bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Simple Manganese(I) Catalyst for the Efficient and Selective Hydrophosphination of Olefins with PH3, Primary, and Secondary Phosphanes
Authors: Wani Aabid A. , Carballo Juan José Gamboa , Jayaprakash Harikrishnan , Wörle Michael , Widera Anna , Togni Antonio , Grützmacher Hansjörg 
Published: February 2024

AbstractA tridentate ligand L with a P,NH,N donor motif was synthesized in few steps from commercially available precursors. Upon reaction with [MnBr(CO)5], an octahedral 18‐electron complex [Mn(CO)3(L)]Br (1) is obtained in which L adopts a facial arrangement. After deprotonation of the NH group in the cationic complex unit, a neutral Mn(I) amido complex [Mn(CO)2(L‐H)] (2) is formed under loss of CO. Rearrangement of L‐H leads to a trigonal bipyramidal structure in which the P and N donor centers are in trans position. Further deprotonation of 2 results in a dep‐blue anionic complex fragment [Mn(CO)2(L‐2H)]− (3). DFT calculations and a QTAIM analysis show that the amido complex 2 contains a Mn‐N bond with partial double bond character and 3 an aromatic MnN2C2 ring. The anion [Mn(CO)2(L‐2H)]− reacts with Ph2PH to give a phosphido complex, which serves as phosphide transfer reagent to activated olefins. But the catalytic activity is low. However, the neutral amido complex 2 is an excellent catalyst and with loadings as low as 0.04 mol %, turn over frequencies of >40’000 h−1 can be achieved. Furthermore, secondary and primary alkyl phosphines as well as PH3 can be added in a catalytic hydrophosphination reaction to a wide range of activated olefins such as α,β‐unsaturated aldehydes, ketones, esters, and nitriles. But also, vinyl pyridine and some styrene derivatives are converted into the corresponding phosphanes.
Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation
Authors: Gulyaeva Ekaterina S. , Buhaibeh Ruqaya , Boundor Mohamed , Azouzi Karim , Willot Jérémy , Bastin Stéphanie , Duhayon Carine , Lugan Noël , Filippov Oleg A. , Sortais Jean‐Baptiste , Valyaev Dmitry A. , Canac Yves 
Published: February 2024

AbstractSystematic modification of the chelating NHC‐phosphine ligand (NHC = N‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac‐[(Ph2PCH2NHC)Mn(CO)3Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000–20000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species fac‐[(Ph2PC(Ph)NHC)Mn(CO)3H]− playing a crucial role in the hydrogenation process. These results highlight the interest of such carbon bridge substitution strategy being rarely employed in the design of chemically non‐innocent ligands.
Palladium‐Catalyzed C‐H Olefination of Imidazo[1,2a] pyridine Carboxamide in Aqueous Ethanol under Oxygen
Authors: Balaso Mohite Sachin , Kousin Mirza Yafia , Kumar Vishal , Partap Sangh , Baji Baba Shaik , Alake John , Bera Milan , Karpoormath Rajshekhar 
Published: February 2024

AbstractThe advancement of sustainable chemistry and changes in the economy are strongly intertwined. Reaction time, cost savings, moderate temperatures, and generation of the fewest byproducts are frequently achieved by using catalytic processes. Herein, we report the C−H olefination of imidazo[1,2a] pyridine carboxamides with various acrylates in the presence of Pd (OAc)2 with O2 as the oxidant in aqueous ethanol rather than using non‐ecofriendly solvents. The C−H activation features most user‐friendly reaction conditions, excellent yield as well as plenty substrate scope and applicable for C−H deuteriation of the corresponding heteroarenes with D2O. Experimental mechanistic studies indicate that C−H activation step succeeded after formation of tetra coordinated square planer Pd‐substrate adduct.
A Versatile, Functional Group‐Tolerant, and Bench‐Stable Iron Precatalyst for Building Arene and Triazine Rings by [2+2+2] Cycloadditions
Authors: Parisot William , Haddad Mansour , Phansavath Phannarath , Lefèvre Guillaume , Ratovelomanana‐Vidal Virginie 
Published: February 2024

