bluuebunny/crossref_metadata_2025 huggingface dataset:
A novel perspective on the role of nucleus accumbens neurons in encoding associative learning
Authors: Domingues Ana Verónica , Rodrigues Ana João , Soares‐Cunha Carina
Published: August 2023

The nucleus accumbens (NAc) has been considered a key brain region for encoding reward/aversion and cue–outcome associations. These processes are encoded by medium spiny neurons that express either dopamine receptor D1 (D1‐MSNs) or D2 (D2‐MSNs). Despite the well‐established role of NAc neurons in encoding reward/aversion, the underlying processing by D1‐/D2‐MSNs remains largely unknown. Recent electrophysiological, optogenetic and calcium imaging studies provided insight on the complex role of D1‐ and D2‐MSNs in these behaviours and helped to clarify their involvement in associative learning. Here, we critically discuss findings supporting an intricate and complementary role of NAc D1‐ and D2‐MSNs in associative learning, emphasizing the need for additional studies in order to fully understand the role of these neurons in behaviour.
Benthic foraminiferal growth seasons implied from Mg/Ca‐temperature correlations for three Arctic species
Authors: Skirbekk Kari , Hald Morten , Marchitto Thomas M. , Junttila Juho , Klitgaard Kristensen Dorthe , Aagaard Sørensen Steffen
Published: August 2023

Core‐top sediment samples from Kongsfjorden, Svalbard, and adjacent fjord and shelf areas were collected in order to investigate a potential relationship between Mg/Ca‐ratios of Arctic benthic foraminifera and the ambient bottom water temperatures (BWT). The area is influenced by large seasonal variation in factors such as light and temperature, which is further strengthened by oceanographic shifts, including inflow of relatively warm Atlantic water. Four hydrological seasons have been defined. The studied samples were collected during the years 2005–2010 and comprise data from three hydrological seasons: spring, summer, and autumn. Five common species of cold‐water benthic foraminifera were investigated: Islandiella helenae/norcrossi, Buccella frigida, Nonionellina labradorica, Elphidium clavatum, and Cassidulina reniforme. For E. clavatum and C. reniforme, the investigations failed. For the remaining three species, the Mg/Ca‐temperature correlations initially appeared stochastic holding correlation coefficients between 0.01 and 0.15. However, grouping the data based on seasons gave stronger Mg/Ca‐temperature correlations, indicating specific growing seasons for the three species. The equations represent a starting point for a discussion on seasonality rather than robust, “ready‐to‐use” equations. I. helenae/norcrossi seems to reproduce and grow during summer (July/August) in outer Kongsfjorden. For B. frigida, a Mg/Ca‐temperature correlation is seen both in summer (July/August) and autumn (October/November) samples, indicative of a continuous reproduction/growth‐season lasting from July to November. N. labradorica appears to reproduce and grow during autumn (October/November). The results indicate that temperature reconstructions based on these benthic foraminifera reproduce seasonal temperatures rather than annual average temperatures.
Orelabrutinib for the treatment of relapsed or refractory marginal zone lymphoma: A phase 2, multicenter, open‐label study
Authors: Deng Lijuan , Li Zhiming , Zhang Huilai , Huang Haiwen , Hu Jianda , Liu Lihong , Liu Ting , Jin Jie , Zhu Zunmin , Li Wenyu , Huang Zhenqian , Huang Wenrong , Zhou Keshu , Yang Haiyan , Zhang Mingzhi , Ding Kaiyang , Zhou Hui , Hu Yu , Shuang Yuerong , Cao Junning , Gao Sujun , Li Dengju , Sun Zimin , Zhang Qingyuan , Yi Shuhua , Ji Chunyan , Zhang Liansheng , Hou Cheng , Du Yue , Wang Weige , Zhao Renbin , Song Yuqin , Zhu Jun
Published: August 2023

Marginal zone lymphoma (MZL) is an indolent type of non‐Hodgkin lymphoma that develops through pathological B cell receptor signaling. Orelabrutinib, a new‐generation oral small molecule Bruton's tyrosine kinase inhibitor, was evaluated in relapsed/refractory (r/r) MZL patients. Previously treated r/r MZL patients received orelabrutinib 150 mg once daily in a phase 2, multicenter, single‐arm study conducted in China. The primary endpoint was overall response rate (ORR) assessed by an Independent Review Committee (IRC) based on the Lugano 2014 classification. Other efficacy, safety, and pharmacokinetic profiles were evaluated as secondary outcome measures. A total of 111 patients were enrolled, of which 90 patients had MZL confirmed by central pathology review, who were mainly with extra‐nodal MZL of mucosa‐associated lymphoid tissue (MALT, 46.7%) and nodal MZL (35.6%). The majority had late‐stage disease, with stage IV accounting for 75.6%. After a median follow‐up duration of 24.3 months, the IRC‐assessed ORR was 58.9% (95% confidence interval [CI], 48.0–69.2), with rates of complete response and partial response being 11.1% and 47.8%, respectively. The IRC‐assessed median duration of response was 34.3 months, and the IRC‐assessed median progression‐free survival (PFS) was not reached with a 12‐month PFS rate of 82.8% (95% CI, 72.6–89.5). The rate of overall survival at 12 months was 91.0% (95% CI, 82.8–95.4). Common all‐grade treatment‐related adverse events (TRAEs) included anemia (27.9%), neutrophil count decrease (23.4%), white blood cell count decrease (18.0%), platelet count decrease (17.1%), blood present in urine (16.2%), rash (14.4%), and upper respiratory tract infection (10.8%). Thirty‐four patients (30.6%) experienced grade 3 or higher TRAEs. Serious TRAEs occurred in 18 patients (16.2%), of which pneumonia (5.4%) was the most common. Seven patients (6.3%) discontinued orelabrutinib due to TRAEs. Orelabrutinib demonstrated high response rates with durable disease remission and was well tolerated in Chinese patients with r/r MZL.
Risk of progression in chronic phase‐chronic myeloid leukemia patients eligible for tyrosine kinase inhibitor discontinuation: Final analysis of the TFR‐PRO study
Authors: Zambrotta Giovanni Paolo Maria , Nicolini Franck E. , Assouline Sarit , Busque Lambert , Pungolino Ester , Abruzzese Elisabetta , Miggiano Maria Cristina , Elena Chiara , Alvarez‐Larran Alberto , Triguero Ana , Iurlo Alessandra , Bucelli Cristina , Cerrano Marco , Capodanno Isabella , Lunghi Francesca , le Coutre Philipp , Galimberti Sara , Caocci Giovanni , Maffioli Margherita , Stagno Fabio , Saussele Susanne , Piazza Rocco , Druker Brian J. , Fava Carmen , Guglielmana Veronica , Colombo Federica , Antolini Laura , Gambacorti‐Passerini Carlo
Published: August 2023

