bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Cyclometalated Gold(III) Complexes via Catalytic Rhodium to Gold(III) Transmetalation
Authors: Martín Jaime , Gómez‐Bengoa Enrique , Genoux Alexandre , Nevado Cristina 
Published: February 2022

AbstractA catalytic method to synthesize a broad array of cyclometalated (C^N)gold(III) complexes is reported here. An unprecedented Rh‐to‐AuIII transmetalation allows the facile transfer of (C^N) ligands between these two metals in a redox‐neutral process. The reaction employs commercially available precursors and proceeds under mild and environmentally benign conditions. Both experimental and computational studies support a multistep transmetalation from rhodium to gold as the underlying mechanism for these transformations. This process involves first, a rate‐determining transfer of the C ligand followed by the subsequent incorporation of the N donor to form the monocyclometalated (C^N)gold(III) species.
Carbon Dioxide Chemically Responsive Switchable Gas Valves with Protonation‐Induced Liquid Gating Self‐Adaptive Systems
Authors: Lei Jinmei , Hou Yaqi , Wang Huimeng , Fan Yi , Zhang Yunmao , Chen Baiyi , Yu Shijie , Hou Xu 
Published: February 2022

AbstractCarbon dioxide (CO2) capture and storage technologies are promising to limit CO2 emission from anthropogenic activities, to achieve carbon neutrality goals. CO2 capture requires one to separate CO2 from other gases, and therefore a gas flow system that exhibits discernible gating behaviors for CO2 would be very useful. Here we propose a self‐adaptive CO2 gas valve composed of chemically responsive liquid gating systems. The transmembrane critical pressures of the liquid gate vary upon the presence of CO2, due to the superamphiphiles assembled by poly(propylene glycol) bis(2‐aminopropyl ether) and oleic acid in gating liquids that are protonated specifically by CO2. It is shown that the valve can perform self‐adaptive regulation for specific gases and different concentrations of CO2. This protonation‐induced liquid gating mechanism opens a potential platform for applications of CO2 separators, detectors, sensors and beyond.
Construction of Mechanofluorochromic and Aggregation‐Induced Emission Materials Based on 4‐Substituted Isoquinoline Derivatives
Authors: Wang Dan , Chen Yating , Zhu Junyi , Lei Yunxiang , Zhou Yunbing , Gao Wenxia , Liu Miaochang , Wu Huayue , Huang Xiaobo 
Published: February 2022

AbstractAlthough many organic mechanofluorochromic (MFC) materials have been reported, the design strategy and formation mechanism are still unclear, and thus some of their discoveries are based on chance or a result of blind screening of some compounds. Herein, we show a strategy for constructing MFC materials from a multisubstituted isoquinoline compound with excellent crystallinity. The introduction of bromine atom at 4‐position realizes the morphological change from crystalline state to amorphous state under the stimulation of external pressure, but it is not enough to generate MFC phenomenon. Similarly, although naphthalene, benzofuran, and benzothiophene endow the resultant isoquinolines with twisted molecular conformations and aggregation‐induced emission (AIE) activities, no obvious solid‐state emission color changes are observed. However, the introduction of 2‐benzylidenemalononitrile and (E)‐2‐cyano‐3‐phenylacrylate leads not only to the AIE activities of IQ‐M and IQ‐A, but also to their outstanding and reversible MFC properties. The MFC activities of these two derivatives are demonstrated to come from more twisted molecular conformations, larger deformation spaces, and stronger intramolecular charge transfer compared with the other isoquinolines. This work offers important reference value for the construction of MFC and AIE materials from traditional fluorophores.
Spatiotemporal trends in burden of uterine cancer and its attribution to body mass index in 204 countries and territories from 1990 to 2019
Authors: Li Songbo , Chen Hui , Zhang Tongchao , Li Rongrong , Yin Xiaolin , Man Jinyu , He Qiufeng , Yang Xiaorong , Lu Ming 
Published: February 2022

