bluuebunny/crossref_metadata_2025 huggingface dataset:
Cold Neutron Scattering at CH3‐, CH2‐ and OH‐Protons in Methanol and Ethanol
Authors: Fischer C. O.
Published: November 2023

Total cross sections of CH3OH, CH3OD, CH2DOH, CHD2OH, CD3OH, and CH3CH2OH, CH3CH2OD, CH3CD2OH, CD3CH2OH have been measured with cold neutrons between 5 Å and 15 Å. The slopes S of the scattering cross section per proton vs the neutron wavelength indicate the different microdynamic behaviour of the individual protons inside the molecule. In methanol S = 3.4 ± 0.8 barn/Å for an OH‐proton and S = 12.1 ± 0.5 barn/Å for a CH3‐proton is explained by a relatively free internal CH3 rotation and a hindered motion of the OH‐proton. In ethanol the OH‐proton with 1.3 ± 0.8 barn/Å seems to be much more hindered than in methanol, whereas a CH3‐proton with S = 9.8 ± 0.4 barn/Å behaves quite similar to a CH2‐proton with 9.1 ± 0.5 barn/Å.
Untersuchungen zu der Wasserstoffentwicklung an der Quecksilberkathode bei der Chloralkali‐Elektrolyse, veranlaßt durch von „Störelementen”︁ gebildete Deckschichten
Authors: Stackelberg M. V. , Wolter M. , Lieberz F.
Published: November 2023

Bei der Chloralkalielektrolyse nach dem Amalgamverfahren können anwesende Schwermetallionen Störungen hervorrufen. Sie bilden Deckschichten auf dem Quecksilber, die die Wasserstoffüberspannung herabsetzen.

Die Bildung dieser Deckschichten aus den Ionen des Vanadium, Molybdän und Chrom wurde an großflächigen Hg‐Bodenelektroden und am hängenden Hg‐Tropfen potentiostatisch und mit der Dreieckspannungsmethode untersucht. Daraus ergeben sich Folgerungen über die Natur der Deckschichten und den Mechanismus der Herabsetzung der Wasserstoffüberspannung durch diese Schichten.
Das Infrarotspektrum von Chlorwasserstoff bis 400 °C und bis zu Drucken von 1250 bar
Authors: Buback M. , Franck E. U.
Published: November 2023

Die Grundschwingungsbande von HCl bei 2886 cm−1 wurde zwischen 24 °C und 400 °C und bei Drucken zwischen 10 und 1250 bar gemessen. Dazu diente eine Hochdruckmeßzelle vom Reflexionstyp mit Saphirfenster. Oberhalb der kritischen Temperatur von 51,4 °C wurde die Gasdichte um fast drei Größenordnungen bis maximal 1,0 g/cm3 variiert.

Mit steigender Dichte verschwindet die Rotationsstruktur zugunsten einer neuen intensiven “Zentralbande”, deren Maximumsfrequenz mit steigender Dichte sinkt. Steigende Temperatur bei konstanter hoher Dichte erzeugt eine geringe Frequenzerhöhung. Maximumsfrequenz und integrierte Bandenintensität hängen linear voneinander ab. Die Banden können durch Annahme “gasartiger” und “flüssigkeitsartiger” Zustände gedeutet werden. Die Resultate werden mit den analogen Spektren des überkritischen Wassers verglichen.
General Co‐operative Kinetics on a Linear ISING Lattice
Authors: Schwarz Gerhard
Published: November 2023

In view of its significance for co‐operative reactions of linear (bio)polymers a set of rate equations is derived which describes the general non‐equilibrium behavior of a linear ISING lattice (i.e. a chain of equivalent reaction sites with nearest‐neighbor interactions). End effects are included in the treatment. The approach is essentially based on the existence of a so‐called triplet‐closure which permits any time‐dependent variable of the system to be expressed in terms of a limited number of triplet concentrations (refering to sequences of three individual states on the lattice). In the important case of negligible end effects the quantitative formulation requires only four comparatively simple differential equations. Potential applications to special problems of practical interest and to non‐linear ISING models are indicated.
Application of ESR‐Methods in Chemisorption and Catalysis
Authors: van Reijen L. L.
Published: November 2023

Die drei wichtigsten Anwendungsgebiete der ESR‐Methode in der Katalyse sind:

Bestimmung der Wertigkeit und der Symmetrie der Anionenumgebung von übergangsmetallionen, die aktive Zentren an der Katalysatoroberfläche bilden können.

Bestimmung der Anwesenheit und Art von Gitterfehlstellen, die in der Chemisorption und der Katalyse eine Rolle spielen können.

Bestimmung von oberflächlich adsorbierten organischen und anorganischen Radikalen, die den aktivierten Reaktionspartnern sehr ähnlich sein können.

In indirekter Weise kann die ESR‐Methode weiterhin wichtige Auskünfte über die Festkörperreaktionen geben, die während der Katalysatorherstellung stattfinden.

In diesen übersicht werden die genannten Anwendungsmöglichkeiten von einigen charakteristischen Beispielen erläutert.
Zur Charakterisierung der Oberflächen von Rußen und hochdispersen Kieselsäuren
Authors: Koberstein E. , Lakatos E. , Voll M.
Published: November 2023

Bei der Anwendung heute verfügbarer Methoden zur Charakterisierung der Oberflächen hochdisperser Kieselsäuren und Ruße auftretende Probleme werden diskutiert (Elektronenmikroskopie, Gasadsorption, Oberflächenreaktionen, Infrarotspektroskopie). Erst durch die Kombination mehrerer Verfahren lassen sich zutreffende Aussagen über die Mikroporosität bzw. die für bestimmte Reaktionen zugänglichen Anteile der Gesamtoberfläche gewinnen.