Disease progression to accelerated/blast phase (AP/BP) in patients with chronic phase chronic myeloid leukemia (CP‐CML) after treatment discontinuation (TD) has never been systematically reported in clinical trials. However, recent reports of several such cases has raised concern. To estimate the risk of AP/BP among TD‐eligible patients, we conducted TFR‐PRO, a cohort retro‐prospective study: 870 CP‐CML patients eligible for TD formed a discontinuation cohort (505 patients) and a reference one (365 patients). The primary objective was the time adjusted rate (TAR) of progression in relation to TD. Secondary endpoints included the TAR of molecular relapse, that is, loss of major molecular response (MMR). With a median follow up of 5.5 years and 5188.2 person‐years available, no events occurred in the TD cohort. One event of progression was registered 55 months after the end of TD, when the patient was contributing to the reference cohort. The TAR of progression was 0.019/100 person‐years (95% CI [0.003–0.138]) in the overall group; 0.0 (95% CI [0–0.163]) in the discontinuation cohort; and 0.030 (95% CI [0.004–0.215]) in the reference cohort. These differences are not statistically significant. Molecular relapses occurred in 172/505 (34.1%) patients after TD, and in 64/365 (17.5%) patients in the reference cohort, p < .0001. Similar rates were observed in TD patients in first, second or third line of treatment. CML progression in patients eligible for TD is rare and not related to TD. Fears about the risk of disease progression among patients attempting TD should be dissipated.
2024 Update: Advances in the risk stratification and management of large B‐cell lymphoma
Authors: Tavakkoli Montreh , Barta Stefan K.
Published: August 2023

Diffuse large B‐cell lymphoma (DLBCL) is a heterogeneous disease with varying clinical outcomes. Our understanding of its molecular makeup continues to improve risk stratification, and artificial‐intelligence and ctDNA‐based analyses have the potential to enhance risk assessment and disease monitoring. R‐CHOP and Pola‐R‐CHP are used in the frontline setting; chimeric antigen receptor therapy (CART) is now the new standard‐of‐care for most with primary refractory disease; both CART and autologous stem cell transplantation are utilized in the relapsed and refractory setting. In this review, we summarize the classification and management of DLBCL with an emphasis on recent advances in the field.
Ultra‐Small Air‐Stable Triplet‐Triplet Annihilation Upconversion Nanoparticles for Anti‐Stokes Time‐Resolved Imaging
Authors: Zhang Bolong , Richards Kieran D. , Jones Beatrice E. , Collins Abigail R. , Sanders Rosie , Needham Sarah R. , Qian Pu , Mahadevegowda Amoghavarsha , Ducati Caterina , Botchway Stanley W. , Evans Rachel C.
Published: August 2023

Image contrast is often limited by background autofluorescence in steady‐state bioimaging microscopy. Upconversion bioimaging can overcome this by shifting the emission lifetime and wavelength beyond the autofluorescence window. Here we demonstrate the first example of triplet‐triplet annihilation upconversion (TTA‐UC) based lifetime imaging microscopy. A new class of ultra‐small nanoparticle (NP) probes based on TTA‐UC chromophores encapsulated in an organic–inorganic host has been synthesised. The NPs exhibit bright UC emission (400–500 nm) in aerated aqueous media with a UC lifetime of ≈1 μs, excellent colloidal stability and little cytotoxicity. Proof‐of‐concept demonstration of TTA‐UC lifetime imaging using these NPs shows that the long‐lived anti‐Stokes emission is easily discriminable from typical autofluorescence. Moreover, fluctuations in the UC lifetime can be used to map local oxygen diffusion across the subcellular structure. Our TTA‐UC NPs are highly promising stains for lifetime imaging microscopy, affording excellent image contrast and potential for oxygen mapping that is ripe for further exploitation.
An Asymmetric Hydrogenation/N‐Alkylation Sequence for a Step‐Economical Route to Indolizidines and Quinolizidines
Authors: Zhao Wei , Wang Wenji , Zhou Huan , Liu Qishan , Ma Zhiqing , Huang Haizhou , Chang Mingxin
Published: August 2023

The direct catalytic asymmetric hydrogenation of pyridines for the synthesis of piperidines remains a challenge. Herein, we report a one‐pot asymmetric hydrogenation of pyridines with subsequent N‐alkylation using a traceless Brønsted acid activation strategy. Catalyzed by an iridium‐BINAP complex, the substrates undergo ketone reduction, cyclization and pyridine hydrogenation in sequence to form indolizidines and quinolizidines. The absolute configuration of the stereocenter of the alcohol is retained and influences the formation of the second stereocenter. Experimental and theoretical mechanistic studies reveal that the chloride anion and certain noncovalent interactions govern the stereoselectivity of the cascade reaction throughout the catalytic process.
Multitargeting Prodrugs that Release Oxaliplatin, Doxorubicin and Gemcitabine are Potent Inhibitors of Tumor Growth and Effective Inducers of Immunogenic Cell Death
Authors: Sarkar Amrita , Novohradsky Vojtech , Maji Moumita , Babu Tomer , Markova Lenka , Kostrhunova Hana , Kasparkova Jana , Gandin Valentina , Brabec Viktor , Gibson Dan
Published: August 2023

