bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Substituted β‐Functionalised Styrenes by Microwave‐Assisted Olefin Cross‐Metathesis and Scalable Synthesis of Apremilast
Authors: Jana Anupam , Zieliński Grzegorz Krzysztof , Czarnocka‐Śniadała Sylwia , Grudzień Krzysztof , Podwysocka Dominika , Szulc Marcin , Kajetanowicz Anna , Grela Karol 
Published: August 2019

AbstractPreparation of diversely substituted β‐functionalised styrenes by microwave‐assisted olefin cross‐metathesis (CM) is described. This method can be also employed in the synthesis of β‐deuterated α,β‐unsaturated sulfones from inexpensive allylbenzenes, though unprecedented one‐pot isomerisation/deuteration/cross‐metathesis sequence. One of such obtained CM products has been utilised in a new scalable synthesis of Apremilast (6), a potent and orally active phosphodiesterase 4 and tumour necrosis factor‐α inhibitor. The same strategy was used in synthesis of an optical antipode of 6, ent‐Apremilast.
Towards Identification of Essential Structural Elements of Organoruthenium(II)‐Pyrithionato Complexes for Anticancer Activity
Authors: Kladnik Jerneja , Kljun Jakob , Burmeister Hilke , Ott Ingo , Romero‐Canelón Isolda , Turel Iztok 
Published: August 2019

AbstractAn organoruthenium(II) complex with pyrithione (2‐mercaptopyridine N‐oxide) 1 a has previously been identified by our group as a compound with promising anticancer potential without cytotoxicity towards non‐cancerous cells. To expand the rather limited research on compounds of this type, an array of novel chlorido and 1,3,5‐triaza‐7‐phosphaadamantane (pta) organoruthenium(II) complexes with methyl‐substituted pyrithiones has been prepared. After thorough investigation of the aqueous stability of these complexes, their modes of action have been elucidated at the cellular level. Minor structural alterations in the ruthenium‐pyrithionato compounds resulted in fine‐tuning of their cytotoxicities. The best performing compounds, 1 b and 2 b, with a chlorido or pta ligand bound to ruthenium, respectively, and a methyl group at the 3‐position of the pyrithione scaffold, have been further investigated. Both compounds trigger early apoptosis, induce the generation of reactive oxygen species and G1 arrest in A549 cancer cells, and show no strong interaction with DNA. However, only 1 b also inhibits thioredoxin reductase. Wound healing assays and mitochondrial function evaluation have revealed differences between these two compounds at the cellular level.
Dynamic Interplay between Defective UiO‐66 and Protic Solvents in Activated Processes
Authors: Caratelli Chiara , Hajek Julianna , Meijer Evert Jan , Waroquier Michel , Van Speybroeck Veronique 
Published: August 2019

AbstractUiO‐66, composed by Zr‐oxide inorganic bricks [Zr6(μ3‐O)4(μ3‐OH)4] and organic terephthalate linkers, is one of the most studied metal–organic frameworks (MOFs) due to its exceptional thermal, chemical, and mechanical stability. Thanks to its high connectivity, the material can withstand structural deformations during activation processes such as linker exchange, dehydration, and defect formation. These processes do alter the zirconium coordination number in a dynamic way, creating open metal sites for catalysis and thus are able to tune the catalytic properties. In this work, it is shown, by means of first‐principle molecular‐dynamics simulations at operating conditions, how protic solvents may facilitate such changes in the metal coordination. Solvent can induce structural rearrangements in the material that can lead to undercoordinated but also overcoordinated metal sites. This is demonstrated by simulating activation processes along well‐chosen collective variables. Such enhanced MD simulations are able to track the intrinsic dynamics of the framework at realistic conditions.
Reversible C=C Bond Activation by an Intramolecularly Coordinated Antimony(I) Compound
Authors: Kořenková Monika , Hejda Martin , Erben Milan , Jirásko Robert , Jambor Roman , Růžička Aleš , Rychagova Elena , Ketkov Sergey , Dostál Libor 
Published: August 2019

