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Current Organic Chemistry

Editor-in-Chief

ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

Mini-Review Article

Carboxylation of Alkenes and Alkynes Using CO2 as a Reagent: An Overview

Author(s): Rupak Chatterjee and Asim Bhaumik*

Volume 26, Issue 1, 2022

Page: [60 - 70] Pages: 11

DOI: 10.2174/1385272825666211206090621

Price: $65

Abstract

CO2 fixation reactions are of paramount interest both from economical and environmental perspectives. As an abundant, non-toxic, and renewable C1 feedstock, CO2 can be utilized for the synthesis of fuels and commodity chemicals under elevated reaction conditions. The major challenge in the CO2 utilization reactions is its chemical inertness due to high thermodynamic stability and kinetic barrier. The carboxylation of unsaturated hydrocarbons with CO2 is an important transformation as it forms high-value reaction products having industrial as well as medicinal importance. This mini-review is mainly focused on the recent developments in the homogeneously and heterogeneously catalyzed carboxylation of alkenes and alkynes by using carbon dioxide as a reagent. We have highlighted various types of carboxylation reactions of alkenes and alkynes involving different catalytic systems, which comprise mainly C-H bond activation, hydrocarboxylation, carbocarboxylation, heterocarboxylation, and ring-closing carboxylation, including visible-light assisted synthesis processes. The mechanistic pathways of these carboxylation reactions have been described. Moreover, challenges and future perspectives of these carboxylation reactions are discussed.

Keywords: Carbon-dioxide fixation, alkenes, alkynes, carboxylation, homogeneous catalysis, heterogeneous catalysis, renewable feedstock.