Aufgrund der vorliegenden Meßergebnisse werden Modellvorstellungen über die Oberflächenstrukturen und die Wirkungsweise dieser Oberflächen bei technischen Anwendungen besprochen.
Präzisionsmessungen des Diffusionskoeffizienten des Protons mit Hilfe einer rotierenden Scheibenelektrode
Authors: Gostiša‐Mihelčić B. , Vielstich W. , Heindrichs A.
Published: November 2023

Mit einer rotierenden Scheibenelektrode großer mechanischer Präzision wurde der Diffusionskoeffizient des Protons in wäβriger In KCl‐Lösung im Temperaturintervall von 12‐40°C bestimmt und für 25°C mit Literatur‐Daten verglichen.

Aus den Meßdaten errechnet sich für die Diffusion des Protons eine Aktivierungsenergie von 3,1 kcal/mol.

Der relative Fehler einer Einzelmessung von DH + betrug bei unseren Untersuchungen etwa 1,2%. Bei Erhöhung der Frequenzgenauigkeit auf ± 0,1 Hz ist mit der verwendeten Apparatur für die Messung von Spuren‐Diffusionskoeffizienten ein relativer Fehler von nur 0.34% zu erwarten.
Polarographische Untersuchungen der Substituenteneffekte in Triarylmethylkationen
Authors: Strohbusch Frank
Published: November 2023

Die polarographischen Reduktionshalbstufenpotentiale E1/2 von 14 p‐substituierten Triphenylmethylkationen wurden in wasserfreiem Benzonitril gemessen. Die E1/2‐Werte können zusammen mit weiteren Daten aus der Literatur mit den a+‐Konstanten korreliert werden. Mono‐, di‐ und trisubstituierte Kationen geben unterschiedliche lineare Beziehungen. Die Reaktionskonstanten pro Substituent betragen in den drei Reihen: p1 = 0,298 V, p2 = 0,247 V, p3 = 0,218 V. Die Veränderung des Substituenteneffekts mit zunehmender Substitution (Sättigungseffekt) wird anhand von HMO‐ und SCF‐Rechnungen auf Änderungen der Gleichgewichtskonformation durch die Substituenten zurückgeführt. Der verstärkte Sättigungseffekt der Ionen mit Aminogruppen wird diskutiert.
Zur Debye‐Hückel‐Extrapolation der Aktivitätskoeffizienten von 1:6‐Elektrolyten
Authors: Stock H.‐P. , Plewinsky B.
Published: November 2023

Die Aktivitätskoeffizienten von Kalium‐ und Natriummetawolframat in wäßriger Lösung werden bei 0°C durch kryoskopische und bei 25°C durch Ultrazentrifugenmessungen bestimmt. Dabei erweist sich die Auftragung von ∂ ln y/° über c‐1/2 als besonders vorteilhaft, weil bei ihr der nach Debye‐Hückel geforderte lineare Verlauf bereits bei viel höherer Konzentration erreicht wird, als bei der üblichen Auftragung von ln y über c1/2. Auf diese Weise kann der nach der Debye‐Hückel‐Theorie berechnete Grenzanstieg erstmalig für 1 : 6‐Elektrolyte experimentell bestätigt werden. Für die Logarithmen der Aktivitätskoeffizienten werden Polynome in c1/2 und in m1/2 angegeben. Der mittlere Ionendurchmesser ergibt sich bei 25°C für das Natriumsalz zu a = 5,1 Å (kryoskopisch 6,7 Å) und für das Kaliumsalz zu 4,9 Å. Aus Leitfähigkeitsmessungen wird für den Anionenradius des Natriummetawolframats ein Wert von 4,7 Å erhalten.
Elektronenspektren und Bindungsverhältnisse in Thio‐ und Selenometallaten der Übergangsmetalle mit d°‐Konfiguration) des Zentralatoms
Authors: Diemann E. , Müller A.
Published: November 2023

Wir haben uns in letzter Zeit mit präparativen, spektroskopischen und röntgenographischen Untersuchungen an Thio‐ und Selenoverbin‐dungen der Übergangsmetalle beschäftigt. Aufgrund von SCCC‐MO‐Rechnungen [1] und spektroskopischen Überlegungen war es bereits möglich, im Falle von Ionen des Typs MX4n− (M = V, Cr, Mn, Mo, W, Re, Ru, Os; X = O, S, Se) mit Td‐Symmetrie eine Zuordnung der längst‐welligen Elektronenübergänge zu treffen [2]. Die experimentell ermittelten Übergangsenergien stimmten sehr gut mit denjenigen überein, die mit einer einfachen SCCC‐MO‐Methode berechnet wurden.In der vorliegenden Untersuchung werden weitere Gesetzmäßigkeiten bezüglich der Interpretation der Elektronenspektren der oben angegebenen Ionen diskutiert sowie erstmalig Zuordnungen anhand einfacher MO‐Diagramme für Ionen des Typs MX3Yn−(C3v) wie z. B. WO3S2−, WOS32−, MoOSe32− u. ä. getroffen. Die Interpretation der Spektren ergibt interessante allgemeingültige Gesetzmäßigkeiten für ähnlich aufgebaute Ionen.
East Ionic Reactions in Solution IX [1] The Formation and Dissociation of the Hexanuclear Bismuthyl Cluster Complex Bi6(OH)6+12
Authors: Frei Vaclav , Mages Gert , Wendt Hartmut
Published: November 2023

The kinetics of the formation and dissociation of the bismuthyl cluster complex Bi6(OH)6+12 have been investigated with the p‐jump and the stopped flow method.

