bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Crucial Role of Sb2F10 in the Chemical Synthesis of F2
Authors: Möbs Martin , Dixon David A. , de Melo Gabriel F. , Vasiliu Monica , Graubner Tim , Christe Karl O. , Kraus Florian 
Published: July 2023

AbstractThe purely chemical synthesis of fluorine is a spectacular reaction which for more than a century had been believed to be impossible. In 1986, it was finally experimentally achieved, but since then this important reaction has not been further studied and its detailed mechanism had been a mystery. The known thermal stability of MnF4 casts serious doubts on the originally proposed hypothesis that MnF4 is thermodynamically unstable and decomposes spontaneously to a lower manganese fluoride and F2. This apparent discrepancy has now been resolved experimentally and by electronic structure calculations. It is shown that the reductive elimination of F2 requires a large excess of SbF5 and occurs in the last reaction step when in the intermediate [SbF6][MnF2][Sb2F11] the addition of one more SbF5 molecule to the [SbF6]− anion generates a second tridentate [Sb2F11]− anion. The two tridentate [Sb2F11]− anions then provide six fluorine bridges to the Mn atom thereby facilitating the reductive elimination of the two fluorine ligands as F2.
A Modular Approach for the Synthesis of Natural and Artificial Terpenoids
Authors: Wang Weiyi , Huang Dongyu , Yu Yibo , Qian Hui , Ma Shengming 
Published: July 2023

AbstractMany terpenoids with isoprene unit(s) demonstrating critical biological activities have been isolated and characterized. In this study, we have developed a robust chem‐stamp strategy for the construction of the key isoprene unit, which consists of two steps: one‐carbon extension of aldehydes to the alkenyl boronates by the boron‐Wittig reaction and the rhodium‐catalyzed reaction of alkenyl boronates with 2,3‐allenols to yield enals. This chem‐stamp could readily be applied repeatedly and separately, enabling the modular concise synthesis of many natural and pharmaceutically active terpenoids, including retinal, β‐carotene, vitamin A, tretinoin, fenretinide, acitretin, ALRT1550, nigerapyrone C, peretinoin, and lycopene. Owing to the diversified availability of the starting materials, aldehydes and 2,3‐allenols, creation of new non‐natural terpenoids has been realized from four dimensions: the number of isoprene units, the side chain, and the two terminal groups.
Low Pressure Carbonylation of Benzyl Carbonates and Carbamates for Applications in13C Isotope Labeling and Catalytic CO2Reduction
Authors: Day Craig S. , Ton Stephanie J. , Kaussler Clemens , Vrønning Hoffmann Daniel , Skrydstrup Troels 
Published: July 2023

AbstractHerein, we report a methodology to access isotopically labeled esters and amides from carbonates and carbamates employing an oxygen deletion strategy. This methodology utilizes a decarboxylative carbonylation approach for isotope labeling with near stoichiometric, ex situ generated12C, or13C carbon monoxide. This reaction is characterized by its broad scope, functional group tolerance, and high yields, which is showcased with the synthesis of structurally complex molecules. A complementary method that operates by the catalytic in situ generation of CO via the reduction of CO2liberated during decarboxylation has also been developed as a proof‐of‐concept approach that CO2‐derived compounds can be converted to CO‐containing frameworks. Mechanistic studies provide insight into the catalytic steps which highlight the impact of ligand choice to overcome challenges associated with low‐pressure carbonylation methodologies, along with rational for the development of future methodologies.
Synthesis and Characterization of a New Perovskite Nanocatalyst in CO Hydrogenation
Authors: Sayadi Borazjani Kamran , Pouranfard Abdolrasoul , Razmjooei Sam 
Published: July 2023

AbstractOperating conditions and selectivity of a new perovskite nanocatalyst were studied in Fischer‐Tropsch synthesis using a fixed‐bed microreactor. Selectivity equations were obtained using the experimental data collected from a hydrogenation process in a fixed‐bed microreactor. The operating conditions were obtained by defining the design‐of‐experiment scope based on response surface methodology, on 3 levels and in 15 tests. The optimum selectivity for alkenes relative to alkanes was obtained at 349.7 °C, 3.2 bar, and a H2/CO volumetric ratio of 1. Also, the optimum selectivity for alkenes relative to the overall selectivity for other products was attained at 250 °C, 2.3 bar, and a feed volumetric ratio of 2.
Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe3)2, OtBu) with an Iridium Hydride
Authors: Saint‐Denis Tyler G. , Zhang Bowen , Settineri Nicholas S. , Handford Rex C. , Hall Michael B. , Tilley T. Don 
Published: July 2023