Graphical Abstract

[1]
Tortajada, A.; Juliá-Hernández, F.; Börjesson, M.; Moragas, T.; Martin, R. Transition metal-catalyzed carboxylation reactions with carbon dioxide. Angew. Chem. Int. Ed. Engl., 2018, 57(49), 15948-15982.
[http://dx.doi.org/10.1002/anie.201803186] [PMID: 29722461]
[2]
Our Planet's CO2 Home Page. 2018. Available from:. https://www.co2.earth
[3]
Hansen, J.; Kharecha, P.; Sato, M.; Masson-Delmotte, V.; Ackerman, F.; Beerling, D.J.; Hearty, P.J.; Hoegh-Guldberg, O.; Hsu, S.L.; Parmesan, C.; Rockstrom, J.; Rohling, E.J.; Sachs, J.; Smith, P.; Steffen, K.; Van Susteren, L.; von Schuckmann, K.; Zachos, J.C. Assessing “dangerous climate change”: required reduction of carbon emissions to protect young people, future generations and nature. PLoS One, 2013, 8(12)e81648
[http://dx.doi.org/10.1371/journal.pone.0081648] [PMID: 24312568]
[4]
Saini, S.; Prajapati, P.K.; Jain, S.L. Transition metal-catalyzed carboxylation of olefins with carbon dioxide: a comprehensive review. Catal. Rev., Sci. Eng., 2020, 1-47.
[http://dx.doi.org/10.1080/01614940.2020.1831757]
[5]
Cai, X.; Xie, B. Direct carboxylative reactions for the transformation of carbon dioxide into carboxylic acids and derivatives. Synth, 2013, 45(24), 3305-3324.
[http://dx.doi.org/10.1055/s-0033-1340061]
[6]
Sakakura, T.; Choi, J.C.; Yasuda, H. Transformation of carbon dioxide. Chem. Rev., 2007, 107(6), 2365-2387.
[http://dx.doi.org/10.1021/cr068357u] [PMID: 17564481]
[7]
Mikkelsen, M.; Jørgensen, M.; Krebs, F.C. The teraton challenge. A review of fixation and transformation of carbon dioxide. Energy Environ. Sci., 2010, 3, 43-81.
[http://dx.doi.org/10.1039/B912904A]
[8]
Bhunia, S.; Molla, R.A.; Kumari, V.; Islam, S.M.; Bhaumik, A. Zn(ii) assisted synthesis of porous salen as an efficient heterogeneous scaffold for capture and conversion of CO2. Chem. Commun. (Camb.), 2015, 51(86), 15732-15735.
[http://dx.doi.org/10.1039/C5CC06868A] [PMID: 26365199]
[9]
Bhanja, P.; Modak, A.; Bhaumik, A. Supported porous nanomaterials as efficient heterogeneous catalysts for CO2 fixation reactions. Chemistry, 2018, 24(29), 7278-7297.
[http://dx.doi.org/10.1002/chem.201800075] [PMID: 29396871]
[10]
Kaur, P.; Chopra, H.K. Recent advances in applications of supported ionic liquids. Curr. Org. Chem., 2019, 23(26), 2881-2915.
[http://dx.doi.org/10.2174/1385272823666191204151803]
[11]
Bhanja, P.; Modak, A.; Bhaumik, A. Porous organic polymers for CO2 storage and conversion reactions. ChemCatChem, 2019, 11(1), 244-257.
[http://dx.doi.org/10.1002/cctc.201801046]
[12]
Modak, A.; Bhanja, P.; Dutta, S.; Chowdhury, B.; Bhaumik, A. Catalytic reduction of CO2 into fuels and fine chemicals. Green Chem., 2020, 22(13), 4002-4033.
[http://dx.doi.org/10.1039/D0GC01092H]
[13]
Marciniak, A.A.; Henrique, F.J.F.S.; de Lima, A.F.F.; Alves, O.C.; Moreira, C.R.; Appel, L.G.; Mota, C.J.A. What are the preferred CeO2 exposed planes for the synthesis of dimethyl carbonate? Answers from theory and experiments. Mol. Catal, 2020, 493111053
[http://dx.doi.org/10.1016/j.mcat.2020.111053]