AbstractWe report an efficient iron‐catalyzed cycloaddition procedure leading to the construction of (hetero)aromatic rings by alkyne [2+2+2] cycloisomerization. This method relies on the use of an air‐stable (N,N)Fe(II) precursor easily prepared from a commercially available ligand derived from 1,10‐phenanthroline, reduced in situ into a catalytically active non‐innocent (N,N ⋅−)2Fe(II) species. This system displays a large scope application, operates under mild conditions and at low catalytic charges (25 cycloadducts formed, up to 1.5 mol% catalyst). Moreover, this method also enables access to 29 cycloadducts by cross‐cycloisomerization between 1,6‐ or 1,7‐diynes and alkynes in near‐equimolar conditions. 1,3,5‐Triazines can also be prepared with this procedure starting from the corresponding cyanamides. Scale‐up reactions and post‐functionalization of several cycloadducts also show that this [2+2+2] cycloaddition can be used in multistep sequences.
Synthesis of [1]Benzothieno[3,2‐b][1]benzothiophenes through Iodine‐Mediated Sulfur Insertion Reaction
Authors: Ito Kazuki , Nakamura Kohei , Yoshida Kazuhiro 
Published: February 2024

Abstract[1]Benzothieno[3,2‐b][1]benzothiophenes (BTBTs) are important molecules that have been extensively studied as high‐performance organic field‐effect transistors (OFETs). Therefore, it is important to develop a simple synthetic method for these molecules. In this paper, a synthetic method to obtain the BTBTs from 2‐arylbenzo[b]thiophenes and elemental sulfur, in which two C−S bonds are formed at once, is described. In this method, molecular iodine plays a very important role as an additive. The role of iodine is discussed in the presumed reaction pathways.
Photochemical Synthesis of Lactones, Cyclopropanes and ATRA Products: Revealing the Role of Sodium Ascorbate**
Authors: Rrapi Marie , Batsika Charikleia S. , Nikitas Nikolaos F. , Tappin Nicholas D. C. , Triandafillidi Ierasia , Renaud Philippe , Kokotos Christoforos G. 
Published: February 2024

AbstractLight‐mediated processes have received significant attention, since they have re‐surfaced unconventional reactivity platforms, complementary to conventional polar chemistry. γ‐Lactones and cyclopropanes are prevalent moieties, found in numerous natural products and pharmaceuticals. Among various methods for their synthesis, light‐mediated protocols are coming to the spotlight, although these are contingent upon the use of photoorgano‐ or metal‐based catalysts. Herein, we introduce a novel photochemical activation of iodo‐reagents via the use of cheap sodium ascorbate or ascorbic acid to enable their homolytic scission and addition onto double bonds. The developed protocol was applied successfully to the formal [3+2] cycloaddition for the synthesis of γ‐lactones, traditional atom transfer radical addition (ATRA) reactions and the one‐pot two‐step conversion of alkenes to cyclopropanes. In all cases, the desired products were obtained in good to high yields, while the reaction mechanism was thoroughly investigated. Depending on the nature of the iodo‐reagent, a halogen or a hydrogen‐bonded complex is formed, which initiates the process.
Kraft‐Wärme‐Kopplung für Hybridspeicher
Authors: Kupper Christian 
Published: February 2024

AbstractDer Ausbau erneuerbarer Energien erfordert zukünftig große Kapazitäten von Energiespeichern. Alternativen zur Lithium‐Ionen‐Technologie sind Flüssigbatterie bzw. Flow‐Batterie. Im Projekt BiFlow hat das Karlsruher Institut für Technologie (KIT) gemeinsam mit dem Fraunhofer Institut für Chemische Technologie ICT und der 1st Flow Energy Solutions ein neuartiges Hybridspeichersystem entwickelt, welches die spezifischen Vorteile der Lithium‐Ionen‐Batterie und der Flow‐Batterie kombinier und dabei die Abwärme nutzt.
Determination of vapour pressures of FAME industrial mixtures by ebullioscopic and thermogravimetric experimental methods
Authors: Tonsi Giulia , Zanella Elisa , Grainca Arian , Tondelli Giacomo , Capelli Sofia , Albertini Stefano , Pirola Carlo 
Published: February 2024

AbstractVapour pressure (VP) is a parameter that characterizes, by principle, only pure compounds. Nevertheless, it can refer also to mixtures in order to characterize their volatility or to be inserted in technical documents. The measurement of VP for mixtures is strongly dependent on the possible variation of the composition, during experiments, due to the different volatility of the constituent compounds. It is possible to calculate the VP of the mixture starting from its composition, but different thermodynamic scenarios must be considered. Moreover, for industrial samples, possible effects due to the presence of impurities must be considered. In this work, two different experimental methods have been employed to determine VP of some acetates esters and two industrial mixtures of fatty acid methyl esters (FAME). The first method is a direct ebullioscopic method, while the second is an indirect thermogravimetric analysis (TGA). An error function was calculated to compare the experimental results of VPs obtained with the two methodologies with the theoretical ones. Ebullioscopic measures resulted suitable only for acetates esters, as FAME mixtures are characterized by VPs too low to be quantified with this technique. On the contrary, TGA methodology is more accurate for FAME than acetates. It allows the collection of a great number of VP values with a very fast analysis. This method is less accurate than others, but it can be useful for a fast screening of the FAME mixtures, also contaminated with light impurities.
A review of Faisal Khan's contribution to process monitoring
Authors: Amin Md Tanjin , Qian Yutian 
Published: February 2024