A multitargeting prodrug (2) that releases gemcitabine, oxaliplatin, and doxorubicin in their active form in cancer cells is a potent cytotoxic agent with nM IC50s; it is highly selective to cancer cells with mean selectivity indices to human (136) and murine (320) cancer cells. It effectively induces release of DAMPs (CALR, ATP & HMGB1) in CT26 cells facilitating more efficient phagocytosis by J774 macrophages than the FDA drugs or their co‐administration. The viability of CT26 cells co‐cultured with J774 macrophages and treated with 2 was reduced by 32 % compared to the non‐treated cells, suggesting a synergistic antiproliferative effect between the chemical and immune reactions. 2 inhibited in vivo tumor growth in two murine models (LLC and CT26) better than the FDA drugs or their co‐administration with significantly lower body weight loss. Mice inoculated with CT26 cells treated with 2 showed slightly better tumor free survival than doxorubicin.
In‐Situ‐Formed Potassium‐Modified Nickel‐Zinc Carbide Boosts Production of Higher Alcohols beyond CH4 in CO2 Hydrogenation
Authors: Wang Jia , Wang Tingting , Xi Yongjie , Gao Guang , Sun Peng , Li Fuwei
Published: August 2023

Ni‐based catalysts have been widely studied in the hydrogenation of CO2 to CH4, but selective and efficient synthesis of higher alcohols (C2+OH) from CO2 hydrogenation over Ni‐based catalyst is still challenging due to successive hydrogenation of C1 intermediates leading to methanation. Herein, we report an unprecedented synthesis of C2+OH from CO2 hydrogenation over K‐modified Ni−Zn bimetal catalyst with promising activity and selectivity. Systematic experiments (including XRD, in situ spectroscopic characterization) and computational studies reveal the in situ generation of an active K‐modified Ni−Zn carbide (K‐Ni3Zn1C0.7) by carburization of Zn‐incorporated Ni0, which can significantly enhance CO2 adsorption and the surface coverage of alkyl intermediates, and boost the C−C coupling to C2+OH rather than conventional CH4. This work opens a new catalytic avenue toward CO2 hydrogenation to C2+OH, and also provides an insightful example for the rational design of selective and efficient Ni‐based catalysts for CO2 hydrogenation to multiple carbon products.
Improved Interfacial Ion Migration and Deposition through the Chain‐Liquid Synergistic Effect by a Carboxylated Hydrogel Electrolyte for Stable Zinc Metal Anodes
Authors: Tian Cong , Wang Jielei , Sun Ruoxuan , Ali Tariq , Wang Hongfei , Xie Bin‐Bin , Zhong Yijun , Hu Yong
Published: August 2023

The large‐scale applicability of Zn‐metal anodes is severely impeded by the issues such as the dendrite growth, complicated hydrogen evolution, and uncontrollable passivation reaction. Herein, a negatively charged carboxylated double‐network hydrogel electrolyte (Gelatin/Sodium alginate‐acetate, denoted as Gel/SA‐acetate) has been developed to stabilize the interfacial electrochemistry, which restructures a type of Zn2+ ion solvent sheath optimized via a chain‐liquid synergistic effect. New hydrogen bonds are reconstructed with water molecules by the zincophilic functional groups, and directional migration of hydrated Zn2+ ions is therefore induced. Concomitantly, the robust chemical bonding of such hydrogel layers to the Zn slab exhibits a desirable anti‐catalytic effect, thereby greatly diminishing the water activity and eliminating side reactions. Subsequently, a symmetric cell using the Gel/SA‐acetate electrolyte demonstrates a reversible plating/stripping performance for 1580 h, and an asymmetric cell reaches a state‐of‐the‐art runtime of 5600 h with a high average Coulombic efficiency of 99.9 %. The resultant zinc ion hybrid capacitors deliver exceptional properties including the capacity retention of 98.5 % over 15000 cycles, energy density of 236.8 Wh kg−1, and high mechanical adaptability. This work is expected to pave a new avenue for the development of novel hydrogel electrolytes towards safe and stable Zn anodes.
Adsorptive removal of dibenzothiophene from model fuel over activated carbon developed by KOH activation of pinecone: Equilibrium and kinetic studies
Authors: Khalid Rand Y. , Fadhil Abdelrahman B.
Published: August 2023

Activated carbon (AC) was developed from pinecone using KOH as an activator to eliminate dibenzothiophene (DBT) from a synthetic model of gasoline fuel. The best sample was the AC prepared, employing a 1.5:1 KOH: feed impregnation ratio at 750°C for 1 h. Thus, it was tested in the adsorptive elimination of DBT from the fuel after being identified by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FESEM), energy dispersive X‐ray (EDX), N2 adsorption–desorption isotherms, pore volume distribution, Fourier transform infrared spectroscopy (FTIR), total basic and acid groups, and pHPZC. The as‐obtained AC exhibited a Brunauer–Emmett–Teller (BET) surface area of 478.89 m2/g with an average pore size of 2.0 nm, indicating its micropores structure. A removal performance of 97.90% was obtained using 0.30 g of AC at 20°C for 30 min, while the adsorptive capacity amounted to 34.38 mg/g as per the Langmuir isotherm. The as‐synthesized AC exhibited a good adsorptive performance for eliminating S compounds from commercial gasoline (42.11%) under the optimal experimental conditions, which increased to 88.16% with increasing the mass of AC implemented in the adsorption process. The adsorption of DBT through the fixed‐bed approach was also adopted, and the results at various flow rates of the effluent through fixed bed of the AC were close to that obtained via the batch‐adsorption system. The regenerated AC exhibited excellent adsorptive performance for DBT until 5 cycles of reuse, reflecting the effectiveness of the obtained AC. Finally, the Langmuir adsorption isotherm and pseudo‐second‐order kinetics model best described the DBT adsorption by the AC developed from pinecone.
Comparing vagus nerve stimulation and resective surgery outcomes in patients with co‐occurring autism and epilepsy to patients with epilepsy alone: A population‐based study
Authors: Subramaniam Varun R. , Mu Lan , Kwon Churl‐Su
Published: August 2023