[14]
Ballatore, C.; Huryn, D.M.; Smith, A.B. III Carboxylic acid (bio)isosteres in drug design. ChemMedChem, 2013, 8(3), 385-395.
[http://dx.doi.org/10.1002/cmdc.201200585] [PMID: 23361977]
[15]
Goossen, L.J.; Rodríguez, N.; Goossen, K. Carboxylic acids as substrates in homogeneous catalysis. Angew. Chem. Int. Ed. Engl., 2008, 47(17), 3100-3120.
[http://dx.doi.org/10.1002/anie.200704782] [PMID: 18357604]
[16]
Correa, A.; Martín, R. Metal-catalyzed carboxylation of organometallic reagents with carbon dioxide. Angew. Chem. Int. Ed. Engl., 2009, 48(34), 6201-6204.
[http://dx.doi.org/10.1002/anie.200900667] [PMID: 19544522]
[17]
Wu, X.F.; Fang, X.; Wu, L.; Jackstell, R.; Neumann, H.; Beller, M. Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account. Acc. Chem. Res., 2014, 47(4), 1041-1053.
[http://dx.doi.org/10.1021/ar400222k] [PMID: 24564478]
[18]
Katagiri, T.; Amao, Y. Recent advances in light-driven C-H bond activation and building C-C bonds with CO2 as a feedstock for carbon capture and utilization technology. Green Chem., 2020, 22(20), 6682-6713.
[http://dx.doi.org/10.1039/D0GC01796E]
[19]
Colby, D.A.; Bergman, R.G.; Ellman, J.A. Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. Chem. Rev., 2010, 110(2), 624-655.
[http://dx.doi.org/10.1021/cr900005n] [PMID: 19438203]
[20]
Liu, Y.; Kim, J.; Chae, J. Heterocycle construction via transition metal-catalyzed C-H functionalization and C-heteroatom bond formation. Curr. Org. Chem., 2014, 18(16), 2049-2071.
[http://dx.doi.org/10.2174/1385272819666140728174621]
[21]
Dodangeh, M.; Ramazani, A.; Maghsoodlou, M.T.; Zarei, A.; Rezayati, S. Application of readily available metals for C-H activation. Curr. Org. Chem., 2020, 24(14), 1582-1609.
[http://dx.doi.org/10.2174/1385272824999200616114037]
[22]
Nemoto, K.; Yoshida, H.; Egusa, N.; Morohashi, N.; Hattori, T. Direct carboxylation of arenes and halobenzenes with CO2 by the combined use of AlBr3 and R3SiCl. J. Org. Chem., 2010, 75(22), 7855-7862.
[http://dx.doi.org/10.1021/jo101808z] [PMID: 21033692]
[23]
Nemoto, K.; Onozawa, S.; Konno, M.; Morohashi, N.; Hattori, T. Direct carboxylation of thiophenes and benzothiophenes with the aid of EtAlCl2. Bull. Chem. Soc. Jpn., 2012, 85(3), 369-371.
[http://dx.doi.org/10.1246/bcsj.20110335]
[24]
Nemoto, K.; Tanaka, S.; Konno, M.; Onozawa, S.; Chiba, M.; Tanaka, Y.; Sasaki, Y.; Okubo, R.; Hattori, T. Me2AlCl-mediated carboxylation, ethoxycarbonylation, and carbamoylation of indoles. Tetrahedron, 2016, 72(5), 734-745.
[http://dx.doi.org/10.1016/j.tet.2015.12.028]
[25]
Tanaka, S.; Watanabe, K.; Tanaka, Y.; Hattori, T. EtAlCl2/2,6-disubstituted pyridine-mediated carboxylation of alkenes with carbon dioxide. Org. Lett., 2016, 18(11), 2576-2579.
[http://dx.doi.org/10.1021/acs.orglett.6b00918] [PMID: 27187716]
[26]
Ostapowicz, T.G.; Hölscher, M.; Leitner, W. Catalytic hydrocarboxylation of olefins with CO2 and H2- a DFT computational analysis. Eur. J. Inorg. Chem., 2012, 34, 5632-5641.
[http://dx.doi.org/10.1002/ejic.201200965]
[27]