AbstractProcess monitoring is pivotal in process system engineering for abnormal situation management and ensuring process safety. This paper presents a review of Professor Khan's works on process monitoring. It examines (i) the number of publications, (ii) the type of publications, (iii) key sources, (iv) focused areas and their evolvement, and (v) the research impact by Professor Khan in process monitoring. The results suggest that journals are the primary sources he has used to disseminate research results. Over the years, his research focus evolved from detection to root cause diagnosis, fault propagation pathway analysis, and failure prognosis. Professor Khan has immensely impacted his peers, evidenced by his theoretical contributions, a higher number of recognitions by other researchers, and diversified workforce development.
Twisted Phosphors that Violate Kasha's Exciton Model in Organic Systems
Authors: Fu Boyi , Wang Guangming , Li Jiuyang , Li Junbo , Li Xun , Zhao Xiaoya , Ding Shuhui , Yan Guoping , Yan Qianqian , Zhang Kaka 
Published: February 2024

Comprehensive SummaryKasha's exciton model proposes that T1 energy levels of organic compounds are insensitive to molecular aggregation and microenvironment change because of negligible small transition dipole moments of T1 states. This model holds true in most organic systems till now. Here we report the fabrication of twisted organic phosphors with intramolecular charge transfer characters and flexible molecular structures. When doped into different organic matrices, the twisted phosphor adopts different conformation, exhibits distinct phosphorescence colors and T1 energy levels, which violates Kasha's exciton model in organic system. Given that the change of phosphorescence colors and maxima can be readily distinguished by human eyes and conventional instrument, the twisted phosphors would be exploited as a new type of molecular probe, which would exhibit potential application in optical sensing and stimuli‐responsive systems.
Visible‐Light‐Mediated Photocatalyst‐Free Hydroacylation of Azodicarboxylic Acid Derivatives with 4‐Acyl‐1,4‐dihydropyridines
Authors: Liu Li , Wang Jing , Feng Xiaoying , Xu Kun , Liu Wei , Peng Xia , Du Hongguang , Tan Jiajing 
Published: February 2024

Comprehensive SummaryA visible‐light‐enabled, photocatalyst‐free hydroacylation reaction of azodicarboxylic acid derivatives was described. This radical conjugate addition (RCA) protocol relied on the dual role of 4‐acyl‐1,4‐dihydropyridine (acyl‐DHP) reagents that besides being as radical reservoirs, they also enabled the conversion of radical adducts to anion intermediates via reduction. Under “catalyst‐oxidant‐additive free” conditions, a wide range of structurally different acyl hydrazide products were readily obtained in 56%—99% yields. The utility of this transformation was further demonstrated by the scale‐up synthesis and downstream derivatization.
Applying ensemble climate models to predict the fate of marginal coral reefs already existing at thermal and turbidity limits in arid tropical Australia
Authors: Cartwright Paula , Browne Nicola , Fearns Peter , O'Leary Mick , Lowe Ryan 
Published: February 2024

AbstractMarine fauna, including coral reefs, exist under particular oceanographic and meteorological (metocean) processes that maintain water quality within the range limits to which they have adapted over millennia. Climate‐induced changes to these metocean processes could alter ambient marine water quality to ranges beyond those limits and at rates faster than species can adapt. Extreme (or marginal) coral reefs, such as those in arid tropical regions, already exist at the limits of their ranges for water quality parameters such as temperature and turbidity. Here, we apply projected anomalies from ensemble climate models to the metocean processes that drive turbidity in the Exmouth Gulf region of north Western Australia where habitats of significant environmental value exist. We also apply projected sea surface temperature anomalies to look at how a combined effect of turbidity and temperature might impact important habitats. We find that turbidity is predicted to increase in some parts of the Gulf and decrease in others due to differing metocean drivers of turbidity throughout the region. Temperature anomalies reveal year‐round increases in temperature consistent with current summer marine heat wave events (>2.5°C above mean temperatures). Climate models used in the predictions varied between themselves underscoring the importance of model choice and of using ensembles.
Effective Anticancer Potential of a New Sulfonamide as a Carbonic Anhydrase IX Inhibitor Against Aggressive Tumors
Authors: Koyuncu Ismail , Temiz Ebru , Güler Eray Metin , Durgun Mustafa , Yuksekdag Ozgür , Giovannuzzi Simone , Supuran Claudiu T. 
Published: February 2024