Autism and epilepsy commonly co‐occur. Understanding trends in healthcare utilization and in‐hospital outcomes amongst patients with autism and epilepsy can help optimize care and reduce costs. We compared hospital outcomes amongst patients with autism and epilepsy to those with epilepsy alone undergoing vagus nerve stimulation (VNS) and resective/disconnective surgery. Differences in discharge status, in‐hospital mortality, mean length of stay (LOS), cost and surgical/medical complications were examined. Elective surgical admissions amongst patients with epilepsy alone and co‐occurring autism and epilepsy were identified in the 2003–14 National Inpatient Sample (NIS) using previously validated ICD‐9‐CM case definitions. One patient with co‐occurring epilepsy and autism was matched to three epilepsy patients for age, sex and (1) VNS and (2) resective/disconnective surgery. Multinomial logistic regressions were performed to examine the outcomes of interest. Data were collected on: (1) VNS‐52 (mean age: 12.79 ± 1.03; 19.27% female) hospital admissions in persons with comorbid autism and epilepsy, 156 (mean age: 12.84 ± 0.71; 19.31% female) matched controls with epilepsy alone; (2) resective/disconnective surgery‐113 (mean age: 12.99 ± 0.84; 24.55% female) with comorbid autism and epilepsy, 339 (mean age: 13.37 ± 0.68; 23.86% female) matched controls with epilepsy alone. Compared to patients with epilepsy alone, patients with autism and epilepsy who underwent either surgery showed no differences for in‐hospital mortality, discharge status, mean LOS, hospitalization cost, and surgical/medical complications. Our study shows the feasibility and safety of epilepsy VNS and resective surgery in those with ASD do not differ with those with epilepsy alone, contrary to the prevalent safety concerns of epilepsy surgery in patients with ASD.
Der Neuentwurf zur DEGA Richtlinie 103‐1: Schallschutz im Wohnungsbau – Schallschutzklassen und erhöhter Schallschutz
Authors: Schneider Martin , Nocke Christian , Burkhart Christian
Published: August 2023

In diesem Beitrag wird der Entwurf der DEGA‐Richtlinie 103‐1 : 2023‐05 „Schallschutz im Wohnungsbau Teil 1: Schallschutzklassen und erhöhter Schallschutz“ vorgestellt [1]. Dieser Entwurf basiert auf der DEGA‐Empfehlung 103, Ausgabe 2018. Einsprüche zu diesem Entwurf können bis zum 09. 10. 2023 an die DEGA gesendet werden. Der hier vorgestellte Teil 1 behandelt die Schallschutzklassen mit den dazu gehörenden Anforderungen. In einem noch zu erarbeitenden Teil 2 soll dann der Schallschutzausweis behandelt werden. Im Entwurf wird das Konzept der sieben Schallschutzklassen aus der DEGA‐Empfehlung 103 weitergeführt. Wesentliche Änderung ist die Einführung eines parallelen Konzepts bauteilbezogener und raumbezogener Kenngrößen zum Schallschutz. Bezüglich der subjektiven Wahrnehmung von Geräuschen wird die Anwendung der raumbezogenen Kenngrößen (DnT,w, LnT,w und LAF,max,nT) empfohlen. Die Klassifizierung erfolgt anhand dieser Kenngrößen, kann aber auch mithilfe der bisher gewohnten Größen für die Schalldämmung von Bauteilen (R'w, L'n,w) erfolgen. Die aktuell diskutierten Änderungen bei der geplanten Überarbeitung der DIN 4109 Reihe wurden dabei berücksichtigt.
Ein Beitrag zur Kenntnis der Anomalien des Chroms und seines Verhaltens gegen Wechselstrom bei der Elektrolyse
Authors: Isgarischew N. , Obrutschewa A.
Published: August 2023

1. Es wurde die Löslichkeit von Chrom unter dem Einflusse von Gleich‐ und Wechselstrom untersucht; auch die gemeinsame Wirkung beider Ströme in sauren, neutralen und Alkalilösungen.

2. Die beobachteten Erscheinungen bekamen eine Erklärung, die sich auf der Annahme einer kolloidalen deckenden Haut gründet. Diese Haut ist die Ursache der Passivität, die ihrerseits die Hauptursache von den vielen Chromanomalien ist.

3. Bei der Elektrolyse unter den früher angegebenen Bedingungen löst sich Chrom zwei‐, drei‐ und sechswertig. Die Menge jeder der drei Wertigkeiten des Metalls kann je nach den Verhältnissen verschieden sein.

4. Es wurde die eigentümliche aktivierende Wirkung von verschiedenen Anionen und Kationen auf passives Chrom untersucht und vom Standpunkte kolloidchemischer Umwandlungen erklärt.
Kurzvorträge zum Hauptthema. Untersuchung der Sauerstoffbeweglichkeit in Titandioxyd, Quarz und Quarzglas mit Hilfe des heterogenen Isotopenaustausches
Authors: Haul R. , Dümbgen G.
Published: August 2023

Aus der Abhängigkeit der Austauschgeschwindigkeit von Temperatur und Sauerstoffdruck sowie dem Einfluß von Fremdoxyden ergeben sich Aufschlüsse über die Fehlordnung der untersuchten Oxyde und den Mechanismus der Sauerstoffselbstdiffusion. Die Messungen an TiO2 sprechen für das Vorliegen von Anionenleerstellen. Beim Quarzglas liegen insofern besondere Verhältnisse vor, als eine Wanderung des Sauerstoffs in molekularer Form zu berücksichtigen ist. Die Sauerstoffselbstdiffusion in Quarzkristallen erfolgt im Vergleich zum Quarzglas mit erheblich geringerer Geschwindigkeit.
Über die Reduktion von Oxyd‐Mischkristallen
Authors: Engell H.‐J. , Kohl H. K.
Published: August 2023