The rate law under equilibrium condition (p‐jump) is

magnified image

The rate of disappearance of the hexamer at high acid concentrations (stopped flow) is described by

magnified image

The first two terms in Equation (b) correspond to the direct and proton catalized dissociation of the hexamer to less stable rapidly decomposing oligomers. The third term in Equation (b) is due to the decomposition of an intermediate trimer Bi3(OH)4+5. Its formation and decomposition according to Equation (a) are rate determining for the formation and decomposition of the hexamer under equilibrium conditions.
Der kontinuierliche Übergang vom Isolator zum Ionenleiter am Beispiel des Wismutchlorids
Authors: Treiber G. , Tödheide K.
Published: November 2023

Die spezifische elektrische Leitfähigkeit und die PVT‐Daten von geschmolzenem Wismutchlorid wurden bis 1200°C und 4 kbar gemessen und daraus die molare Leitfähigkeit berechnet. Im Bereich überkritischer Temperaturen (T > 905°C), wo die Dichte des Salzes kontinuierlich von der eines verdünnten Dampfes auf die einer Flüssigkeit variiert werden kann, ändert sich die molare Leitfähigkeit um etwa fünf Größenordnungen. Sie steigt stark mit zunehmender Dichte, aber nur schwach mit zunehmender Temperatur. Aus der molaren Leitfähigkeit und extrapolierten Ionenbeweglichkeiten wurde der Dissertationsgrad des Salzes als Funktion von Druck und Temperatur ermittelt. Er ändert sich im ausgemessenen Druckbereich von 10−5 auf 1, so daβ der kontinuierliche Übergang vom Isolator zum Ionenleiter beim Wismutchlorid experimentell verfolgt werden konnte. In der Umgebung seines kritischen Punktes liegt das Wismutchlorid vorwiegend molekular vor, da dort weniger als ein Prozent der Moleküle in Ionen dissoziiert sind.
Semiclassical Evaluation of the Translational‐Vibrational Coupling from the Potential Energy Surface of an Atom‐Diatom Reaction
Authors: Hofacker G. Ludwig , Rösch Notker
Published: November 2023

Given a potential energy surface for a linear triatomic system, it is shown how internal coordinates leading to natural separation of translational and vibrational kinetic energy can be introduced. On this basis the coupling constant for translational‐vibrational interaction is calculated within the framework of a semiclassical approximation. Applying a strong coupling scheme to highly exoergic reactions an estimate of the product vibrational energy can be made. The procedure is applied to the system F + H2 for which recently an ab initio‐computed potential energy surface has become available.
Determination of Rate Constants for the Reactions of OH with Propylene and Ethylene by a Pulsed Photolysis‐Resonance Fluorescence Method
Authors: Stuhl F.
Published: November 2023

Absolute rate constants for the reactions of OH radicals with CH3CHCH2, CD3CHCH2, CH3CDCD2, CD3CDCD2, and CH2CH2 were determined at 298°K. Hydroxyl radicals were generated in the pulsed vacuum‐uv photolysis of H2O. Decays of OH were monitored by resonance fluorescence in an excess of hydrocarbons. The rate constants for the reactions with propylene and ethylene were determined to be 1.45 (±0.22)·10−11 and 3 (±1)·10−12 cm3 molecule−1 sec−1, respectively. The kinetic isotope effect for deuterated propylene was found to be small, thus supporting the proposed addition mechanism.
Modellrechnungen zur Deutung der 23Na‐Resonanz im entwässerten Zeolithen Linde 13 X
Authors: Lechert Hans
Published: November 2023

Modellrechnungen mit einem vereinfachten Punktmultipolmodell für die Feldgradiententensoren an den Plätzen der Natriumionen im Zeolithen Linde 13 X zeigen, daβ die beobachteten 23Na‐Resonanzen ihren Ursprung in den Ionen an S1‐Plätzen haben.

Diese Plätze liegen im Zentrum der Doppelsechsringe, die an den Verknüpfungsstellen der Kubooktaeder entstehen, aus denen die Struktur aufgebaut ist.

Die beobachteten Linienbreiten können durch die Annahme einer Dipolpolarisierbarkeit der Sauerstoffionen des Alumosilikatgerüstes von 1,7 Å3 und einer Quadrupolpolarisierbarkeit von 0,1 Å5 gedeutet werden.

Die Natriumionen, die röntgenographisch nicht lokalisierbar sind, scheinen Plätze vor den Vierringen der großen Hohlräume gegenüber Plätzen an der Außenseite der Doppelsechsringe zu bevorzugen.

The observed line widths can be explained by using a dipole polarizability of the oxygen ions of 1.7 Å3 and a quadrupole polarizability of 0.1 Å5.

The sodium ions, not being localised by x‐ray diffraction, seem to prefer the sites at the four‐membered rings in the large cage instead of sites at the outer side of the double six‐membered rings.
Raman and infrared spectra of thiocarbohydrazide‐do and d6' force constant calculations and vibrational assignments
Authors: Dwarakanath K. , Sathyanarayana D. N. , Volka K.
Published: November 2023

The infrared and Raman spectra of thiocarbohydrazide and deuterated thiocarbohydrazide have been measured between 4000 and 30 cm−1. The force constant calculations for both the molecules have been carried out for in‐plane as well as out‐of‐plane modes. The normal coordinate treatment has also been carried out for the in‐plane vibrations of selenocarbohydrazide. Vibrational assignments have been discussed by referring to characteristic group frequencies of related molecules and force constant calculations.
Preparation of cis‐ and trans‐3,5‐dimethyl‐1‐silacyclohexane and 3‐silabicyclo [3.2.1] octane.
Authors: Carleer Robert , Hosten NoËL , Anteunis Marc J. O.
Published: November 2023

The preparation of cis‐, and trans‐3,5‐dimethyl‐l‐silacyclohexane and 3‐silabicyclo [3,2,1]‐octane is reported.
Did the court dismiss student‐athlete's harassment claim?
Authors: Lyerly Eric
Published: November 2023

A University of Arizona track team member endured “sexual and homophobic bullying” during his first year on the team. His teammates allegedly called him “gay” and “fag” on an almost daily basis. On one occasion, the student‐athlete's team members posted a false obscene video about him in the team's public chat group. The coaches didn’t respond to the posting.
Attorney and coach weigh in on males participating in women's sports
Authors: McCarthy Claudine
Published: November 2023

If you’re keeping up with the latest in college athletics, you’ve heard about Kim Russell, the former Oberlin College women's lacrosse coach who was reprimanded by leadership and removed from her coaching position after sharing an Instagram post criticizing the participation of biological males in women's sports. Now, you can hear directly from Russell, who recently became an Ambassador with Independent Women's Forum, and May Mailman, J.D., Senior Legal Fellow at Independent Women's Law Center.
Longtime AD offers insight into preparing for changes
Authors: McCarthy Claudine
Published: November 2023