AbstractInvited for the cover of this issue is the group of Libor Dostál at the University of Pardubice, Czech Republic, and colleagues at the G. A. Razuvaev Institute of Organometallic Chemistry, Nizhny Novgorod, Russia. The image depicts an amusement park designed around the antimony compounds reported in this paper. Read the full text of the article at 10.1002/chem.201902968.
Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH2 Groups (E=P, As)
Authors: Li Bin , Bauer Susanne , Seidl Michael , Timoshkin Alexey Y. , Scheer Manfred 
Published: August 2019

AbstractThe pnictogenyl Group 13 compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl and (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac=HC[C(Me)N(Ar)]2, Ar: Dipp=2,6‐iPr2C6H3; M=Al, Ga, In; E=P, As) were successfully synthesized. The salt metathesis between (Dipp2Nacnac)MCl2 and LiE(SiMe3)2 only led to monosubstituted compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl [E=P, M=Ga(1), In (2); E=As, M=Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe3 groups in 1–4, the reactions of the corresponding halides with LiPH2⋅DME (or KAsH2) facilely yielded the dipnictogenide compounds (Dipp2Nacnac)M(EH2)2 (E=P, M=Al (5), Ga (6), In (7); E=As, M=Al (8), Ga (9)), avoiding the use of flammable and toxic PH3 and AsH3 for their synthesis. The compounds 5–9 are the first examples of monomeric Group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH2 and AsH2 groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp2Nacnac)In(PH2)2, the reaction of (Dipp2Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.
Construction of All‐Carbon Chiral Quaternary Centers through CuI‐Catalyzed Enantioselective Reductive Hydroxymethylation of 1,1‐Disubstituted Allenes with CO2
Authors: Qiu Jia , Gao Shen , Li Chaopeng , Zhang Lei , Wang Zheng , Wang Xiaoming , Ding Kuiling 
Published: August 2019

AbstractA catalytic enantioselective construction of all‐carbon chiral quaternary centers through reductive hydroxymethylation of 1,1‐disubstituted allenes with CO2 has been developed. In the presence of a copper/Mandyphos catalyst, CO2 is transformed into an alcohol oxidation level by an asymmetric reductive C−C bond formation with allenes by using hydrosilane (HSi(OMe)2Me) as a reductant. The resulting chiral homoallylic alcohols are versatile synthetic intermediates and can be conveniently converted into a variety of useful chiral chemicals.
A Coumarin Triflate Reagent Enables One‐Step Synthesis of Photo‐Caged Lipid Metabolites for Studying Cell Signaling
Authors: Wagner Nicolai , Schuhmacher Milena , Lohmann Annett , Nadler André 
Published: August 2019

AbstractPhotorelease of caged compounds is among the most powerful experimental approaches for studying cellular functions on fast timescales. However, its full potential has yet to be exploited, as the number of caged small molecules available for cell biological studies has been limited by synthetic challenges. Addressing this problem, a straightforward, one‐step procedure for efficiently synthesizing caged compounds was developed. An in situ generated benzylic coumarin triflate reagent was used to specifically functionalize carboxylate and phosphate moieties in the presence of free hydroxy groups, generating various caged lipid metabolites, including a number of GPCR ligands. By combining the photo‐caged ligands with the respective receptors, an easily implementable experimental platform for the optical control and analysis of GPCR‐mediated signal transduction in living cells was developed. Ultimately, the described synthetic strategy allows rapid generation of photo‐caged small molecules and thus greatly facilitates the analysis of their biological roles in live cell microscopy assays.
Self‐Assembled Polyamidoamine Dendrimer on Poly (methyl meth‐ acrylate) for Plasmonic Fiber Optic Sensors
Authors: Divagar M. , Saumey Jain , Satija Jitendra , Sai V. V. R. 
Published: August 2019