Bei der Reduktion von binären oxydischen Mischkristallen reichert sich die metallische Komponente mit dem geringeren Absolutwert der freien Enthalpie der Oxydbildung in der Metallphase, die andere Komponente in der Oxydphase an. Im stationären Ablauf der Reduktion muß daher ein Materialtransport in der Oxydphase stattfinden. Unter der Annahme von idealem Verhalten von Metall‐ und Oxydphase werden die Transportgleichungen aufgestellt. Es zeigt sich, daß bei ablaufender Reduktion im Oxyd fast ausschließlich das unedlere Metall diffundiert, das edlere Metall dagegen kaum an der Diffusion teilnimmt. Daher muß sich die Metallphase nicht auf der Oberfläche, sondern im Innern des Oxyds ausscheiden. Reduktionsversuche an verschiedenen Oxydmischkristallen bestätigen diese Folgerung.
Crystal Growth by Chemical Transport Reactions II: Equilibrium Measurements in the System Cadmium Sulfide‐Iodine
Authors: Nitsche R. , Richman D.
Published: August 2023

The gas phase equilibria in the system cadmium sulfide‐iodine have been studied in the temperature range 400–800 °C. The total pressure of the reaction mixture as a function of temperature was measured with a quartz Bourdon gauge. Absorption spectroscopy was used to evaluate the iodine concentration in the gas phase. From these data the reaction can be described by

By considering the iodine dissociation as well as the equilibria between the various sulfur species S2, S4, S6, S8, the equilibrium constant for the above reaction is given by

in the entire temperature range studied.
Chemisorption und Widerstandsänderungen an aufgedampften Zirkoniumfilmen
Authors: Hansen N.
Published: August 2023

An im Höchstvakuum aufgedampften Zirkoniumfilmen wurde die Oberfläche gemessen und die Kinetik und die elektrischen Widerstandsänderungen bei der Adsorption von Kohlenmonoxid untersucht. Es treten verschiedene Chemisorptionsmechanismen auf, die sich in der Kinetik und der relativen Widerstandsänderung unterscheiden. Die Widerstandsänderungen lassen sich durch eine Verbindungsbildung mit einer bestimmten Zahl von Oberflächenatomen des Metalls und einer damit verbundenen Verringerung der effektiven Schichtdicke deuten.
Rotational and Translational Diffusion and Dipolar Spin Relaxation in Diamagnetic Electrolyte Solutions
Authors: Hertz H. C.
Published: August 2023

The present paper starts from the question to what an extent correlation times for the molecular rotation (or reorientation times) in the hydration shells may be derived from the nuclear magnetic relaxation times of the protons in diamagnetic electrolyte solutions.

The intramolecular relaxation rate of the protons in aqueous electrolyte solutions is calculated. Use is made of a model in which the reorientation times in the hydration shells and the free water are different. Moreover, the various regions of the solution are characterized by different rotation‐step constants. The treatment is closely related to a work by Beckert and Pfeifer concerning the same subject. The results of the theorie are discussed with regard to the above mentioned question.

Further, the calculation of the self‐diffusion coefficient of the water molecules in an electrolyte solution is described. The theory given is a random‐walk treatment, the procedure is similar to that presented for the rotational motion in the first part of this paper.

In the last section the problem of the separation of the electrolyte solution in hydration shells and free water in its special concern to the rotational correlation times is dealt with.
A Microdynamic Model of Electrolyte Solutions as Derived from Nuclear Magnetic Relaxation and Self‐Diffusion Data
Authors: Endom L. , Hertz H. G. , Thül B. , Zeidler M. D.
Published: August 2023

Experimental data of the proton relaxation rate in aqueous solutions of alkali and alkaline earth halides at four different temperatures (0, 25, 50, 80 °C) are reported. A number of measured self‐diffusion coefficients of water in electrolyte solutions at various temperatures are also given. From these experimental data models of the electrolyte solutions are derived which are characterized by certain hydration numbers, reorientational correlation times for the water molecules, translational jumping times, and by the activation energies connected with the respective microdynamic processes.
Die Strömungsmethode mit integrierender Anzeige zur Untersuchung schneller Reaktionen in Lösung unter Einbeziehung des Mischvorgangs
Authors: Gerischer H. , Heim W.
Published: August 2023

Es wird für das Verfahren der Strömungsmethode mit integrierender Anzeige eine neue Meßzellenkonstruktion angegeben, mit welcher der Ablauf des Mischvorgangs zugleich mit der eigentlichen chemischen Reaktion erfaßt werden kann. Mit Hilfe der empirisch gefundenen Beziehung für die Zeitabhängigkeit des Mischprozesses können dann Reaktionen noch erfaßt werden, deren Abklingzeiten von gleicher Größenordnung sind wie die Abklingzeiten der Vermischung. Das sind bei den hier verwandten Meßzellen Zeiten in der Größenordnung von 10−5 sec. Mit diesem Verfahren wurde die Geschwindigkeitskonstante der Reaktion K4 [Fe(CN)6] + Fe(phen)3(ClO4)3 in 0,5 n Perchlorsäure gemessen. Es wurde an dieser Reaktion zugleich die Übereinstimmung der Resultate mit dem normalen integrierenden Verfahren überprüft.
Diffusionsüberspannung, Durchtrittsüberspannung und Doppelschichtaufladung beim galvanostatischen Einschaltvorgang
Authors: Bachmann K. J.
Published: August 2023