Omae, I. Recent developments in carbon dioxide utilization for the production of organic chemicals. Coord. Chem. Rev., 2012, 256(13-14), 1384-1405.
[http://dx.doi.org/10.1016/j.ccr.2012.03.017]
[28]
Andrushko, N.; Andrushko, V.; Thyrann, T.; König, G.; Börner, A. ynthesis of enantiopure (R)-2-(4-methoxy-3-(3-methoxypropoxy)-benzyl)-3-methylbutanoic acid - a key intermediate for the preparation of Aliskiren. 2008, 49, 5980-5982.,
[http://dx.doi.org/10.1016/j.tetlet.2008.07.150]
[29]
Xiong, W.; Shi, F.; Cheng, R.; Zhu, B.; Wang, L.; Chen, P.; Lou, H. Palladium-catalyzed highly regioselective hydrocarboxylation of alkynes with carbon dioxide. ACS Catal., 2020, 10(14), 7968-7978.
[http://dx.doi.org/10.1021/acscatal.0c01687]
[30]
Simonato, J.; Walter, T.; Métivier, P. Iridium-formic acid based system for hydroxycarbonylation without CO Gas. J. Mol. Catal. Chem., 2001, 171(1-2), 91-94.
[http://dx.doi.org/10.1016/S1381-1169(01)00114-5]
[31]
Ostapowicz, T.G.; Schmitz, M.; Krystof, M.; Klankermayer, J.; Leitner, W. Carbon dioxide as a C1 building block for the formation of carboxylic acids by formal catalytic hydrocarboxylation. Angew. Chem., 2013, 125(46), 12341-12345.
[http://dx.doi.org/10.1002/ange.201304529]
[32]
Yuan, Q.; Song, X.; Feng, S.; Jiang, M.; Yan, L.; Li, J.; Ding, Y. An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins. Chem. Commun. (Camb.), 2021, 57(4), 472-475.
[http://dx.doi.org/10.1039/D0CC06863B] [PMID: 33326517]
[33]
Hou, J.; Ee, A.; Cao, H.; Ong, H.W.; Xu, J.H.; Wu, J. Visible-light-mediated metal-free difunctionalization of alkenes with CO2 and silanes or C(Sp3)−H alkanes. Angew. Chem. Int. Ed. Engl., 2018, 57(52), 17220-17224.
[http://dx.doi.org/10.1002/anie.201811266] [PMID: 30411439]
[34]
Nan, S.; Hai-Bin, W.; Li, G.; Jing-Yao, Z.; Jian-Feng, G.; Fang, W.; Ebadi, A. A. Sila-, bora-, thio-, and phosphono-carboxylation of unsaturated compounds with carbon dioxide: an overview. J. CO2 Util, 2021, 48, 101522.,
[http://dx.doi.org/10.1016/j.jcou.2021.101522]
[35]
Butcher, T.W.; McClain, E.J.; Hamilton, T.G.; Perrone, T.M.; Kroner, K.M.; Donohoe, G.C.; Akhmedov, N.G.; Petersen, J.L.; Popp, B.V. Regioselective copper-catalyzed boracarboxylation of vinyl arenes. Org. Lett., 2016, 18(24), 6428-6431.
[http://dx.doi.org/10.1021/acs.orglett.6b03326] [PMID: 27978640]
[36]
Ye, J.H.; Miao, M.; Huang, H.; Yan, S.S.; Yin, Z.B.; Zhou, W.J.; Yu, D.G. Visible-light-driven iron-promoted thiocarboxylation of styrenes and acrylates with CO2. Angew. Chem. Int. Ed. Engl., 2017, 56(48), 15416-15420.
[http://dx.doi.org/10.1002/anie.201707862] [PMID: 29024349]
[37]
Fu, Q.; Bo, Z.Y.; Ye, J.H.; Ju, T.; Huang, H.; Liao, L.L.; Yu, D.G. Transition metal-free phosphonocarboxylation of alkenes with carbon dioxide via visible-light photoredox catalysis. Nat. Commun., 2019, 10(1), 3592.
[http://dx.doi.org/10.1038/s41467-019-11528-8] [PMID: 31399588]
[38]
Takimoto, M.; Mori, M. Novel catalytic CO2 incorporation reaction: nickel-catalyzed regio- and stereoselective ring-closing carboxylation of bis-1,3-dienes. J. Am. Chem. Soc., 2002, 124(34), 10008-10009.