As he looks through his lens of expertise and knowledge gained from decades of on‐the‐job experience, Ron Prettyman is concerned about the future of college athletics. “College sports is in a major state of flux right now. There's a need for strong leadership,” said Prettyman, who devoted 41 years to college athletics administration, including some consulting work along the way. He now serves as Interim Athletics Director at the University of New Haven and Vice President and Consultant at SP Athletics, which provides athletics‐related executive searches at the collegiate, professional, organization, and club levels, as well as 360‐degree evaluations of athletics departments and athletics organizations, identifying strengths and weaknesses and making recommendations, he explained.
Jael's syndrome: Hemostatic management of an impacted knife in the facial site—A case report
Authors: Alam Mostafa , Golkar Mohsen , Badkoobeh Ashkan , Baseri Milad
Published: November 2023

Key Clinical Message

It is essential to take a specific multidisciplinary approach in penetrating maxillofacial traumas; securing the airway, completing the hemodynamic stabilization, and systemic evaluation and consideration regarding the beneficial therapeutic regime.

Jael's syndrome is defined as a deliberate injury caused by a knife to the skull and facial area. This article describes the case of a young male patient with a penetrating knife on the left side of the face following an assault. Due to the high probability of injury to the descending palatine artery, it was decided to make a femoral pathway for catheter angiography in the operation room and have a standby vascular surgeon for selective embolization of the external carotid artery in case of severe bleeding. The treatment plan included removing the foreign body, exploring the wound, suturing, tetanus immunization, and prescribing antibiotics. There was no significant complication in the postoperative period. However, In the 6‐month follow‐up, the patient complained of weakness in the left upper lip and hypoesthesia in the pathway of the left infraorbital nerve. Jael's syndrome can be life‐threatening, so there is a need for accurate initial management performed by a multidisciplinary team to raise the survival rate of these patients.
Diffuse large B‐cell lymphoma presenting as postmenopausal bleeding
Authors: Cai Jennifer , Parnall Taylor , Tomassetti Sarah , Qing Xin
Published: November 2023

Key Clinical Message

Endometrial lymphoma is a rare etiology of abnormal uterine bleeding and endometrial thickening, and often shares similar clinical and imaging characteristics with other uterine malignancies such as endometrial carcinoma. Chemotherapy appears adequate for treating primary endometrial lymphoma.

We report a case of primary endometrial diffuse large B‐cell lymphoma to increase awareness of this condition which is essential for correct diagnosis and treatment.
Daptomycin‐induced hyperkalemia: A case report and brief description of mechanism
Authors: Errabelli Praveen , Lathiya Maulik , Roy Sasmit
Published: November 2023

Key Clinical Message

Daptomycin causes serious side effects like rhabdomyolysis at high doses. At lower doses it can cause isolated hyperkalemia without frank rhabdomyolysis. Checking BMP along with CK helps taking timely measures to prevent adverse consequences.

Hyperkalemia is a common yet challenging clinical condition faced daily by physicians worldwide. Accurate etiology and timely management are paramount in correcting this preventable yet life‐threatening electrolyte imbalance. Very seldom has Daptomycin been implicated as a culprit for hyperkalemia. We present one such unique case where a low dose of Daptomycin led to hyperkalemia, and timely identification improved patient outcomes. We present a 69‐year‐old woman with multiple comorbidities admitted to the intensive care unit to manage diabetic ketoacidosis and sepsis. She developed acute kidney injury due to intravenous contrast, volume depletion, and obstructive uropathy. Interestingly although initially normokalemic, as her renal function started improving with sound urine output, she developed recurrent hyperkalemia, which required medical management. The etiology of hyperkalemia was initially unclear, but on closer review, it was discovered that Daptomycin was the potential culprit. Although case studies with high‐dose Daptomycin causing rhabdomyolysis and hyperkalemia have been reported, low‐dose Daptomycin causing hyperkalemia without rhabdomyolysis has never been reported, bringing forth the uniqueness of our article.
Aromaticity and Magnetic Behavior in Benzenoids: Unraveling Ring Current Combinations
Authors: Leyva‐Parra Luis , Pino‐Rios Ricardo , Inostroza Diego , Solà Miquel , Alonso Mercedes , Tiznado William
Published: November 2023

Nowadays, an active research topic is the connection between Clar's rule, aromaticity, and magnetic properties of polycyclic benzenoid hydrocarbons. In the present work, we employ a meticulous magnetically induced current density analysis to define the net current flowing through any cyclic circuit, connecting it to aromaticity based on the ring current concept. Our investigation reveals that the analyzed polycyclic systems display a prominent global ring current, contrasting with subdued semi‐local and local ring currents. These patterns align with Clar's aromatic π‐sextets only in cases where migrating π‐sextet structures are invoked. The results of this study will enrich our comprehension of aromaticity and magnetic behavior in such systems, offering significant insights into coexisting ring current circuits in these systems.
Human bocavirus 1 coinfection is associated with decreased cytokine expression in the rhinovirus‐induced first wheezing episode in children
Authors: Hurme Pekka , Sahla Reetta , Rückert Beate , Vahlberg Tero , Turunen Riitta , Vuorinen Tytti , Akdis Mübeccel , Söderlund‐Venermo Maria , Akdis Cezmi , Jartti Tuomas
Published: November 2023

Background

Rhinovirus (RV)‐induced first wheezing episodes in children are associated with a markedly increased risk of asthma. Previous studies have suggested that human bocavirus 1 (HBoV1) may modify RV‐induced immune responses in young children. We investigated cytokine profiles of sole RV‐ and dual RV‐HBoV1‐induced first wheezing episodes, and their association with severity and prognosis.