AbstractReactions of the IrVhydride [MeBDIDipp]IrH4{BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐iPr2C6H3} with E[N(SiMe3)2]2(E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([MeBDIDipp]IrH)2(μ2‐E)2in good yields. Moreover, ([MeBDIDipp]IrH)2(μ2‐Ge)2was formed in situ from thermal decomposition of [MeBDIDipp]Ir(H)2Ge[N(SiMe3)2]2. These reactions are accompanied by liberation of HN(SiMe3)2and H2through the apparent cleavage of an E−N(SiMe3)2bond by Ir−H. In a reversal of this process, ([MeBDIDipp]IrH)2(μ2‐E)2reacted with excess H2to regenerate [MeBDIDipp]IrH4. Varying the concentrations of reactants led to formation of the trimeric ([MeBDIDipp]IrH2)3(μ2‐E)3. The further scope of this synthetic route was investigated with group 15 amides, and ([MeBDIDipp]IrH)2(μ2‐Bi)2was prepared by the reaction of [MeBDIDipp]IrH4with Bi(NMe2)3or Bi(OtBu)3to afford the first example of a “naked” two‐coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir2E2(E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir2Bi2is characterized as having a closed‐shell singlet ground state.
Omalizumab prevents respiratory illnesses in non‐atopic chronic spontaneous urticaria patients: A prospective, parallel‐group, pilot pragmatic trial
Authors: Konstantinou George N. , Podder Indrashis , Karapiperis Dimitrios 
Published: July 2023

AbstractBackgroundOmalizumab is the recommended treatment for antihistamine‐refractory chronic spontaneous urticaria (CSU) and severe allergic asthma. In addition, it has been shown to reduce the frequency of viral respiratory infections in allergic asthma. Respiratory illness is a known trigger for asthma and CSU.ObjectivesTo explore whether the antiviral effect of omalizumab may be extended to CSU patients independent of their atopic status.MethodsWe conducted a prospective parallel‐group pilot pragmatic trial including 30 non‐allergic and non‐atopic CSU patients (cases) under omalizumab 300 mg Q4‐weeks (due to refractory to H1‐antihistamines) and 30 age‐matched healthy controls. All CSU patients had to have a weekly urticaria activity score UAS7 <15 at least 4 weeks before recruitment. Using the self‐filled validated Jackson scale, we evaluated all study participants for common cold symptoms. All cases and controls rated weekly their respiratory symptoms. An increase in the symptom score of at least 4 points compared to baseline (defined as the minimum weekly report of symptoms) was considered an episode suggestive of a viral infection of the upper respiratory tract (URT). The patients were follow‐up every 4 weeks throughout the study period (10 months).ResultsCSU patients under omalizumab reported fewer episodes suggestive of an URT viral infection than the healthy controls (median of reported episodes: 0 vs. 1, inter‐quartile range 0–1 vs. 1–1, min–max: 0–3 vs. 0–4, respectively; p = 0.0095). The duration of each episode was the same in both cases and controls.ConclusionsOmalizumab can reduce the number of common cold episodes in CSU patients and consequently may minimize viral‐related CSU exacerbations. This beneficial effect is exerted independently of the atopic status, even in non‐asthmatic individuals or non‐allergic patients without any evidence of respiratory susceptibility. Further large‐scale studies are needed to validate the current findings and elucidate the underlying relevant pathophysiology.
Key Pharmacokinetic Parameters of 74 Pediatric Anticancer Drugs Providing Assistance in Preclinical Studies
Authors: Jamaladdin Nora , Sigaud Romain , Kocher Daniela , Kolodziejczak Anna S. , Nonnenbroich Leo F. , Ecker Jonas , Usta Diren , Benzel Julia , Peterziel Heike , Pajtler Kristian W. , van Tilburg Cornelis M. , Oehme Ina , Witt Olaf , Milde Till 
Published: July 2023