[http://dx.doi.org/10.1021/ja026620c] [PMID: 12188663]
[39]
Takimoto, M.; Nakamura, Y.; Kimura, K.; Mori, M. Highly enantioselective catalytic carbon dioxide incorporation reaction: nickel-catalyzed asymmetric carboxylative cyclization of bis-1,3-dienes. J. Am. Chem. Soc., 2004, 126(19), 5956-5957.
[http://dx.doi.org/10.1021/ja049506y] [PMID: 15137747]
[40]
Tsuda, T.; Ueda, K.; Saegusa, T. Carbon dioxide insertion into organocopper and organosilver compounds. J. Chem. Soc. Chem. Commun., 1974, 5(10), 380-381.
[http://dx.doi.org/10.1039/c39740000380]
[41]
Fukue, Y.; Oi, S.Y.I. Direct synthesis of alkyl-2-alkynoates from alk-l-ynes, CO2, and bromoalkanes catalysed by copper(1) or silver(1) salt. J. Chem. Soc. Chem. Commun., 1994, 18, 2091.
[http://dx.doi.org/10.1039/c39940002091]
[42]
Dang, Q.Q.; Liu, C.Y.; Wang, X.M.; Zhang, X.M. Novel covalent triazine framework for high-performance CO2 capture and alkyne carboxylation reaction. ACS Appl. Mater. Interfaces, 2018, 10(33), 27972-27978.
[http://dx.doi.org/10.1021/acsami.8b08964] [PMID: 30040377]
[43]
Lan, X.; Du, C.; Cao, L.; She, T.; Li, Y.; Bai, G. Ultrafine Ag nanoparticles encapsulated by covalent triazine framework nanosheets for CO2 conversion. ACS Appl. Mater. Interfaces, 2018, 10(45), 38953-38962.
[http://dx.doi.org/10.1021/acsami.8b14743] [PMID: 30338979]
[44]
Liu, X.H.; Ma, J.G.; Niu, Z.; Yang, G.M.; Cheng, P. An efficient nanoscale heterogeneous catalyst for the capture and conversion of carbon dioxide at ambient pressure. Angew. Chem. Int. Ed. Engl., 2015, 54(3), 988-991.
[http://dx.doi.org/10.1002/anie.201409103] [PMID: 25385217]
[45]
Molla, R.A.; Ghosh, K.; Banerjee, B.; Iqubal, M.A.; Kundu, S.K.; Islam, S.M.; Bhaumik, A. Silver nanoparticles embedded over porous metal organic frameworks for carbon dioxide fixation via carboxylation of terminal alkynes at ambient pressure. J. Colloid Interface Sci., 2016, 477, 220-229.
[http://dx.doi.org/10.1016/j.jcis.2016.05.037] [PMID: 27309859]
[46]
Sun, L.; Yun, Y.; Sheng, H.; Du, Y.; Ding, Y.; Wu, P.; Li, P.; Zhu, M. Rational encapsulation of atomically precise nanoclusters into metal-organic frameworks by electrostatic attraction for CO2 conversion. J. Mater. Chem. A Mater. Energy Sustain., 2018, 6(31), 15371-15376.
[http://dx.doi.org/10.1039/C8TA04667K]
[47]
Zhou, Z.; Yang, L.; Wang, Y.F.; He, C.; Duan, C.Y. Recent advance on chemical fixation of carbon dioxide by metal-organic frameworks as heterogeneous catalysts. Curr. Org. Chem., 2018, 22(18), 1809-1824.
[http://dx.doi.org/10.2174/1385272822666180423144934]
[48]
Yu, D.; Tan, M.X.; Zhang, Y. Carboxylation of terminal alkynes with carbon dioxide catalyzed by poly(N-heterocyclic carbene)-supported silver nanoparticles. Adv. Synth. Catal., 2012, 354(6), 969-974.
[http://dx.doi.org/10.1002/adsc.201100934]
[49]
Zhang, X.; Liu, H.; Shi, Y.; Han, J.; Yang, Z.; Zhang, Y.; Long, C.; Guo, J.; Zhu, Y.; Qiu, X.; Xue, G.; Zhang, L.; Zhang, B.; Chang, L.; Tang, Z. Boosting CO2 conversion with terminal alkynes by molecular architecture of graphene oxide-supported Ag nanoparticles. Matter, 2020, 3(2), 558-570.