Ausgehend von einer Theorie von Berzins und Delahay [1] wird die Abhängigkeit der Konzentrationen der an der Durchtrittsreaktion magnified image beteiligten reduzierten und oxydierten Substanzen Sr, Sox vom Abstand x von der Elektrodenoberfläche und der Zeit t berechnet. Mit Hilfe der Funktionen cr (0, t), cox (0, t) kann eine Beziehung für die Zeitabhängigkeit der Diffusionsüberspannung ηd(t) hergeleitet werden. Eine Kombination dieser Beziehung mit der bereits von Berlins und Delahay angegebenen Gleichung für die Gesamtüberspannung η(t) ermöglicht die Berechnung der Zeitabhängigkeit der Durchtrittsüberspannung ηD(t). Die Aufladung der Doppelschicht wird dabei berücksichtigt. Der Anwendungsbereich dieser Theorie ist auf Systeme beschränkt, für die eine Aufteilung der konstant vorgegebenen Stromdichte i in einen kapazitiven Anteil ic zur Aufladung der Doppelschicht und einen Faradayschen Anteil iF sinnvoll ist (hinreichend kleine Austauschstromdichten i0 und Gleichgewichtskonzentrationen ocj, großer Fremdelektrolytüberschuß, kleine Zeiten t).
Raman‐ und Ultrarotspektren kristallisierter primärer aliphatischer Amine und ihrer N‐Deuteroderivate. Wasserstoff‐ und Deuteriumbrückenbindung kristallisierter primärer aliphatischer Amine
Authors: Wolff H. , Ludwig H.
Published: August 2023

Es werden die Raman‐ und Ultrarotspektren von kristallisiertem Äthyl‐, n‐Propyl‐ und n‐Butylamin sowie ihren N‐Deuteroderivaten ermittelt und die von kristallisiertem Methylamin früher gewonnenen Ultrarotspektren im niederfrequenten Gebiet ergänzt. Die Spektren werden zugeordnet und auf das Verhalten von Wasserstoff‐ und Deuteriumbrückenbindung der Amine im Kristall untersucht.

Aus dem Auftreten von zwei NH‐ und zwei ND‐Valenzbanden in den Spektren der halbdeuterierten Verbindungen ergibt sich, daß auch die Methylaminhomologen im Kristall zwei verschieden starke H‐ oder D‐Brücken aufweisen.

Aus der Verschiebung der NH‐ oder ND‐Banden gegenüber der Lage bei den Monomeren folgt, daß die beiden Brücken von Propylamin ebenso wie die von Methylamin nur wenig in der Stärke voneinander abweichen, die beiden Äthyl‐ und Butylaminbrücken sich aber in der Stärke erheblich unterscheiden und dabei die eine der beiden ungleichen Brücken jeweils nur sehr schwach ist. Der größere Unterschied der Brücken bei gerader C‐Atom‐Anzahl der aliphatischen Kette wird darauf zurückgeführt, daß die Anordnung der Molekeln im Kristall eine etwas andere als bei ungerader C‐Atom‐Anzahl ist.

Aus den Verschiebungen errechnen sich die Energien der beiden Deuteriumbrücken mit 2000 bzw. 4300 cal/mol jeweils um rund 300 cal/mol größer als die der beiden Wasserstoffbrücken.
Experimentelle Bestimmung der Keimgrößenverteilung einer belichteten photographischen Emulsion in Abhängigkeit von der Zahl der je Korn absorbierten Röntgenquanten
Authors: Simon F. J.
Published: August 2023

Es wird eine Methode beschrieben, in welcher die Aufnahme von Fading‐Kurven die Größenverteilung der durch eine Rö‐Belichtung erzeugten latenten Bildkeime in einer Photoplatte quantitativ zu bestimmen gestattet. Es wird das Verhalten der Verteilungsparameter als Funktion der je Korn absorbierten Quanten quantitativ bestimmt. Hierbei zeigt sich, daß die Größenverteilung der Bildkeime einer lognormalen Verteilung genügt. Das zweite Moment der Verteilung nimmt diskontinuierlich ab mit zunehmender Zahl je Korn absorbierter Rö‐Quanten, während das erste Moment der 2/3‐Potenz der Zahl je Korn absorbierter Quanten direkt proportional ist, und der Proportionalitätsfaktor durch das Oxydationspotential bestimmt wird.
Nuclear Magnetic Relaxation in Liquids
Authors: Zeidler M. D.
Published: August 2023

It is my task to show how nuclear magnetic relaxation experiments can yield information about the molecular motion in liquids. I will begin by considering those relaxation mechanisms which have been of major importance for this purpose. In a second part of my paper I will mention common experimental techniques and finally I will review typical applications of the method.
Translational and Anisotropic Rotational Diffusion in Liquid Chloroform as Studied by NMR Relaxation
Authors: Bender H. J. , Zeidler M. D.
Published: August 2023

The proton spin‐lattice relaxation rate of liquid chloroform was measured in the neat liquid and in CHCl3/CDCl3mixtures over the temperature range – 18° to 47°C. Translational self‐diffusion constants are reported in the same temperature range.

The intramolecular proton rate obtained from the isotopic dilution measurements is split into a spin‐rotational part and a contribution from the proton‐chlorine dipolar interaction. The spin‐rotational rate is then evaluated by use of a formula which takes into account the anisotropic rotational diffusion of a symmetric‐top molecule. This equation is derived in a theoretical section. The results show that the diffusion equation provides the correct description for the rotational motion.

The intermolecular dipolar proton‐proton relaxation rate obtained from the dilution experiments is used to check current theories. None of these describes the experimental results adequately. Various reasons for this failure are discussed.
Spin‐lattice Relaxation of 1,4‐Paradioxane in Different solvents
Authors: Czubryt J. , Tomchuk E. , Bock E.
Published: August 2023