Novel drug treatments for pediatric patients with cancer are urgently needed. Success of drug development in pediatric oncology has been promising, but many drugs still fail in translation from preclinical to clinical phases. To increase the translational potential, several improvements have been implemented, including the use of clinically achievable concentrations in the drug testing phase. Although pharmacokinetic (PK) parameters of numerous investigated drugs are published, a comprehensive PK overview of the most common drugs in pediatric oncology could guide preclinical trial design and improve the translatability into clinical trials. A review of the literature was conducted for PK parameters of 74 anticancer drugs, from the drug sensitivity profiling library of the INdividualized Therapy FOr Relapsed Malignancies in Childhood (INFORM) registry. PK data in the pediatric population were reported and complemented by adult parameters when no pediatric data were available. In addition, blood–brain barrier (BBB)‐penetration assessment of drugs was provided by using the BBB score. Maximum plasma concentration was available for 73 (97%), area under the plasma concentration‐time curve for 69 (92%), plasma protein binding for 66 (88%), plasma half‐life for 57 (76%), time to maximum concentration for 54 (72%), clearance for 52 (69%), volume of distribution for 37 (49%), lowest plasma concentration reached by the drug before the next dose administration for 21 (28%), and steady‐state concentration for 4 (5%) of drugs. Pediatric PK data were available for 48 (65%) drugs. We provide a comprehensive review of PK data for 74 drugs studied in pediatric oncology. This data set can serve as a reference to design experiments more closely mimicking drug PK conditions in patients, and may thereby increase the probability of successful clinical translation.
Multifunctional Role of Ag‐Substitution in Enhancing the Photoelectrochemical Properties of LaFeO3 Photocathodes
Authors: Sun Xin , Lan Zhineng , Wang Min , Geng Qi , Lv Xiaojun , Li Meicheng 
Published: July 2023

AbstractEarth‐abundant LaFeO3 is a promising p‐type semiconductor for photoelectrochemical cells due to its stable photoresponses, high photovoltages and appropriate band alignments, but the photoelectrochemical properties of LaFeO3, especially the incident‐photon‐to‐current conversion efficiency, need to be further improved. Herein, we propose to partially substitute La3+ of LaFeO3 with Ag+ to enhance the photoelectrochemical performance of LaFeO3. The combined experimental and computational studies show that Ag‐substitution improves surface charge transfer kinetics through introducing active electronic states and increasing electrochemically active surface areas. Furthermore, Ag‐substitution decreases grain boundary number and increases majority carrier density, which promotes bulk charge transports. Ag‐substitution also reduces the bandgap energy, increasing the flux of carriers involved in photoelectrochemical reactions. As a result, after 8 % Ag‐substitution, the photocurrent density of LaFeO3 is enhanced by more than 6 times (−0.64 mA cm−2 at 0.5 V vs RHE) in the presence of oxygen, which is the highest photocurrent gain compared with other cation substitution or doping. The corresponding photocurrent onset potential also demonstrates a positive shift of 30 mV. This work highlights the versatile effects of Ag‐substitution on the photoelectrochemical properties of LaFeO3, which can provide useful insights into the mechanism of enhanced photoelectrochemical performance by doping or substitution.
Individual‐based analyses reveal effects of behavioral and demographic variables associated with multi‐annual reproductive success of male and female lake sturgeon
Authors: Duong Thuy‐Yen , Bence James , Forsythe Patrick S. , Crossman James A. , Baker Edward A. , Sard Nicholas M. , Scribner Kim T. 
Published: July 2023