AbstractBackgroundUterine cancer is one of the most common female cancers worldwide, with huge heterogeneity in morbidity and mortality. Although a high body‐mass index (BMI) has been linked to uterine cancer, systematic reports about the influence of high BMI and its temporal trends are scarce.MethodsThe annual morbidity, mortality, and disability‐adjusted life years (DALYs) of uterine cancer in 204 countries or territories were retrieved from the GBD 2019 study. To reflect trends in disease burden, we also calculated the estimated annual percentage change (EAPC) based on the age‐standardized rates of uterine cancer from 1990 to 2019.ResultsThe global incident cases of uterine cancer increased 2.3 times from 187,190 in 1990 to 435,040 in 2019. Although the age‐standardized incidence rate (ASIR) of uterine cancer increased worldwide from 8.67/100,000 in 1990 to 9.99/100,000 in 2019, the age‐standardized death rate (ASDR) and DALY rate decreased during the same period. High socio‐demographic index (SDI) countries tended to have a higher ASIR than developing regions, and their increasing trend in ASIR was also more pronounced. The disease was rare before 40 years old, but its risk rose sharply among women aged 50–70. A high BMI was linked to more than one‐third of deaths from uterine cancer in 2019.ConclusionsThe incidence in developed areas was significantly higher than in developing areas and also increased much more rapidly. Elderly females, especially those with a high BMI, have a higher risk of uterine cancer. Therefore, more health resources may be needed to curb the rising burden in specific populations.
Femtosecond Spectroscopy and Nonlinear Optical Properties of aza‐BODIPY Derivatives in Solution
Authors: Chang Hao‐Jung , Bondar Mykhailo V. , Munera Natalia , David Sylvain , Maury Olivier , Berginc Gerard , Le Guennic Boris , Jacquemin Denis , Andraud Chantal , Hagan David J. , Van Stryland Eric W. 
Published: February 2022

AbstractThe fast relaxation processes in the excited electronic states of functionalized aza‐boron‐dipyrromethene (aza‐BODIPY) derivatives (1–4) were investigated in liquid media at room temperature, including the linear photophysical, photochemical, and nonlinear optical (NLO) properties. Optical gain was revealed for nonfluorescent derivatives 3 and 4 in the near infrared (NIR) spectral range under femtosecond excitation. The values of two‐photon absorption (2PA) and excited‐state absorption (ESA) cross‐sections were obtained for 1–4 in dichloromethane using femtosecond Z‐scans, and the role of bromine substituents in the molecular structures of 2 and 4 is discussed. The nature of the excited states involved in electronic transitions of these dyes was investigated using quantum‐chemical TD‐DFT calculations, and the obtained spectral parameters are in reasonable agreement with the experimental data. Significant 2PA (maxima cross‐sections ∼2000 GM), and large ESA cross‐sections ∼10−20 m2 of these new aza‐BODIPY derivatives 1–4 along with their measured high photostability reveal their potential for photonic applications in general and optical limiting in particular.
Control of Crystallinity of Vinylene‐Linked Two‐Dimensional Conjugated Polymers by Rational Monomer Design
Authors: Pastoetter Dominik L. , Liu Yannan , Addicoat Matthew A. , Paasch Silvia , Dianat Arezoo , Bodesheim David , Waentig Albrecht L. , Xu Shunqi , Borrelli Mino , Croy Alexander , Richter Marcus , Brunner Eike , Cuniberti Gianaurelio , Feng Xinliang 
Published: February 2022

AbstractThe interest in two‐dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene‐linked 2D CPs with fully in‐plane sp2‐carbon‐conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner‐Wadsworth‐Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene‐linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D‐poly(phenylene‐quinoxaline‐vinylene)s (2D‐PPQVs) and 2D‐poly(phenylene‐vinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible C−C single bond formation.
WaterMap‐Guided Structure‐Based Virtual Screening for Acetylcholinesterase Inhibitors
Authors: Targowska‐Duda Katarzyna M. , Maj Maciej , Drączkowski Piotr , Budzyńska Barbara , Boguszewska‐Czubara Anna , Wróbel Tomasz M. , Laitinen Tuomo , Kaczmar Patrycja , Poso Antti , Kaczor Agnieszka A. 
Published: February 2022

AbstractStructure‐based virtual screening of the Enamine database of 1.7 million compounds followed by WaterMap calculations (a molecular‐dynamics‐simulation‐based method) was applied to identify novel acetylcholinesterase (AChE) inhibitors. The inhibitory potency of 29 selected compounds against electric eel (ee) AChE was determined using Ellman's method. Three compounds were found to be active (success rate 10 %). For the most potent compound (∼40 % inhibition at 10 μM), 20 derivatives were discovered based on the Enamine similarity search. Finally, five compounds were found to be promising (IC50 ranged from 6.3 μM to 17.5 μM) inhibitors of AChE. The performed similarity and fragment analysis confirmed significant structural novelty for these AChE inhibitors. Toxicity/safety of selected compounds was determined in zebrafish model.
Pharmacokinetic Interaction Between the MEK1/MEK2 Inhibitor Trametinib and Oral Contraceptives Containing Norethindrone and Ethinyl Estradiol in Female Patients With Solid Tumors
Authors: Arkenau Hendrik‐Tobias , Taylor Donatienne , Xu Xiaoying , Chitnis Shripad , Llacer‐Perez Casilda , Moore Kathleen , Nidamarthy Prasanna Kumar , Ilankumaran Palanichamy , De Vos‐Geelen Judith 
Published: February 2022