[http://dx.doi.org/10.1016/j.matt.2020.07.022]
[50]
Zhang, W.; Mei, Y.; Huang, X.; Wu, P.; Wu, H.; He, M. Size-controlled growth of silver nanoparticles onto functionalized ordered mesoporous polymers for efficient CO2 upgrading. ACS Appl. Mater. Interfaces, 2019, 11(47), 44241-44248.
[http://dx.doi.org/10.1021/acsami.9b14927] [PMID: 31674181]
[51]
Cui, Y.; Xu, Z.; Li, H.Y.; Young, D.J.; Ren, Z.G.; Li, H.X. Synthesis of a pyrazole-based microporous organic polymer for high-performance CO2 capture and alkyne carboxylation. ACS Appl. Polym. Mater., 2020, 2(11), 4512-4520.
[http://dx.doi.org/10.1021/acsapm.0c00592]
[52]
Shi, G.; Xu, W.; Wang, J.; Yuan, Y.; Chaemchuen, S.; Verpoort, F. A Cubased MOF for the effective carboxylation of terminal alkynes with CO2 under mild conditions. J. CO2 Util, 2020, 39, 101177.,
[http://dx.doi.org/10.1016/j.jcou.2020.101177]
[53]
Bondarenko, G.N.; Dvurechenskaya, E.G.; Magommedov, E.S.; Beletskaya, I.P. Copper(0) nanoparticles supported on Al2O3 as catalyst for carboxylation of terminal alkynes. Catal. Lett., 2017, 147(10), 2570-2580.
[http://dx.doi.org/10.1007/s10562-017-2127-0]
[54]
Bu, R.; Zhang, L.; Gao, L.L.; Sun, W.J.; Yang, S.L.; Gao, E.Q. Copper(I)-modified covalent organic framework for CO2 insertion to terminal alkynes. Mol. Catal., 2021, 499111319
[http://dx.doi.org/10.1016/j.mcat.2020.111319]
[55]
Yang, P.; Zuo, S.; Zhang, F.; Yu, B.; Guo, S.; Yu, X.; Zhao, Y.; Zhang, J.; Liu, Z. Carbon nitride-based single-atom Cu catalysts for highly efficient carboxylation of alkynes with atmospheric CO2. Ind. Eng. Chem. Res., 2020, 59(16), 7327-7335.
[http://dx.doi.org/10.1021/acs.iecr.0c00547]
[56]
Burkhart, G.; Hoberg, H. Oxanickelacyclopentene derivatives from Nickel(0), carbon dioxide, and alkynes. Angew. Chem. Int. Ed. Engl., 1982, 21(1), 76-76.
[http://dx.doi.org/10.1002/anie.198200762]
[57]
Saito, S.; Nakagawa, S.; Koizumi, T.; Hirayama, K.; Yamamoto, Y. Nickel-mediated regio- and chemoselective carboxylation of alkynes in the presence of carbon dioxide. J. Org. Chem., 1999, 64(11), 3975-3978.
[http://dx.doi.org/10.1021/jo982443f]
[58]
Takimoto, M.; Shimizu, K.; Mori, M. Nickel-promoted alkylative or arylative carboxylation of alkynes. Org. Lett., 2001, 3(21), 3345-3347.
[http://dx.doi.org/10.1021/ol016585z] [PMID: 11594830]
[59]
Dèrien, S.; Duńach, E.; Périchon, J. From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes magnesium ions as the key for catalysis. J. Am. Chem. Soc., 1991, 113(22), 8447-8454.
[http://dx.doi.org/10.1021/ja00022a037]
[60]
Li, S.; Yuan, W.; Ma, S. Highly regio- and stereoselective three-component nickel-catalyzed syn-hydrocarboxylation of alkynes with diethyl zinc and carbon dioxide. Angew. Chem. Int. Ed. Engl., 2011, 50(11), 2578-2582.
[http://dx.doi.org/10.1002/anie.201007128] [PMID: 21370341]
[61]
Fujihara, T.; Xu, T.; Semba, K.; Terao, J.; Tsuji, Y. Copper-catalyzed hydrocarboxylation of alkynes using carbon dioxide and hydrosilanes. Angew. Chem. Int. Ed. Engl., 2011, 50(2), 523-527.
