroscopy (RS), and Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) analyses. In addition, the free dendrons and the dendrons grafted to GO were tested toward cancerous (HCT116) and non‐cancerous (RPE1) cell lines.
From an Isolable Bismolyl Anion to an Yttrium–Bismolyl Complex with μ‐Bridging Bismuth(I) Centers and Polar Covalent Y‐Bi Bonds
Authors: Pugliese Elizabeth R. , Benner Florian , Demir Selvan
Published: August 2023

The synthesis and first structural characterization of the [K(18‐crown‐6)] bismolyl Bitet (C4Me4Bi) contact ion pair (1) is presented. Notably, according to Natural Resonance Theory calculations, the Bitet anion of 1 features two types of leading mesomeric structures with localized anionic charge and two lone pairs of electrons at the BiI center, as well as delocalized anionic charge in the π‐conjugated C4Bi ring. The lone pairs at Bi enable a unique bridging coordination mode of the bismolyl ligand, as shown for the first rare earth metal bismolyl complex (Cptet2Y)2(μ‐η1‐Bitet)2 (2). The latter results from the salt metathesis reaction of KBitet with Cptet2Y(BPh4) (Cptet=C5Me4H). The Y‐Bi bonding interaction in 2 of 16.6 % covalency at yttrium is remarkably large.
Systeme zur Sauerstoffversorgung
Authors: Imhof Alexander , Kühn Fritz E.
Published: August 2023

Der Mensch kann ohne Nahrung mehrere Wochen überleben, ohne Wasser mehrere Tage aber ohne Sauerstoff nur wenige Minuten. Eine ausreichende Verfügbarkeit von Sauerstoff in der umgebenden Atemluft ist deshalb lebenswichtig. Vor allem in künstlichen Extremlagen wie Bergwerksstollen, Unterseebooten, Tunneln oder in den großen Höhen der Luft‐ und Raumfahrt bedarf es deshalb technischer Lösungen zur Aufrechterhaltung der Sauerstoffversorgung im Regelbetrieb sowie bei Unfällen oder Defekten. Insbesondere die Rolle der dort verwendeten Chemikalien und Verfahren zur Sauerstofffixierung und ‐freisetzung werden beschrieben. Auch die Natur hat faszinierende Wege gefunden, mit dem Element Sauerstoff umzugehen und in scheinbar lebensfeindlichen Orten auf dem Planeten Erde zu nutzen. So werden neben dem anatomischen Aufbau des Atmungsapparats von Säugetieren wie Walen oder von Vögeln auch unterschiedliche Sauerstoff‐Transportproteine im Blut betrachtet.