AbstractThis study examines efficiency of a newly synthesized sulfonamide derivative 2‐bromo‐N‐(4‐sulfamoylphenyl)propanamide (MMH‐1) on the inhibition of Carbonic Anhydrase IX (CA IX), which is overexpressed in many solid tumors including breast cancer. The inhibitory potential of MMH‐1 compound against its four major isoforms, including cytosolic isoforms hCA I and II, as well as tumor‐associated membrane‐bound isoforms hCA IX and XII, was evaluated. To this context, the cytotoxic effect of MMH‐1 on cancer and normal cells was tested and found to selectively affect MDA‐MB‐231 cells. MMH‐1 reduced cell proliferation by holding cells in the G0/G1 phase (72 %) and slowed the cells′ wound healing capacity. MMH‐1 inhibited CA IX under both hypoxic and normoxic conditions and altered the morphology of triple negative breast cancer cells. In MDA‐MB‐231 cells, inhibition of CA IX was accompanied by a decrease in extracellular pH acidity (7.2), disruption of mitochondrial membrane integrity (80 %), an increase in reactive oxygen levels (25 %), and the triggering of apoptosis (40 %). In addition, the caspase cascade (CASP‐3, ‐8, ‐9) was activated in MDA‐MB‐231 cells, triggering both the extrinsic and intrinsic apoptotic pathways. The expression of pro‐apoptotic regulatory proteins (Bad, Bax, Bid, Bim, Cyt‐c, Fas, FasL, TNF‐a, TNF‐R1, HTRA, SMAC, Casp‐3, ‐8, P21, P27, and P53) was increased, while the expression of anti‐apoptotic proteins, apoptosis inhibitor proteins (IAPs), and heat shock proteins (HSPs) (Bcl‐2, Bcl‐w, cIAP‐2, HSP27, HSP60, HSP70, Survivin, Livin, and XIAP) was decreased. These results propose that the MMH‐1 compound could triggers apoptosis in MDA‐MB‐231 cells via the pH/MMP/ROS pathway through the inhibition of CA IX. This compound is thought to have high potential and promising anticancer properties in the treatment of aggressive tumors.
Comparison of long‐term outcomes between imatinib and dasatinib prophylaxis after allogeneic stem cell transplantation in patients with Philadelphia‐positive acute lymphoblastic leukemia: A multicenter retrospective study
Authors: Guan Fangshu , Yang Luxin , Chen Yi , Shi Jimin , Song Xiaolu , Lai Xiaoyu , Lu Ying , Liu Lizhen , Ouyang Guifang , Zhao Yanmin , Yu Jian , Xu Yang , Lan Jianping , Fu Huarui , Zhao Yi , Qiu Xi , Zhu Panpan , Cai Zhen , Huang He , Luo Yi 
Published: February 2024

AbstractBackgroundAlthough the prognosis of Philadelphia‐positive acute lymphoblastic leukemia (Ph+ ALL) has improved with the introduction of tyrosine kinase inhibitors (TKIs) and stem cell transplantation, prevention of relapse after transplantation remains a concern. The aim of this study was to compare the impact of TKI prophylaxis with imatinib and dasatinib on long‐term outcomes after transplantation.MethodsPatients with Ph+ ALL who underwent allogeneic hematopoietic stem cell transplantation (allo‐HSCT) at first complete remission (CR1) and received TKI prophylaxis after allo‐HSCT were included in this retrospective analysis. Two cohorts were established based on the choice of TKI prophylaxis: the imatinib (Ima) and dasatinib (Das) cohorts. The survival and safety outcomes of these cohorts were compared.ResultsNinety‐one patients in the Ima cohort and 50 in the Das cohort were included. After a median follow‐up of 50.6 months, the 5‐year cumulative incidence of relapse, nonrelapse mortality rate, and overall survival in the Ima and Das cohorts were 16.1% and 12.5%, 5.2% and 9.8%, and 86.5% and 77.6%, respectively, with no statistical differences. The cumulative incidence of mild chronic graft‐versus‐host disease was higher in the Das cohort. The most common adverse event was neutropenia (64.7% vs. 69.5%). The Das cohort had a higher incidence of gastrointestinal bleeding (25.5% vs. 2.3%) and gastrointestinal reaction (48.9% vs. 31.4%) than the Ima cohort. The proportion of patients treated on schedule was significantly lower in the Das cohort than in the Ima cohort, and drug intolerance was the main reason for protocol violation.ConclusionsFor patients with Ph+ ALL undergoing allo‐HSCT in CR1, imatinib prophylaxis achieved long‐term outcomes similar to those of dasatinib.
Research on the application of bilateral collaborative algorithm in hotel tourism consumption preference recommendation
Authors: Wang Qi 
Published: February 2024