The nuclear magnetic spin‐lattice relaxation time, T1, of 1,4‐paradioxane in deuterated 1,4‐paradioxane, deuterated chloroform, deuterated cyclohexane, deuterated benzene, and carbon tetrachloride was determined as a function of concentration and temperature over the temperature range of 10°C – 100°C. It was found that the rotational correlation time of the p‐dioxane molecule in infinitely dilute CDCl3 solution was significantly longer than in the other four solvents. In particular it was found that when the rotational correlation time of the p‐dioxane molecule measured at 20°C in CDCl3 solution was‐corrected for the difference in the viscosities of CDCl3 and p‐dioxane there resulted a corrected rotational correlation time of 17·10−12 s. This value is in fair agreement with the dielectric relaxation time of the CHCl3 molecule in infinitely dilute p‐dioxane solution reported by Antony and Smyth [1], viz. 16.5 · 10−12 sat 20°C. It was also found that the activation energy for molecular reorientation, ΔEτ of the p‐dioxane molecule in infinitely dilute CDCl3 was significantly higher than the activation energy for viscous flow, ΔEη in CHCl3, viz. 2.6 kcal/mol and 1.8 kcal/mol respectively. On the other hand it was found that in the case of the other four solvents ΔEτ, ≤ ΔEeta. It is suggested that the experimental results are best interpreted in terms of the formation of a complex between p‐dioxane and CDCl3 molecules which reorients as a single unit.
High Pressure NMR Relaxation Studies of Liquids
Authors: Jonas J.
Published: August 2023

Several recent high pressure nuclear magnetic resonance relaxation studies of molecular liquids are reviewed.
Internal Rotation of Nitroanilines in Liquids III. N‐n‐Alkyl‐2,4,6‐Trinitroanilines
Authors: Jouanne Jorn Von , Heidberg Joachim
Published: August 2023

The kinetic parameters of the internal rotation about the amino nitrogen‐ring carbon bond in N‐R‐2,4,6‐trinitroanilines with

in dichloromethane at temperatures between 25° and –80°C were determined by comparison of measured and calculated complete NMR line shapes. It was found that the height of the barrier to internal rotation is constant within the above class of compounds in concert with a previous model, and that the frequency of jumping over the barrier only slightly decreases with increasing chain length of the n‐alkyl substituents as estimated for n‐alkyl chains moving freely in the liquid.
Spin Relaxation in solutions of K3Mo(CN)8, K3W(CN)8 and K4Mo(CN)8
Authors: Poupko R. , Gilboa H. , Silver Brian L. , Loewenstein A.
Published: August 2023

The ESR linewidths in solutions of K3W(CN)8 and K3Mo(CN)8 were measured as a function of temperature and viscosity in various solvents. In addition the 14N NMR linewidths were measured in aqueous solutions of K4Mo(CN)8 as a function of the temperature. The results were interpreted using two approaches (a) The theory due to Kivelson and McClung [4], and (b) Attempting to obtain the best fit to a parametric equation in τC and τN, the correlation times for reorientation and angular momentum respectively. The model of Hubbard fails to account for the experimental results. The introduction of a temperature independent parameter κ, as suggested by Kivelson and coworkers, only partly improves the fit between experiment and theory. The correlation times, τc, derived from NMR measurements are in reasonable agreement with those obtained from ESR data.
Light Scattering by the Tight Binding of Molecular Reorientation to Collective Motions in Liquids
Authors: Ben‐Reuven A. , Gershon N. D.
Published: August 2023

A molecular explanation is offered for the fine structure observed in the sharp component of the depolarized Rayleigh wings in the spectrum of light scattered by various organic liquids previously attributed by hydrodynamic theory to the coupling of reorientational motion to longitudinal and transverse sound waves. The present explanation is based on the suggestion that a collective motion, with a non‐uniform displacement velocity in space, will exert a torque on the molecules if their orientational state is tightly bound to the surrounding medium for most of the time. The strength of the fine structure features is expressed in terms of molecular quantities which, except for a simple geometrical factor, are independent of the character of the collective motion. The line shape pertaining to the coupling to longitudinal sound waves is reproduced with non‐arbitrarily adjusted parameters.
High‐Energy Neutron Scattering from Liquid He4
Authors: Sears V. F.
Published: August 2023

In the limit of large momentum transfer, κ, the cross section for the scattering of neutrons from a macroscopic system is given by the impulse approximation, in which the scattering atom recoils as if it were free, and the energy distribution of the scattered neutrons is the Doppler profile characteristic of the momentum distribution in the initial state. In particular, the zero‐momentum condensate in liquid He4 below the λ‐point will produce a sharp peak in the spectrum of the scattered neutrons at the position of the free‐particle recoil energy and the relative intensity of this peak equals the fraction of atoms in the condensate. For finite momentum transfers the condensate peak tends to be smeared out by final‐state interactions and it is estimated that values of κ ≳ 80 Å−1 are required for the appearance of a well‐defined condensate peak. Available neutron data in the range 4 ≲κ≲ 20 Å−1 show no condensate peak and the main features of the observed scattering can be understood in terms of a truncated expansion of the scattering function as a series of Hermite polynomials.
Vortex Motion in Fluids
Authors: Dymond J. H. , Alder B. J.
Published: August 2023

Molecular dynamics studies on hard sphere systems have shown that the long positive tail found for the velocity autocorrelation function arises from vortex motion on a microscopic scale. Quantitative evidence for this correlated motion in real fluids at super‐critical densities is provided by an analysis of diffusion coefficient data.
Transport Processes Near the Critical Point of Gases and Binary Liquids in the Hydrodynamic Regime
Authors: Sengers J. V.
Published: August 2023

A status report is presented on the anomalies observed in the behavior of transport properties near the critical point of gases and binary liquids. The shear viscosity exhibits a weak singularity near the critical point. An analysis is made of the experimental data for those transport properties, thermal conductivity and thermal diffusivity near the gas —liquid critical point and binary diffusion coefficient near the critical mixing point, that determine the critical slowing down of the thermodynamic fluctuations in the order parameter. The asymptotic behavior of the thermal conductivity appears to be closely related to the asymptotic behavior of the correlation length. The experimental data for the thermal conductivity and diffusivity are shown to be in substantial agreement with current theoretical predictions.
Supercritical Fluids as Mobile Phases in Chromatography
Authors: Bartmann D.
Published: August 2023