AbstractThis phase 1 postapproval study assessed the effect of the mitogen‐activated protein kinase kinase enzyme 1/enzyme 2 inhibitor trametinib (2 mg once daily, repeat dosing) on the pharmacokinetics of combined oral contraceptives (COCs) containing norethindrone (NE; 1 mg daily) and ethinyl estradiol (EE; 0.035 mg daily) in 19 female patients with solid tumors. Compared with NE/EE administered without trametinib, NE/EE administered with steady‐state trametinib was associated with a clinically nonrelevant 20% increase in NE exposure (area under the curve [AUC]) and no effect on EE exposure (geometric mean ratio [geo‐mean] of NE/EE + trametinib to NE/EE [90%CI]: NE AUC calculated to the end of a dosing interval at steady‐state [AUCtau] 1.20 [1.02‐1.41]; NE AUC from time zero to the last measurable concentration sampling time [AUClast] 1.2 [0.999‐1.45]; EE AUCtau 1.06 [0.923‐1.22]; EE AUClast 1.05 [0.883‐1.25]). Maximum serum concentration (Cmax) of NE increased by 13% and Cmax of EE decreased by 8.5% when dosed with steady‐state trametinib compared with COCs administered alone (geo‐mean ratio [90%CI]: NE Cmax 1.13 [0.933‐1.36]; EE Cmax 0.915 [0.803‐1.04]). These results indicate that repeat‐dose trametinib does not lower exposure to NE or EE and, hence, is unlikely to impact the contraceptive efficacy of COCs. The pharmacokinetic parameters of trametinib and its metabolite M5 were consistent with historic data of trametinib alone. Coadministration of trametinib and COCs was generally well tolerated in this study, with observed safety signals consistent with the known safety profile of trametinib and no new reported safety events. Overall, the findings indicate that hormonal COCs can be coadministered in female patients who receive trametinib monotherapy without compromising the contraceptive efficacy.
Exploring human behavior patterns and socio‐demographic factors based on American Time Use Survey
Authors: Song Ling , Liu Hongxin , Lyu Shunming , Niu Xiaofei , Hou Tie , Ma Yuling , Lyu Qiang 
Published: February 2022

SummaryAs human activities in mobile environments are facing an ever‐increasing range of data, it is of great research importance to explore in depth the salient features of data that discriminate human behavior patterns and socio‐demographic factors. However, human activity behavior that consists of a series of complex spatio‐temporal activity processes is difficult to model. In this article, we develop a framework to perform activity behavior pattern mining and recognition, and the proposed framework has been applied to the American Time Use Survey to explore representative activity behavior patterns and socio‐demographic factors. The main contributions are as follows: (1) A method of activity behavior similarity is presented based on daily activities and activity sequences. (2) An activity sequence similarity algorithm with is proposed by line segment tree, greedy algorithm, and dynamic programming. (3) Representative activity behavior patterns and socio‐demographic factors are derived by clustering analysis and mining. (4) The activity behavior pattern is recognized by activity behavior features or socio‐demographic features. Through the experiments, we find that different daily activity behavior patterns are associated with specific socio‐demographic factors.
Strength and Nature of Host‐Guest Interactions in Metal‐Organic Frameworks from a Quantum‐Chemical Perspective
Authors: Ernst Michelle , Gryn'ova Ganna 
Published: February 2022