Methods

Fifty‐two children infected with only RV and nine children infected with dual RV‐HBoV1, aged 3–23 months, with severe first wheezing episodes were recruited. At acute illness and 2 weeks later, peripheral blood mononuclear cells were isolated, and stimulated with anti‐CD3/anti‐CD28 in vitro. Multiplex ELISA was used to quantitatively identify 56 different cytokines at both study points. Patients were prospectively followed for 4 years.

Results

The mean age of the children was 14.3 months, and 30% were sensitized. During the acute illness, the adjusted analyses revealed a decrease in the expression of IL‐1b, MIP‐1b, Regulated upon activation, normal T cell expressed and presumably secreted (CCL5), TNF‐a, TARC, and ENA‐78 in the RV‐HBoV1 group compared with the RV group. In the convalescence phase, the RV‐HBoV1 group was characterized by decreased expression of Fractalkine, MCP‐3, and IL‐8 compared to the RV group. Furthermore, the hospitalization time was associated with the virus group and cytokine response (interaction p < 0.05), signifying that increased levels of epidermal growth factor and MIP‐1b were related with a shorter duration of hospitalization in the RV‐HBoV1 coinfection group but not in the RV group.

Conclusions

Different cytokine response profiles were detected between the RV and the RV‐HBoV1 groups. Our results show the idea that RV‐induced immune responses may be suppressed by HBoV1.
Ligand 1H NMR Chemical Shifts as Accurate Reporters for Protein‐Ligand Binding Interfaces in Solution**
Authors: Platzer Gerald , Ptaszek Aleksandra L. , Böttcher Jark , Fuchs Julian E. , Geist Leonhard , Braun Daniel , McConnell Darryl B. , Konrat Robert , Sánchez‐Murcia Pedro A. , Mayer Moriz
Published: November 2023

The availability of high‐resolution 3D structural information is crucial for investigating guest‐host systems across a wide range of fields. In the context of drug discovery, the information is routinely used to establish and validate structure‐activity relationships, grow initial hits from screening campaigns, and to guide molecular docking. For the generation of protein‐ligand complex structural information, X‐ray crystallography is the experimental method of choice, however, with limited information on protein flexibility. An experimentally verified structural model of the binding interface in the native solution‐state would support medicinal chemists in their molecular design decisions. Here we demonstrate that protein‐bound ligand 1H NMR chemical shifts are highly sensitive and accurate probes for the immediate chemical environment of protein‐ligand interfaces. By comparing the experimental ligand 1H chemical shift values with those computed from the X‐ray structure using quantum mechanics methodology, we identify significant disagreements for parts of the ligand between the two experimental techniques. We show that quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) ensembles can be used to refine initial X‐ray co‐crystal structures resulting in a better agreement with experimental 1H ligand chemical shift values. Overall, our findings highlight the usefulness of ligand 1H NMR chemical shift information in combination with a QM/MM MD workflow for generating protein‐ligand ensembles that accurately reproduce solution structural data.
Perspective on the interfacial engineering for electrocatalytic N2 to NH3 conversion from catalysts to systems
Authors: Choe Seokwoo , Kim Nayun , Jang Youn Jeong
Published: November 2023

Ammonia (NH3) has received significant attention due to its increasing demand as a key commodity for industrial chemical production, a green fuel, and a hydrogen (H2) carrier. Electrochemical nitrogen (N2) reduction reaction (ENRR) emerges as the most attractive pathway to produce NH3. The process utilizes H2O as a proton source under mild temperature and pressure, which can reduce CO2 emissions and energy input compared to the traditional Haber‐Bosch process. However, ENRR is severely insufficient for practical applications due to its kinetically sluggish steps compared to its competitive hydrogen evolution reaction. Also, the imbalanced reactant concentrations of N2 and H2O, resulting from the low N2 solubility, and oppositely, free H2O accessibility toward catalysts, cause the ineffective three‐phase‐boundary that acts as active sites for ENRR. To overcome these challenges, it is essential to perform interfacial engineering for each part of the catalyst and reaction environment. In this perspective, recent advances in interfacial engineering are examined and critically reviewed, and further research directions are proposed to develop ENRR significantly. The sections cover catalytic active site modification, hydrophobic/hydrophilic control, electrolyte engineering, and system design. The insights and prospects in this perspective will be effective for developing ENRR in a scientific and practical manner.
The suppression of a selfish genetic element increases a male's mating success in a fly
Authors: Lyth Sophie , Betancourt Andrea J. , Price Tom A. R. , Verspoor Rudi L.
Published: November 2023

X chromosome meiotic drive (XCMD) kills Y‐bearing sperm during spermatogenesis, leading to the biased transmission of the selfish X chromosome. Despite this strong transmission, some natural XCMD systems remain at low and stable frequencies, rather than rapidly spreading through populations. The reason may be that male carriers can have reduced fitness, as they lose half of their sperm, only produce daughters, and may carry deleterious alleles associated with XCMD. Thus, females may benefit from avoiding mating with male carriers, yielding a further reduction in fitness. Genetic suppressors of XCMD, which block the killing of Y sperm and restore fair Mendelian inheritance, are also common and could prevent the spread of XCMD. However, whether suppressed males are as fit as a wild‐type male remains an open question, as the effect that genetic suppressors may have on a male's mating success is rarely considered. Here, we investigate the mating ability of XCMD males and suppressed XCMD males in comparison to wild‐type males in the fruit fly Drosophila subobscura, where drive remains at a stable frequency of 20% in wild populations where it occurs. We use both competitive and non‐competitive mating trials to evaluate male mating success in this system. We found no evidence that unsuppressed XCMD males were discriminated against. Remarkably, however, their suppressed XCMD counterparts had a higher male mating success compared to wild‐type controls. Unsuppressed XCMD males suffered 12% lower offspring production in comparison to wild‐type males. This cost appears too weak to counter the transmission advantage of XCMD, and thus the factors preventing the spread of XCMD remain unclear.
Effect of environmental drivers of fish assemblage and diversity patterns in temporal scale in Mongra Reservoir: A case study from one of the tributaries of Mahanadi Basin, Central India
Authors: Das Sarita Kumari , Talagunda Srinivasan Nagesh , Sarang Niranjan , Das Sudhir Kumar , Thangapalam Jawahar Abraham , Canciyal Johnson , Panda Kamalesh
Published: November 2023