Compressed fluids at temperatures in the critical range can be used as mobile phases in chromatography, especially for the separation of substances of low migration rate and/or low thermal stability. By variation of the pressure at supercritical temperatures the density of the mobile phase can be varied continuously from gas‐like to liquid‐like values, and the solvent power of the mobile phase and consequently the migration rate of the substances under test in the column can be increased by orders of magnitude (so‐called “Fluid Chromatography”). An experimental equipment for operating pressures up to 2000 atm is described. Results for a series of test substances (aliphatic and cyclic hydrocarbons) are presented. They illustrate the dependence of migration and resolution from the stationary phase and from the pressure and temperature of the mobile phase.
Photocatalytic Hydrodecarboxylation of Fatty Acids for Drop‐in Biofuels Production
Authors: de Araujo Jhudson G. L. , da Silva Maria do S. B. , Bento Júlia C. C. V. , de Azevêdo Amanda M. , de M. Araújo Aruzza M. , dos Anjos Aecia S. D. , Martínez‐Huitle Carlos A. , dos Santos Elisama V. , Gondim Amanda D. , Cavalcanti Lívia N.
Published: August 2023

A mild, practical, and environmentally friendly method for the hydrodecarboxylation of fatty acids using an acridine‐based photoredox catalyst and thiophenol was developed. Cn‐1 alkanes were synthesized in good to excellent yields (up to 99 %) from C10−C18 saturated fatty acids under visible light irradiation (405 nm). The developed protocol was employed for a mixture of fatty acids obtained from the hydrolysis of Licuri oil, affording a mixture of C9−C17 hydrocarbons in quantitative yield, which demonstrates the potential application of the method to produce drop‐in biofuels.
Warm and cool reheated
Authors: Knoblauch Kenneth , Werner John S. , Webster Michael A.
Published: August 2023

Among more conventional perceptual attributes, such as hue brightness and saturation, color is universally assigned a value along a warm/cool dimension. The source of this aspect of color experience is uncertain and a subject of current debate in color science. An unpublished study from the late twentieth century has recently appeared in an online archive that makes publicly available the results of an extensive set of measurements that document the variation of warm/cool values throughout color space and shows that they relate simply to the sum of the red‐green and blue‐yellow opponent‐color activations (red+yellow vs. blue+green), which the authors suggest is consistent with a sensory basis for this distinction.
Theoretical Understanding on the Facilitated Photoisomerization of a Carbonyl Supported Borane System
Authors: Zhu Hong‐Yang , Li Quan‐Song
Published: August 2023

Boron compound BOMes2 containing an internal B−O bond undergoes highly efficient photoisomerization, followed by sequential structural transformations, resulting in a rare eight‐membered B, O‐heterocycle (S. Wang, et al. Org. Lett. 2019, 21, 5285–5289). In this work, the detailed reaction mechanisms of such a unique carbonyl‐supported tetracoordinate boron system in the first excited singlet (S1) state and the ground (S0) state were investigated by using the complete active space self‐consistent field and its second‐order perturbation (MS‐CASPT2//CASSCF) method combined with time‐dependent density functional theory (TD‐DFT). Moreover, an imine‐substituted tetracoordinated organic boron system (BNMes2) was selected for comparative study to explore the intrinsic reasons for the difference in reactivity between the two types of compounds. Steric factor was found to influence the photoisomerization activity of BNMes2 and BOMes2. These results rationalize the experimental observations and can provide helpful insights into understanding the excited‐state dynamics of heteroatom‐doped tetracoordinate organoboron compounds, which facilitates the rational design of boron‐based materials with superior photoresponsive performances.
The relationship between green transformational leadership, corporate social responsibility, and task performance
Authors: Moin Muhammad Farrukh , Ikhide Juliet Eyore , Li Yi
Published: August 2023

This study investigates the mediating effect of corporate social responsibility (CSR) on the link between green transformational leadership (GTL) and task performance. We collected the time‐lagged data from employees in Chinese hospitality industry. Further, we used regression analysis for testing. We found that GTL has a direct relationship with task performance. Also CSR mediates the positive link between GTL and performance. We highlighted the key relationship of CSR concept in linking GTL with workers task performance in hotel industry. Our study showed that supervisor leadership style can help the firm to engage in sustainability practices which enable workers to improve their performance. Literature on CSR calls for more research to explore about the causes and consequences of it. Responding to those calls, we proposed and tested a model wherein GTL links with CSR and thus affects workers performance. Implications and future research directions are discussed.
Administration study of recombinant erythropoietin on the carriers of variant c.577del in EPO gene
Authors: He Sen , Liu Xinchao , Song Huifang , Zhou Xinmiao
Published: August 2023

The issue of misjudgment in recombinant erythropoietin (rEPO) detection caused by the variant c.577del in human EPO gene has been found in recent years. Though the method of analyzing de‐N‐glycosylated erythropoietins (EPO) in blood samples was developed for identifying both EPO_p.Arg193AspfsTer28 (VAR‐EPO) and rEPO, it cannot be applied without the evaluation of excreted samples. For this purpose, five heterozygous carriers of the variant c.577del were recruited in an administration study of rEPO. Urine and blood samples were collected at different times before and after subcutaneous injection with a single‐dose of 50 IU/kg. The urine samples were analyzed for intact EPO, while the serum samples were analyzed for both intact and de‐N‐glycosylated EPO. A typical mixed band was detected in all blank and wash‐out urine samples, which all displayed a similar result with rEPO abuse. For the analysis of intact EPO in serum samples, a typical mixed band was detected in the wash‐out samples from day 1 to day 3, which could be identified as rEPO directly, while double‐band was observed in other samples with inconclusive results. The result of de‐N‐glycosylated EPO in all serum samples showed two separated bands, and the ratioL/U decreased along with wash‐out periods. Also, compared with the intact EPO analysis, a longer detection window without false positive results was obtained when analyzing de‐N‐glycosylated EPO. Analysis of de‐N‐glycosylated EPO is not only able to recognize the variant carriers directly but also able to detect rEPO abuse in the blood samples from the variant carriers with higher efficiency than the analysis of intact EPO.