AbstractWe report a novel one‐step polyamidoamine (PAMAM) dendrimer based polymethyl methacrylate (PMMA) surface functionalization strategy for the development of polymeric optical fiber (POF) based plasmonic sensors utilizing gold nanoparticles (AuNP). Simple contact angle measurements over PMMA sheets reveal the ability of the dendrimers to strongly bind to PMMA surface without additional acid/alkali pretreatment, unlike the conventional hexamethylene diamine (HMDA) based surface modification. Subsequently, U‐bent POF probes with high evanescent wave absorbance sensitivity were exploited for relative quantification of the surface amine groups using fluorescein isothiocyanate (FITC) binding and efficient chemisorption of gold nanoparticles (AuNP) in order to identify the optimum conditions viz. dendrimer concentration, incubation time and dendrimer generation. While FITC binding showed a proportional increase in amine functional density with PAMAM concentration and time, interestingly the AuNP (40 nm) binding studies revealed the formation of loose PAMAM multilayers and their desorption. PAMAM (G4) concentration as low as 5 mM and incubation time of 24 h provide faster binding rate with densely packed AuNP and the RI sensitivity of ∼15 (A546 nm/RIU). This simpler and inexpensive strategy could also be exploited for the development of functional PMMA substrates for various applications including nanotechnology, bio‐imaging, drug delivery and analytical separations.
Efficacy of S‐1 in second‐line chemotherapy after nab‐paclitaxel plus gemcitabine for patients with advanced pancreatic cancer
Authors: Iede Kiyotsugu , Yamada Terumasa , Kato Ryo , Ueda Masami , Tsuda Yujiro , Nakashima Shinsuke , Ohta Katsuya , Matsuyama Jin , Ikenaga Masakazu , Tominaga Shusei 
Published: August 2019

AbstractBackgroundSecond‐line (2 L) chemotherapy is important for improved survival. However, the efficacy of S‐1 after nab‐paclitaxel plus gemcitabine (AG) for advanced pancreatic cancer (APC) remains unclear.AimWe retrospectively investigated the clinical impact of S‐1 after AG.Methods and resultsFrom January 2015 to July 2018, 37 patients with APC underwent AG as first‐line chemotherapy at our institute. Of these patients, 14 (38%) underwent S‐1 as 2 L chemotherapy after AG (S‐1 group), five (14%) received another agent after AG, and 18 (49%) underwent no 2 L chemotherapy (best supportive care [BSC] group). The clinical features were retrospectively compared between the S‐1 and BSC groups. Prognostic factors for residual survival (RS) were analyzed using a Cox proportional hazards model. The induction rate of 2 L chemotherapy was 51%, and most patients received S‐1 monotherapy (74%). The disease control rate and progression‐free survival duration were 57.1% and 2.8 months, respectively. The median RS duration in the S‐1 and BSC groups was 5.2 and 2.4 months, respectively; this difference was statistically significant (hazard ratio, 0.33; P = .005). The median overall survival duration in the S‐1 and BSC groups was 12.3 and 5.0 months, respectively; this difference was also statistically significant (hazard ratio, 0.26; P = .001). The efficacy of S‐1 in 2L chemotherapy for RS was identified in the multivariate analysis, as was age (<65 vs ≥65 y) and the presence of liver metastasis.ConclusionThe antitumor activity of S‐1 was retained after AG, and the induction of S‐1 after AG might improve the prognosis of patients with APC.
Impressive Enrichment of Semiempirical Quantum Mechanics‐Based Scoring Function: HSP90 Protein with 4541 Inhibitors and Decoys
Authors: Eyrilmez Saltuk M. , Köprülüoğlu Cemal , Řezáč Jan , Hobza Pavel 
Published: August 2019

AbstractThis paper describes the excellent performance of a newly developed scoring function (SF), based on the semiempirical QM (SQM) PM6‐D3H4X method combined with the conductor‐like screening implicit solvent model (COSMO). The SQM/COSMO, Amber/GB and nine widely used SFs have been evaluated in terms of ranking power on the HSP90 protein with 72 biologically active compounds and 4469 structurally similar decoys. Among conventional SFs, the highest early and overall enrichment measured by EF1and AUC% obtained using single‐scoring‐function ranking has been found for Glide SP and Gold‐ASP SFs, respectively (7, 75 % and 3, 76 %). The performance of other standard SFs has not been satisfactory, mostly even decreasing below random values. The SQM/COSMO SF, where P−L structures were optimised at the advanced Amber level, has resulted in a dramatic enrichment increase (47, 98 %), almost reaching the best possible receiver operator characteristic (ROC) curve. The best SQM frame thus inserts about seven times more active compounds into the selected dataset than the best standard SF.
Efficient Conversion of Carbon Dioxide by Imidazolium‐Based Cross‐Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks
Authors: Calabrese Carla , Fusaro Luca , Liotta Leonarda Francesca , Giacalone Francesco , Comès Adrien , Campisciano Vincenzo , Aprile Carmela , Gruttadauria Michelangelo 
Published: August 2019

AbstractPolyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross‐linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid‐state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal‐ and solvent‐free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values, up to 5502 and 1081 respectively for glycidol conversion at 100 °C and up to 4942 and 1122 for epichlorohydrin conversion at 150 °C after 3 h, were obtained. Such outstanding productivity values were ascribed to the optimal organic/inorganic (i. e., imidazolium moiety/POSS support) weight ratio. The recyclability of the materials was successfully verified for five consecutive runs allowing their consideration as promising candidates for continuous flow technologies.
New Ni0.5Ti2 (PO4)3@C NASICON‐type Electrode Material with High Rate Capability Performance for Lithium‐Ion Batteries: Synthesis and Electrochemical Properties
Authors: Srout Mohammed , Kwon Nam Hee , Luo Wen , Züttel Andreas , Fromm Katharina M. , Saadoune Ismael 
Published: August 2019

AbstractNi0.5Ti2(PO4)3/C NASICON‐type phosphate is introduced as a new anode material for lithium‐ion batteries (LIBs). Ni0.5Ti2(PO4)3/C was synthesized through the sol–gel route and delivered some remarkable electrochemical performances. Specifically, the Ni0.5Ti2(PO4)3/C electrode demonstrates a high rate capability performance and delivers high reversible capacities ranging from 130 mAh g−1 to about 111 mAh g−1 at current rates ranging from 0.1 C to 5 C in the voltage window of 1.85–3 V (vs. Li+/Li). In the same voltage range, the material reaches an initial capacity of 105 mAh g−1 with a capacity retention of about 82 % after 1000 cycles at the high current rate of 10 C. The electrodes are also tested in the wider voltage range of 0.5–3 V (vs. Li+/Li) and show good reversibility and rate capability performance. Moreover, the Ni0.5Ti2(PO4)3/C electrodes enable fast Li+ diffusion (in the order of 10−13 cm2 s−1) compared with other NASICON‐type materials. As a result, a first discharge capacity of 480 mAh g−1 is reached.
Amperometric Biosensors Based on Recombinant Bacterial Laccase CotA for Hydroquinone Determination
Authors: Zhang Yue , Lv Ziyao , Zhou Jie , Fang Yan , Wu Hao , Xin Fengxue , Zhang Wenming , Ma Jiangfeng , Xu Ning , He Aiyong , Dong Weiliang , Jiang Min 
Published: August 2019

AbstractIn this study, stable CotA laccase from Bacillus subtilis 168 was adsorbed on electrode modified with a thiol graphene‐gold nanoparticle (thGP‐AuNPs) nanocomposite film. The novel bacterial laccase biosensor was employed for quantitative detection of hydroquinone (HQ) and the electrochemical properties of this laccase biosensor were investigated. The results indicate that the immobilized CotA shows great oxidation activity towards HQ in the presence of oxygen and the biosensor shows linear electrocatalytic activity in the concentration range from 1.6 to 409.6 μM, with a detection limit of 0.3 μM. Further, the CotA modified electrode, when compared to fungal laccase‐modified biosensors, shows better alkaline stability (retaining approximately 80 % and 70 % of response current at pH 8 and 9, respectively) and reusability (retaining ∼87 % of response current after 100 days). The development of this new kind of laccase on a biosensor will offer a novel tool for substance detection applications in hostile environments, especially for industrial pollutants.
Nano zerovalent iron (NZVI) adsorption performance on acidic dye 36 removal: Optimization of effective factors, isotherm and kinetic study
Authors: Delnavaz Mohammad , Kazemimofrad Zahra 
Published: August 2019