AbstractMetal‐organic frameworks (MOFs) offer a convenient means for capturing, transporting, and releasing small molecules. Their rational design requires an in‐depth understanding of the underlying non‐covalent host‐guest interactions, and the ability to easily and rapidly pre‐screen candidate architecturesin silico. In this work, we devised a recipe for computing the strength and analysing the nature of the host‐guest interactions in MOFs. By assessing a range of density functional theory methods across periodic and finite supramolecular cluster scale we find that appropriately constructed clusters readily reproduce the key interactions occurring in periodic models at a fraction of the computational cost. Host‐guest interaction energies can be reliably computed with dispersion‐corrected density functional theory methods; however, decoding their precise nature demands insights from energy decomposition schemes and quantum‐chemical tools for bonding analysis such as the quantum theory of atoms in molecules, the non‐covalent interactions index or the density overlap regions indicator.
Reversible Stimuli‐Responsive Transmembrane Ion Transport Using Phenylhydrazone‐Based Photoswitches
Authors: Ahmad Manzoor , Mondal Debashis , Roy Naveen J. , Vijayakanth Thangavel , Talukdar Pinaki 
Published: February 2022

AbstractPhenylhydrazone‐based synthetic receptors are reported as stimuli‐responsive anion transporters. The X‐ray crystallographic studies confirmed the preorganized anion binding E‐state and closed non‐binding Z‐state. The detailed ion transport mechanistic studies confirmed Cl−/anion exchange as the primary ion transport process. Their light‐stimulated E‐to‐Z isomerization led to a substantial decrease in the ion transport activity across the lipid bilayer membrane. Reversible “OFF” and “ON” activity switching was studied by light and acid stimuli, respectively.
Soft Metal Cations Trigger Sandwich‐Cluster Luminescence of a New Au(I)‐Vinylimidazolate Cyclic Trinuclear Complex
Authors: Lu Zhou , Burini Alfredo , McDougald Roy N. , Ricci Simone , Luciani Lorenzo , Nesterov Vladimir N. , Rawashdeh Abdel‐Monem M. , Omary Mohammad A. , Galassi Rossana 
Published: February 2022

AbstractThe formation of heterobimetallic complexes from parent cyclic trinuclear complexes (CTCs) of gold(I) has become straightforward in recent years with this team and others showing that the strategy leads to strengthened Au−M’ bonding and optoelectronic properties. A new gold(I)‐vinylimidazolate CTC, 1, was prepared and the formation of highly emissive sandwich adducts with the soft metal cations Cu+, Ag+, and Tl+, 2–4, respectively, was investigated. Compound 1 does not exhibit peculiar emissive properties at room or cryogenic temperatures as the adducts do. Its unit cell packing displays an unprecedented collection of repeating units for CTCs. While the intermolecular Au…Au distances are versatile (3.470, 3.673, and 4.045 Å), they connect only single Au centres from adjacent CTCs and form extended circular networks. Hirshfeld surface analyses mapped the new CTC contours underlining the possible cooperative effects of not only metallophilic interactions but also C−H…π and hydrogen bonding in the packing of 1 (as opposed to the dominance of the former in most other reported CTCs). DFT calculations validate the formation of sandwich‐like structures for compounds 2–4 with averaged Au−M distances of 2.665 Å, 2.802 Å, and 3.036 Å, respectively, close by to experimental crystal data obtained for similar sandwich compounds.
Dinuclear Palladium(II) and Platinum(II) Complexes of a Readily Accessible Bicyclic Diphosphane
Authors: Edgar Mark , Elsegood Mark R. J. , Liu Pingchuan , Miles Christopher R. , Smith Martin B. , Wu Shimeng 
Published: February 2022

AbstractThe one‐step synthesis (33 % isolated yield) of a novel bicyclic diphosphane, [P(CH2)2NC6H4(4‐NMe2)]2, P−P(NMe2), from the reaction of [P(CH2OH)4]Cl and H2NC6H4(4‐NMe2) in methanol is described. Surprisingly, P−P(NMe2) displays excellent air/solution stability (towards H2O, CH3OH) and can also function efficiently as a bridging ligand. Hence reaction of P−P(NMe2) with [Pd(μ−Cl)(η3‐allyl)]2 (η3‐allyl=C3H5, C4H7) or [Pd(μ−Cl)(κ2−C9H12N)]2 affords the singly‐bridged complexes {Pd(Cl)(η3‐allyl)}2{μ‐P−P(NMe2)} 1 a/1 b and {Pd(Cl)(κ2−C9H12N)}2{μ‐P−P(NMe2)} 1 c whereas treatment with [MX2(η4‐cod)] (M=Pd, Pt; X=Cl, Br, I, Me; η4‐cod=cycloocta‐1,5‐diene) gave (MX2)2{μ‐P−P(NMe2)}2 2 a–e in high yields. Protonation of 2 a–d with HBF4 ⋅ OEt2 gave the corresponding dimethylammonium salts 3 a–d. Single crystal X‐ray studies have been undertaken on P−P(NMe2), 1 b, 2 a, 2 b ⋅ 2CDCl3, 2 d, 2 e, 3 a ⋅ 12CD3CN and 3 b ⋅ 12CD3CN. The P−P bond lengths in free/coordinated P−P(NMe2) remain similar across all compounds studied here and no M ⋅⋅⋅ M contacts were observed within the planar M2P4 ring. In 3 a/3 b the BF4− anion displays a unique secondary interaction with the inorganic six‐membered M2P4 core.
Catalytic Asymmetric Chlorination of Isoxazolinones
Authors: Wannenmacher Nick , Keim Noah , Frey Wolfgang , Peters René 
Published: February 2022