AbstractQuantifying effects of individual attributes and population demographic characteristics that affect inter‐ and intrasexual interactions and adult reproductive success, and the spatial and temporal contexts in which they are expressed is important to effective species management. Multi‐year individual‐based analyses using genetically determined parentage allowed the examination of variables associated with the reproductive success of male and female lake sturgeon (Acipenser fulvescens) in the well‐studied population in Black Lake, Michigan, USA. Spawning lake sturgeon (a total of 599 individuals where many were captured more than once based on 1024 total captures) and larvae (N = 3436) were genotyped during each of seven consecutive years (2001–2007). Factors associated with individual reproductive success differed between sexes and varied among spawning groups within a year and among years depending on spawning date (higher reproductive success earlier in the season for females) and spawning locations (higher reproductive success in upstream spawning zones for females). Female reproductive success increased nonlinearly with increasing body size. Male reproductive success increased with increasing residence time in spawning areas and, to a modest degree, with increasing body size in a nonlinear fashion. Fixed effects of repeatability in spawn timing and location across years led to consistently higher or lower reproductive success for females. Results identified factors, including time spent at spawning areas by males and intersexual encounters and mate number, that contributed to higher interindividual variance in reproductive success and affected population levels of recruitment, the degree of subpopulation genetic structure (lack of isolation by time), and effective population size.
Base Stabilized σ‐Borane Complex of Group 5 Metals: Synthesis and Structure of [(η5‐C5Me5)Ta(H3BNC5H4) (C5H4NS)(η2‐S2)]
Authors: Haridas Anagha , Saha Suvam , Bedajna Shantabh , Ghosh Sundargopal 
Published: July 2023

AbstractAzametallacyclopropane‐containing base stabilized borane complexes of group 5 transition metals have been synthesized and their structural aspects have been described. Treatment of Cp* based Ta and Nb chlorides, Cp*TaCl4 and Cp*NbCl4 with [LiBH4 ⋅ THF] followed by addition of ligands, such as 2‐mercaptobenzothiazole, MBT, (C7H5NS2) and 2‐mercaptobenzoxazole, MBO (C7H5NSO) led to the formation of complexes [Cp*M‐[BHS(CH2ENC6H4)(C7H4NSE)] (1: M=Ta, E=S; 2; M=Nb, E=S; 3: M=Ta, E=O; 4; M=Nb, E=O, Cp*=pentamethyl‐η5‐cyclopentadienyl). By means of UV‐vis absorption spectra, the electronic properties of these complexes associated with central metal atoms and heteroatoms (S or O) have been evaluated. In contrast, treatment of Cp*TaCl4 with 2‐mercaptopyridine, MP, (C5H5NS) under the same reaction conditions yielded the agostic σ‐borane Ta complex, [Cp*Ta(H3BNC5H4) (C5H4NS)(η2‐S2)], 5. Unlike 1–4, where the metals interact with boron through bridging sulphur, 5 shows a notable σ‐B−H bond interaction with Ta. All spectroscopic data of 1–5 along with the X‐ray diffraction studies suggest complexes 2, 4, and 5 are base (amine) stabilized borane species. Computational studies based on Density Functional Theory (DFT) also supported this conclusion.
Electrokinetic motion and viability assessment of algae with a polyethylene glycol–dextran interface
Authors: Xu Runxin , Zhang Junyan , Cao Zhenhao , Song Yongxin , Xin Xiukun 
Published: July 2023

AbstractAt present, there is still limited report on the electrokinetic (EK) behavior of bioparticles at the interface of an aqueous two‐phase system. In this paper, the EK motion and viability assessment of live algae mixed with the NaClO treated dead algae were carried out at the interface formed by polyethylene glycol (PEG)‐rich phase and dextran (DEX)‐rich phase in a straight microchannel. The experimental results show that both the live and dead algae at the PEG–DEX interface migrate from the negative electrode to the positive electrode, and the EK velocity of live algae at the interface is slightly larger than that of the dead ones with similar diameters. For either live or dead algae, the EK velocity at the interface decreases with the increase in diameter. A size–velocity curve was used to evaluate the viability of the algae. As most of the microorganisms in ballast water are algae, the method in this paper provides a promising way to detect and evaluate the live microorganism in treated ballast water of a ship.
Electrophoresis of a dielectric droplet with constant surface charge density
Authors: Tseng Jessica , Su Judy , Chang Kevin , Chang Amy , Chuang Lily , Lu Amanda , Lee Rose , Lee Eric 
Published: July 2023