AbstractThis study focused on the efficiency of nano zerovalent iron (NZVI) for degrading industrial dye (acidic dye 36). To elucidate NZVI characteristics, some advanced analytical experiments such as FTIR, TGA, EDS, XRD, TEM as well as SEM were measured. The performance evaluation of the adsorbent was carried out within variety of adsorption influencing parameters, including pH, contact time, initial dye dosage and NZVI dosage) with the assistance of central composite design (CCD) as a strong tool suggested by response surface methodology software. The results gained through CCD illustrate that the quadratic model is the suggested one with adjusted R2 = 0.896 and predicted R2 = 0.723. The little difference between actual and predicted values proves the power of the model to satisfactorily and reliably predict the efficiency removal. Applying mathematical equations reveal that initial dye dosage and interactive contribution of pH and dye dosage are the most influential single and combined factors, respectively. The optimized condition obtained by RSM for NZVI adsorption process was determined at pH = 5.5, NZVI = 0.5, dye solution = 30 mg/L, and 90 s of contact time. The adsorption kinetic was performed, introducing the second order as the best one and the Langmuir isotherm gained high agreement with experimental data as well.
Effect of boiling time on the contents of flavor and taste in Lentinus edodes
Authors: Li Biao , Liu Changyuan , Fang Donglu , Yuan Biao , Hu Qiuhui , Zhao Liyan 
Published: August 2019

AbstractThe changes of flavor components during boiling in Lentinus edodes were studied by high‐performance liquid chromatography and gas chromatography‐mass spectrometry in this article. Results showed that nonvolatile flavor components in L. edodes gradually transferred into the soup during boiling. Contents of nonvolatile flavor substances in the soup increased significantly (p < .05) compared with the preboiling period (15 minutes) and gradually maintained a balanced situation with the boiling time extended. During boiling, content of alcohols gradually reduced, especially the content of 1‐octen‐3‐ol, which is a typical flavor component in L. edoedes. The contents of sulfur compounds, aldehydes, and hydrocarbons increased first and finally decreased gradually with the boiling time extended. Therefore, the changes of flavor components in the soup almost maintained a balanced situation with the boiling time from 30 to 60 minutes. The results of this article could provide a theoretical basis for the changes of flavor compounds in L. edodes during boiling.
Current understanding of tumor lysis syndrome
Authors: Rahmani Benjamin , Patel Shrey , Seyam Omar , Gandhi Jason , Reid Inefta , Smith Noel , Khan Sardar Ali 
Published: August 2019

AbstractTumor lysis syndrome (TLS) is an oncologic emergency from the intracellular release of material in lysing malignant cells. The earlier it is treated, the less likely it is to be harmful to an individual and spread through the body. Common complications of TLS include arrhythmias, which are caused by hypocalcemia or hyperkalemia, renal failures due to hyperuricemia or hyperphosphatemia, and seizures. Furthermore, the risk to develop TLS varies widely based on several factors including factors that are related to disease, the patient, and the treatment of the patient. Laboratory data can be used to gauge the severity of TLS based on patient serum levels for specific markers. On the contrary, evidence of TLS via radiological imaging and electrocardiogram findings has been a limited way to evaluate TLS, indicating the need for further research in this area. Common trends of treatment have also been seen in the past several years, evident by case studies seen in the following literature review.
Causes of appointment attendance, nonattendance, and cancellation in outpatient consultations at a university hospital
Authors: Briatore Agustina , Tarsetti Estefania Veronica , Latorre Agustin , Gonzalez Bernaldo de Quirós Fernan , Luna Daniel , Fuentes Nora Angélica , Elizondo Cristina Maria , Baum Analia , Alonso Serena Marina , Giunta Diego Hernán 
Published: August 2019

SummaryBackgroundNonattendance to scheduled appointments in outpatient clinics is a frequent problem in ambulatory medicine with an impact on health systems and patients' health. The characterization of nonattendance is fundamental for the design of appropriate strategies for its management.AimsTo identify causes of nonattendance of scheduled ambulatory medical appointments by adult patients.MethodsCase and two controls study nested in a prospective cohort. A telephone‐administered questionnaire was applied within the first 72 hours to identify the causes of attendance, nonattendance, or cancellation in patients who had a scheduled appointment to which they had been present, absent, or cancelled.ResultsA total of 150 absences (cases), 176 attendances, and 147 cancellations (controls) in a prospective cohort of 160 146 scheduled appointments (2012/2013) were included. According to self‐reports in telephone interviews, the most frequent causes of nonattendance were forgetting 44% (66), unexpected competing events 15.3% (23), illness or unwellness 12% (18), work‐related inconvenience 5.3% (8), transport‐related difficulties 4.7% (4), and cause that motivated appointment scheduling already resolved 4.7% (4).DiscussionThe main cause of nonattendance is forgetting the scheduled appointment, but there is a proportion of different causes that do not respond to reminders but could respond to different strategies.