Influence of seasonal variations in environmental parameters on fish assemblage and species diversity patterns was studied in a tropical reservoir of Central India during March 2021 to February 2022. A total of 41 species belonging to 7 orders, 15 families and 29 genera were recorded with highest diversity during post‐monsoon season compared to the pre‐monsoon season and monsoon season. The fish abundance similarity between the monsoon and post‐monsoon reached a maximum of 89%. Seasonal variations in the mean species abundance, Simpson dominance index, Shannon diversity index, Pielou's evenness index and Margalef's richness index were determined. One‐way ANOVA revealed a significant difference (P < 0.05) at the temporal scale. There was a significant seasonal difference in species abundance (P = 0.0006) and evenness index (P = 0.02) among the diversity indices. During the study period, three ‘vulnerable’ species, three ‘near threatened’ species and two ‘endangered’ species were caught. Carnivore dominance was evident throughout the year in the trophic guild of fishes. The Pearson correlation test revealed that water pH, dissolved oxygen, sediment organic carbon and clay percentage were positively correlated to all four diversity indices. Simpson and Margalef species richness diversity indices were positively correlated to sediment pH. Fish abundance was positively associated with sediment pH, silt, phosphorus and nitrogen content. Canonical correspondence analysis was used to investigate the relationships between fish assemblages and environmental conditions. Among the 19 physicochemical parameters, nine (dissolved oxygen, total dissolved solids, conductivity, transparency, hardness, phosphate and chlorophyll‐a, sediment nitrogen and phosphorus) characteristics were shown to be statistically significant (P < 0.05) in determining fish diversity. Dissolved oxygen, total dissolved solids, conductivity, transparency, hardness, phosphate and chlorophyll‐a of water and sediment nitrogen and phosphorus qualities were the key factors for the species abundance. The reservoir boasts a diverse fish population that allows multi‐species fishing and generates revenue for numerous local fishers. Fish habitats should be protected in order to maintain diversity and long‐term ecological benefits.
Difluorocarbene in Cycloadditions and Annulations for the Synthesis of gem‐Difluorocarbocycles and gem‐Difluoroheterocycles
Authors: Xu Jiaxi , Sun Simin
Published: November 2023

Difluorocarbene is a simple, readily prepared, and versatile difluorinated one‐carbon synthon. It can be applied as both the difluoromethylating reagent in the carbene insertion and the difluoromethylenating reagent in various cycloadditions and annulations. This concept article provides an account of applications of difluorocarbene in cycloadditions and annulations for synthesis of gem‐difluorocarbocycles and gem‐difluoroheterocycles. The synthesized gem‐difluorocarbocycles include 2,2‐difluorobicyclo[1.1.1]pentanes, 4,4‐/5,5‐difluoro‐cyclopentenes, 2,2‐difluorocyclopentanones, and 5,5‐difluorocyclopent‐2‐enones via tandem [2+1] cycloaddition and ring‐expansion or [4+1] annulations. The prepared gem‐difluoroheterocycles involve 2,2‐/3,3‐difluoro‐2,3‐dihydrofurans, 2,2‐difluoro‐2,3‐dihydrobenzofurans, 2,2‐difluoro‐2,3‐dihydrobenzothiophenes, 2,2‐difluorobenzofuran‐3(2H)‐ones, 2,2‐difluorobenzothiophen‐3(2H)‐ones, 2,2‐difluoro‐2,3‐dihydrothieno[2,3‐b]pyridines, 2,2‐difluorothieno[2,3‐b]pyridine‐3(2H)‐ones, 5,5‐difluorooxazolines and thiazolines, and spirocyclic 2,2‐difluorobenzo[d][1,3]aza/phosphaborol‐1‐ium‐3‐yliums via [4+1] annulations, 1,1‐difluoro‐1,4,5,9b‐tetrahydro‐2H‐[1,2]diazeto[4,1‐a]isoquinolines and 1,1‐difluoro‐1,4,5,9b‐tetrahydro‐2H‐[1,2]diazeto[1,4‐a]pyrrolo[2,1‐c]pyrazines via [3+1] annulation, 1,1‐difluoro‐1,9a‐dihydropyrido[2,1‐c][1,4]thiazines and 3,3‐difluorobenzo[e][1,4,2]oxaza/phosphaborinin‐4‐ium‐2‐uides via [5+1] annulations, 9,9‐difluoro‐8‐azabicyclo[5.2.0]nona‐2,4,6‐trienes via [8+1] annulation, 4,4‐difluorooxazolidines and 3,3‐difluoropyrrolidines via [2+2+1] annulations. Difluorocarbene generated from different readily available precursors proceeds these cycloadditions and annulations well. The substrate scopes, proposed mechanisms, selected product examples and their applications are discussed.
Upcycling imperfect broccoli and carrots into healthy snacks using an innovative 3D food printing approach
Authors: Ahmadzadeh Safoura , Clary Taylor , Rosales Alex , Ubeyitogullari Ali
Published: November 2023