AbstractElectrophoresis of a dielectric fluid droplet with constant surface charge density is investigated theoretically in this study. A pseudo‐spectral method based on Chebyshev polynomials is adopted to solve the governing electrokinetic equations. It is found, among other things, that the larger the electrolyte strength in the ambient solution is, the slower the droplet moves in general. This is due to the strong screening effect of the large amount of indifferent counterions in the neighborhood of the droplet, with no reinforcement of potential‐determining ions adsorbing to the droplet surface. The droplet comes to a complete halt eventually. Critical points are discovered for highly charged droplets, at which the droplet surface becomes immobile and the interior fluid stops recirculating. The droplet moves like a rigid particle with constant mobility regardless of its viscosity, a situation referred to as the “solidification phenomenon.” The deadlock between the spinning motions on the charged droplet surface induced by the electric driving force and the hydrodynamic driving force respectively is responsible for this peculiar phenomenon. This is also observed for a dielectric droplet with constant surface electric potential. We demonstrate here that it occurs in the constant surface charge density situation as well.
Electrokinetic transport phenomena in nanofluidics and their applications
Authors: Sun Ya , Jiang Rui , Hu Lide , Song Yongxin , Li Mengqi 
Published: July 2023

AbstractMuch progress has been made in the electrokinetic phenomena inside nanochannels in the last decades. As the dimensions of the nanochannels are compatible to that of the electric double layer (EDL), the electrokinetics inside nanochannels indicate many unexpected behaviors, which show great potential in the fields of material science, biology, and chemistry. This review summarizes the recent development of nanofluidic electrokinetics in both fundamental and applied research. First, the techniques for constructing nanochannels are introduced to give a guideline for choosing the optimal fabrication technique based on the specific feature of the nanochannel. Then, the theories and experimental investigations of the EDL, electroosmotic flow, and electrophoresis of nanoparticles inside the nanochannels are discussed. Furthermore, the applications of nanofluidic electrokinetics in iontronics, sensing, and biomolecule separation fields are summarized. In Section 5, some critical challenges and the perspective on the future development of nanofluidic electrokinetics are briefly proposed.
Digital health applications in the self‐management of epilepsy—A survey on patients' perspective
Authors: Houta Salima , Bader Alisa , Effert Jana‐Sophie , Esser Birgitta , Henze Jasmin , Spaic Alexandra , Zocher Feline , Lauerer Michael , Surges Rainer 
Published: July 2023

AbstractObjectiveDigital health applications can be prescribed since 2019 in Germany, which is likely to facilitate a broad use of epilepsy self‐management applications, possibly directly connected to clinical systems via telematics infrastructures. This article reports on patients' interest in digital support for epilepsy self‐management, influencing factors and patients' knowledge about digitization of health care in Germany.MethodsThis work is based on self‐reported data from 115 people with epilepsy participating in an anonymous online survey with a total of 54 questions covering several topics, including sociodemographics and epilepsy manifestation, use of technology in general and for treatment support, training programs, affinity for technology, knowledge on the digital infrastructure in Germany, and self‐efficacy in dealing with chronic illness. The self‐constructed questionnaire uses existing instruments like TA‐EG, SES6G, and Hoffmeyer‐Zlotnik sociodemographic questionnaire. To analyze the knowledge about digitalization in health care, a combination of self‐assessment and knowledge quiz was used. The analysis was performed using descriptive methods and inferential statistics (t‐test, reliability analysis, and correlations).ResultsParticipants were most interested in seizure alerting and documentation with the possibility to share documentation with physicians. The analysis of technology affinity showed medium enthusiasm, with positively perceived consequences being rated higher than the negatively perceived consequences of technology use. Knowledge on national health infrastructures was mediocre and training on this was judged to be essential and desired. Furthermore, a significant correlation was found between interest in use and affinity for technology (enthusiasm for technology [r = 0.29; P = 0.00]) and positively perceived consequences of technology (r = 0.33; P = 0.00).SignificanceOur results underline the high relevance of digital solutions for patients and the importance of individual training opportunities in digital health literacy, thereby enabling patients to decide competently for or against offered digital solutions.
On the existence of k $k$‐cycle semiframes for even k $k$
Authors: Wang Li , Ji Haibo , Cao Haitao 
Published: July 2023

AbstractA ‐semiframe of type is a ‐group divisible design of type in which is the vertex set, is the group set, and the set of ‐cycles can be written as a disjoint union where is partitioned into parallel classes on and is partitioned into holey parallel classes, each parallel class or holey parallel class being a set of vertex disjoint cycles whose vertex sets partition or for some . In this paper, we almost completely solve the existence of a ‐semiframe of type for all and a ‐semiframe of type for all and .