AbstractOrganic compounds featuring a chlorine substituted stereocenter are frequently found in nature and are interesting for pharmaceutical applications and as synthetic building blocks. Catalytic methods to generate such stereocenters by C,H bond functionalization are still relatively rare. Here we report the first catalytic asymmetric chlorination of isoxazolinones, a synthetically and biologically interesting class of heterocycles, which can be considered as precursors for β‐aminoacids. The title reaction was catalyzed with high enantioselectivity by a planar chiral ferrocene based palladacycle in high to excellent yields. It is showcased that the products are valuable for post‐synthetic transformations. An SN2 reaction proceeded with smooth inversion of the absolute configuration. The substitution product could then be transformed into an α‐azido β‐aminoacid derivative via a reductive, diastereoselective ring opening.
Ordinal regression increases statistical power to predict epilepsy surgical outcomes
Authors: Dickey Adam S. , Krafty Robert T. , Pedersen Nigel P. 
Published: February 2022

AbstractStudies of epilepsy surgery outcomes are often small and thus underpowered to reach statistically valid conclusions. We hypothesized that ordinal logistic regression would have greater statistical power than binary logistic regression when analyzing epilepsy surgery outcomes. We reviewed 10 manuscripts included in a recent meta‐analysis which found that mesial temporal sclerosis (MTS) predicted better surgical outcomes after a stereotactic laser amygdalohippocampectomy (SLAH). We extracted data from 239 patients from eight studies that reported four discrete Engel surgical outcomes after SLAH, stratified by the presence or absence of MTS. The rate of freedom from disabling seizures (Engel I) was 64.3% (110/171) for patients with MTS compared to 44.1% (30/68) without MTS. The statistical power to detect MTS as a predictor for better surgical outcome after a SLAH was 29% using ordinal regression, which was significantly more than the 13% power using binary logistic regression (paired t‐test, P < .001). Only 120 patients are needed for this example to achieve 80% power to detect MTS as a predictor using ordinal regression, compared to 210 patients that are needed to achieve 80% power using binary logistic regression. Ordinal regression should be considered when analyzing ordinal outcomes (such as Engel surgical outcomes), especially for datasets with small sample sizes.
A non‐inferiority analysis of hemoglobin levels in postpartum IUD users in Bangladesh
Authors: Bright Suzanna , Gore‐Langton Georgia R. , Fatima Parveen , Dewan Farhana , Yesmin Afroja , Makins Anita 
Published: February 2022

AbstractObjectiveThe objective of this study was to compare postpartum hemoglobin (Hb) between postpartum intrauterine device (PPIUD) and non‐PPIUD users.MethodsA sample of 3697 postpartum women (475 PPIUD users, 3222 non‐PPIUD users) from 5 tertiary referral hospitals in Bangladesh were assessed at multiple time points between 6 weeks and 12 months postpartum. Non‐inferiority linear regression analysis compared changes in Hb levels at 29–52 weeks postpartum between the two groups. Non‐inferiority was declared if the lower 95% confidence interval of the estimated difference in Hb change since delivery between PPIUD and non‐PPIUD users was greater than −0.05 g/dl.ResultsAt approximately 9 months postpartum, 276 women in the PPIUD group (58.1%) and 1086 women in the comparison group (33.7%) attended follow‐up. In total, 57.9% of PPIUD users and 61.0% of non‐PPIUD users had taken iron supplementation. Change in Hb was 0.02 g/dl (95% CI: −0.16, 0.19) higher in the PPIUD users than the comparison group. The lower limit of the 95% CI was greater than −0.05 g/dl, providing good evidence that PPIUD users were non‐inferior to the comparison group in their Hb levels.ConclusionIn the presence of offering iron supplementation, and an uptake of just over 60%, no difference in anemia was observed between the PPIUD and control group.