Vegetables are healthy foods with nutritional benefits; however, nearly one‐third of the world's vegetables are lost each year, and some of the losses happen due to the imperfect shape of the vegetables. In this study, imperfect vegetables (i.e., broccoli and carrots) were upcycled into freeze‐dried powders to improve their shelf‐life before they were formed into food inks for 3D printing. The rheology of the food inks, color analysis of the uncooked and cooked designs, and texture analysis of the cooked designs were determined. The inks with 50% and 75% vegetables provided the best printability and shape fidelity. 3D printing at these conditions retained a volume comparable to the digital file (14.4 and 14.3 cm3 vs. 14.6 cm3, respectively). The control, a wheat flour‐based formulation, showed the lowest level of stability after 3D printing. The viscosity results showed that all the food inks displayed shear‐thinning behavior, with broccoli having the greatest effect on viscosity. There was a significant color difference between uncooked and cooked samples, as well as between different formulations. The hardness of the baked 3D‐printed samples was affected by the type and content of vegetable powders, where carrot‐based snacks were notably harder than snacks containing broccoli. Overall, the results show that 3D food printing can be potentially used to reduce the loss and waste of imperfect vegetables.
Extent of thyroidectomy and paratracheal lymph node dissection in total pharyngolaryngectomy for pyriform sinus cancer, and recurrence, survival, and postoperative hypoparathyroidism: A multicenter retrospective study
Authors: Ariizumi Yosuke , Hanai Nobuhiro , Asakage Takahiro , Seto Akira , Tomioka Toshifumi , Miyabe Junji , Kessoku Hisashi , Mukaigawa Takashi , Omura Go , Teshima Masanori , Nishikawa Daisuke , Saito Yuki , Asada Yukinori , Fujisawa Takuo , Makino Takuma , Nishino Hiroshi , Sano Daisuke , Nakahira Mitsuhiko , Tokashiki Kunihiko , Uemura Hirokazu , Ueda Tsutomu , Sakai Akihiro , Masuda Muneyuki , Tsujikawa Takahiro , Hiei Yusuke , Nishio Naoki , Matsui Hidetoshi , Kiyota Naomi , Homma Akihiro
Published: November 2023

Background

Total pharyngolaryngectomy (TPL) is standard treatment for hypopharyngeal cancer. However, extensive thyroidectomy and paratracheal nodal dissection (PTND) can cause hypoparathyroidism. We sought to determine the optimum extent of resection.

Methods

We analyzed the clinicopathological information of 161 pyriform sinus cancer patients undergoing TPL from 25 Japanese institutions. Rates of recurrence and risk factors for hypoparathyroidism, as well as incidence of pathological contralateral level VI nodal metastasis and stomal recurrence, were investigated.

Results

The extent of thyroidectomy and nodal dissection were not independent risk factors for recurrence. Incidences of contralateral level VI nodal involvement and stomal recurrence were 1.8% and 1.2%, respectively. Patients undergoing hemithyroidectomy/ipsilateral PTND did not develop stomal recurrence and had the lowest incidence of hypoparathyroidism. Prognosis in patients without tracheostomy prior to hemithyroidectomy/ipsilateral PTND was comparable to that with more extensive resections.

Conclusions

Hemithyroidectomy/ipsilateral PTND may be sufficient for pyriform sinus cancer cases without tracheostomy.
Frequency of digital vaginal examination and associated factors among mothers admitted to labor and delivery wards in public health facilities of Arba Minch town, southern Ethiopia
Authors: Afework Bezawit , Birgoda Gebremaryam Temesgen , Leul Hawi , Girma Lamrot , Bekelcho Tariku
Published: November 2023

Objective

To assess the frequency of digital examination and its associated factors among laboring mothers in public health facilities in Arba Minch town, southern Ethiopia. Digital vaginal examination (DVE) is the commonly applied clinical assessment method used to discover the progress of labor and delivery. However, frequent DVE may not be free of risk for maternal and neonatal health, and pain during intrapartum care.

Methods

An institution‐based descriptive cross‐sectional study was employed from May 3 to July 6, 2022. Study participants were selected by a serial sampling method. Data were entered into epi data version 7.2 and exported to SPSS v.25 for data analysis. Binary and multivariate logistic regression analyses were employed to assess associations between study variables. Statistical significance was declared at a P value less than 0.05.

Results

A total of 374 women responded to the interview, making a response rate of 98.4%. In all, 230 (61.5%) of the laboring mothers underwent five or more DVE. Being a primipara, being in latent phase at admission, having augmentation of labor, prolonged labor, being admitted with intact membranes, and vacuum delivery showed significant associations with frequent DVE.

Conclusion

Frequency of DVE among laboring mothers is relatively high in the study area. The frequent DVE were mainly caused by healthcare provider's interventions to shorten the time of labor. Emphasis on training and monitoring the practice of healthcare givers would be helpful to mitigate this problem.
Measurements of the switched gradient magnetic field in MRI: A closer look at some unintuitive spatial characteristics
Authors: Frankel Jennifer , Mild Kjell Hansson , Olsrud Johan , Garpebring Anders , Wilén Jonna
Published: November 2023

Concomitant fields are the unwanted transverse components that arise when spatial encoding gradients are applied in MRI. We measured the changing gradient magnetic field at multiple locations inside the scanner and examined the internal distribution and linearity of the three vector components of the field. Our results illustrate some not‐so‐obvious spatial characteristics of the gradient field, which can seem unintuitive at first glance, but are quite reasonable when considering electromagnetic theory and MRI‐scanner physics constraints.
The Drug War and Regional Social Capital in Mexico
Authors: Vögele Julian‐Ferdinand , Reck Fabian , Fidrmuc Jarko
Published: November 2023

The onset of the war on drugs in Mexico at the beginning of 21st century had far‐reaching effects on its citizens, including most obviously, an unprecedented increase in the homicide rate. We analyse the correlation between violence on social capital in the 32 federal states of Mexico from January 2004 to December 2016. Given the lack of data in the conflict regions of Mexico, we apply the indirect approach proposed by Guriev and Melnikov (2016), which uses internet search engine data to proxy social capital. Our results show a negative relationship between violence and social capital in Mexico. Moreover, we document a positive spatial correlation for social capital. Overall, we present an example of how the analysis of internet‐based data can contribute to the understanding of socioeconomic developments in conflict regions with unreliable standard data.
Glioblastoma and Solitary Brain Metastasis: Differentiation by Integrating Demographic‐MRI and Deep‐Learning Radiomics Signatures
Authors: Zhang Yuze , Zhang Hongbo , Zhang Hanwen , Ouyang Ying , Su Ruru , Yang Wanqun , Huang Biao
Published: November 2023

Background

Studies have shown that deep‐learning radiomics (DLR) could help differentiate glioblastoma (GBM) from solitary brain metastasis (SBM), but whether integrating demographic‐MRI and DLR features can more accurately distinguish GBM from SBM remains uncertain.