SummaryThe continuous expansion of the domestic tourism market has driven the development of the hotel related industry. It is a key focus of the hotel industry to provide accurate supporting services to tourists based on their preferences. However, the current recommendation model mainly considers tourist factors and lacks consideration for hotel factors. In order to address the concerns of recommendation services, a bilateral collaborative recommendation model is proposed, which first analyzes tourist feature data through comprehensive similarity calculation. Firstly, the comprehensive similarity calculation is used to analyze tourist feature data, and the K‐means Clustering Algorithm (K‐means) is introduced to improve the clustering effect between data. And to better distinguish tourist preferences, the Gale Shapley (G‐S) bilateral matching model is introduced to achieve preference matching of consumer features. In the Mean Absolute Error (MAE) analysis of the model, the User‐based Collaborative Filtering (UBCF) model performs the worst. When the k value is 90, the minimum MAE value is 0.7896. The Item‐based Collaborative Filtering (IBCF) model is 0.7776, with the best performance being the improved G‐S model of 0.7325. In the performance testing of three models' preference recommendations, the improved G‐S model achieves an accuracy of over 90% in all three types of feature data recommendations, with the lowest accuracy of 62.5% for UBCF and 71.3% for IBCF. It can be seen that the proposed improved G‐S model can accurately identify tourist and hotel preference data and accurately recommend corresponding projects. The research content provides important technical references for the digital transformation and development of the tourism industry.
Graphene Exfoliation in Binary NMP/Water Mixtures by Molecular Dynamics Simulations
Authors: Gotzias A. , Lazarou Y. G. 
Published: February 2024

AbstractWe investigate the molecular mechanism underlying the liquid‐phase exfoliation of graphene in aqueous/N‐methyl‐2‐pyrrolidone (NMP) solvent mixtures and calculate the associated free energies, considering different NMP concentrations and exfoliation temperatures. We employ steered molecular dynamics to establish a path for the exfoliation of a graphene sheet from graphite within each solvent environment. Then, we conduct umbrella sampling simulations throughout the created paths to compute the potential of mean force (PMF) of the graphene sheet. As the exfoliated nanosheet disperses into the liquid, it becomes fully covered by an adsorbed solvent monolayer. We analyze the composition of the monolayer by measuring the direct contacts of either NMP or water molecules with the carbon surface. The carbon surface exhibits a preference for adsorbing NMP over water. The NMP molecules form a hydrophobic compact monolayer structure, effectively protecting the carbon interface from unfavorable interactions with water. The creation of the hydrophobic monolayer is a key factor in the exfoliation process, as it effectively inhibits the restacking of exfoliated nanosheets. An adequate level of graphene solubility is achieved through the addition of 20 % to 30 % water by weight to the NMP solvent. This finding holds significant importance for improving production efficiency and reducing dependence on organic solvents in the industrial manufacturing of graphene.
GFN‐xTB‐Based Computations Provide Comprehensive Insights into Emulsion Radiation‐Induced Graft Polymerization
Authors: Matsubara Kiho , Takahashi Kei , Matsuda Takeshi , Ueki Yuji , Seko Noriaki , Kakuchi Ryohei 
Published: February 2024

AbstractInvited for this month's cover are the collaborating groups of Dr. Ryohei Kakuchi and Ms. Kiho Matsubara at Gunma University, Japan, Prof. Kei Takahashi at Fukuoka Institute of Technology and The Institute of Statistical Mathematics, Japan, Prof. Takeshi Matsuda at Hannan University, Japan, Dr. Noriaki Seko and Dr. Yuji Ueki at National Institutes for Quantum Science and Technology, Japan. The cover picture shows the machine learning‐based optimization and interpretation of radiation‐induced graft polymerizations under emulsion conditions based on realistic information for monomers calculated by the state‐of‐the‐art semiempirical method. More information can be found in the Research Article by Kiho Matsubara, Kei Takahashi, Ryohei Kakuchi, and co‐workers.