Purpose

To construct and validate a demographic‐MRI deep‐learning radiomics nomogram (DDLRN) integrating demographic‐MRI and DLR signatures to differentiate GBM from SBM preoperatively.

Study Type

Retrospective.

Population

Two hundred and thirty‐five patients with GBM (N = 115) or SBM (N = 120), randomly divided into a training cohort (90 GBM and 98 SBM) and a validation cohort (25 GBM and 22 SBM).

Field Strength/Sequence

Axial T2‐weighted fast spin‐echo sequence (T2WI), T2‐weighted fluid‐attenuated inversion recovery sequence (T2‐FLAIR), and contrast‐enhanced T1‐weighted spin‐echo sequence (CE‐T1WI) using 1.5‐T and 3.0‐T scanners.

Assessment

The demographic‐MRI signature was constructed with seven imaging features (“pool sign,” “irregular ring sign,” “regular ring sign,” “intratumoral vessel sign,” the ratio of the area of peritumoral edema to the enhanced tumor, the ratio of the lesion area on T2‐FLAIR to CE‐T1WI, and the tumor location) and demographic factors (age and sex). Based on multiparametric MRI, radiomics and deep‐learning (DL) models, DLR signature, and DDLRN were developed and validated.

Statistical Tests

The Mann–Whitney U test, Pearson test, least absolute shrinkage and selection operator, and support vector machine algorithm were applied for feature selection and construction of radiomics and DL models.

Results

DDLRN showed the best performance in differentiating GBM from SBM with area under the curves (AUCs) of 0.999 and 0.947 in the training and validation cohorts, respectively. Additionally, the DLR signature (AUC = 0.938) outperformed the radiomics and DL models, and the demographic‐MRI signature (AUC = 0.775) was comparable to the T2‐FLAIR radiomics and DL models in the validation cohort (AUC = 0.762 and 0.749, respectively).

Data Conclusion

DDLRN integrating demographic‐MRI and DLR signatures showed excellent performance in differentiating GBM from SBM.

Level of Evidence

3

Technical Efficacy

Stage 2
Single‐differential difference current conveyor‐based first‐order VM/TAM universal filter and its applications
Authors: Raj Ajishek , Senani Raj , Bhaskar D. R.
Published: November 2023

A new first‐order universal filter structure is presented in this article using a single differential difference current conveyor (DDCC). The proposed circuit can provide three first‐order filter functions namely, high‐pass filter (HPF), low‐pass filter (LPF), and all‐pass filter (APF) in voltage mode (VM) and transadmittance mode (TAM) both. A voltage amplifier with a gain of 2 is required for the realization of the APF functions in both the modes while for LPF and HPF, no condition is required. The pole frequency and gain of the proposed circuit can be controlled separately. The effect of the parasitic impedances of the DDCC has been modeled in the nonideal equivalent circuit from which nonideal parameters have been evaluated and compared with their ideal ones. Application examples of the proposed circuits configured as amplitude equalizer (in both modes) and in the realization of a simple wideband band‐pass filter are also discussed. The functionality of the proposed circuit as well as its mentioned application circuits is verified using complementry metal oxide semiconductor DDCC to support the theoretical propositions. Some experimentally observed frequency responses and transient responses of the various VM filters have also been corroborated using DDCC implemented using AD844 ICs.
Cultivating strategic agility – An empirical investigation into best practice
Authors: Christofi Kyriakos , Chourides Pieris , Papageorgiou George
Published: November 2023

Amidst the fluidity of today's post‐COVID business environment, this paper aims to fortify the discourse on strategic agility, by presenting a comprehensive best practice framework for its development and sustenance. This is achieved by carrying out an empirical investigation on four best practice multinational corporations. Despite abundant scholarly attention, a critical gap persists in the empirical examination of specific functional practices and their role for fostering strategic agility. This research fills this void, leveraging in‐depth interviews with strategic‐level managers and analyzing archival data, revealing that strategic agility necessitates a systemic approach and congruent efforts across organizational functions. Key findings underscore the role knowledge management as the linchpin, with corresponding emphasis on dynamic talent management, strategic partnerships, open innovation, digitalization, and sustainability. As a result, this paper contributes to the strategic management literature by offering practical insights for managers of global businesses in navigating the complexities of a rapidly evolving competitive landscape towards organizational excellence
Estimation of kidney function for medication dosing in adult patients with chronic kidney disease: a practice update
Authors: Mirkov Sanja , Scuderi Carla , Lloyd Jess , Coutsouvelis John , O'Connor Shaun , Potts Simon , Newman Suzanne , Roberts Jason
Published: November 2023

Chronic kidney disease (CKD) is a major health concern with a growing disease burden and inequalities in access to treatments. Glomerular filtration rate (GFR) is accepted as the best overall measure of kidney function and is considered the most important measure for medications cleared by the kidneys. In clinical practice, equations that estimate GFR using validated prediction equations are routinely used. This practice update was developed by a Working Group comprising clinical pharmacists representing the Society of Hospital Pharmacists of Australia (SHPA) Specialty Practice streams of Nephrology, Oncology and haematology, Critical care and Infectious diseases. It is intended to provide practical recommendations for clinical pharmacists who use equations to estimate GFR for medication dosing decisions. The limitations of the various equations in use — such as the Chronic Kidney Disease Epidemiology Collaboration (CKD‐EPI), the Cockcroft–Gault equation and Modification of Diet in Renal Disease — are summarised and compared to direct measures of kidney function using exogenous markers. The CKD‐EPI equation is recommended to be used routinely as a primary measure of kidney function. Dose adjustments should also consider medication‐specific, patient‐related, and disease‐related characteristics. Kidney function and the response to therapy should be continuously assessed by monitoring the signs, symptoms and disease outcomes, the emergence of adverse reactions or medication‐induced disorders and use therapeutic drug monitoring (if available) to adjust doses accordingly.