[http://dx.doi.org/10.1002/anie.201006292] [PMID: 21157832]
[62]
Takimoto, M.; Hou, Z. Cu-catalyzed formal methylative and hydrogenative carboxylation of alkynes with carbon dioxide: efficient synthesis of α,β-unsaturated carboxylic acids. Chemistry, 2013, 19(34), 11439-11445.
[http://dx.doi.org/10.1002/chem.201301456] [PMID: 23852827]
[63]
Santhoshkumar, R.; Hong, Y.C.; Luo, C.Z.; Wu, Y.C.; Hung, C.H.; Hwang, K.Y.; Tu, A.P.; Cheng, C.H. Synthesis of vinyl carboxylic acids using carbon dioxide as a carbon source by iron-catalyzed hydromagnesiation. ChemCatChem, 2016, 8(13), 2210-2213.
[http://dx.doi.org/10.1002/cctc.201600279]
[64]
Shao, P.; Wang, S.; Du, G.; Xi, C. Cp2TiCl2-catalyzed hydrocarboxylation of alkynes with CO2: formation of α,β-unsaturated carboxylic acids. RSC Adv, 2017, 7(6), 3534-3539.
[http://dx.doi.org/10.1039/C6RA25003C]
[65]
Wang, X.; Nakajima, M.; Martin, R. Ni-catalyzed regioselective hydrocarboxylation of alkynes with CO2 by using simple alcohols as proton sources. J. Am. Chem. Soc., 2015, 137(28), 8924-8927.
[http://dx.doi.org/10.1021/jacs.5b05513] [PMID: 26130587]
[66]
Taniguchi, T.; Saito, N.; Doi, R.; Kimoto, A.; Hoshiya, N.; Fujiki, K.; Shuto, S.; Fujioka, H.; Arisawa, M.; Sato, Y. Nickel nanoparticle-catalyzed carboxylation of unsaturated hydrocarbon with CO2 using sulfur-modified Au-supported nickel material. Chem. Lett., 2019, 48(11), 1406-1409.
[http://dx.doi.org/10.1246/cl.190650]
[67]
Mao, J.L.; Ran, X.K.; Tian, J.Z.; Jiao, B.; Zhou, H.L.; Chen, L.; Wang, Z.G. Design, synthesis and biological evaluation of novel 4-hydroxybenzene acrylic acid derivatives. Bioorg. Med. Chem. Lett., 2011, 21(5), 1549-1553.
[http://dx.doi.org/10.1016/j.bmcl.2010.12.063] [PMID: 21288716]
[68]
Louie, J.; Gibby, J.E.; Farnworth, M.V.; Tekavec, T.N. Efficient nickel-catalyzed [2 + 2 + 2] cycloaddition of CO2 and diynes. J. Am. Chem. Soc., 2002, 124(51), 15188-15189.
[http://dx.doi.org/10.1021/ja027438e] [PMID: 12487590]
[69]
Cao, T.; Yang, Z. Selectivities in nickel-catalyzed hydrocarboxylation of enynes with carbon dioxide. ACS Catal., 2017, 7(7), 4504-4508.
[http://dx.doi.org/10.1021/acscatal.7b00556]
[70]
Diccianni, J.B.; Heitmann, T.; Diao, T. Nickel-catalyzed reductive cycloisomerization of enynes with CO2. J. Org. Chem., 2017, 82(13), 6895-6903.
[http://dx.doi.org/10.1021/acs.joc.7b01034] [PMID: 28614656]
[71]
Zhang, L.; Cheng, J.; Carry, B.; Hou, Z. Catalytic boracarboxylation of alkynes with diborane and carbon dioxide by an N-heterocyclic carbene copper catalyst. J. Am. Chem. Soc., 2012, 134(35), 14314-14317.
[http://dx.doi.org/10.1021/ja3063474] [PMID: 22909063]
[72]
Fleming, I.; Roessler, F. Reaction of a silyl-copper reagent with acetylenes: a new synthesis of vinylsilanes. J. Chem. Soc. Chem. Commun., 1980, 1(6), 276-277.
[http://dx.doi.org/10.1039/C39800000276]
[73]
Fujihara, T.; Tani, Y.; Semba, K.; Terao, J.; Tsuji, Y. Copper-catalyzed silacarboxylation of internal alkynes by employing carbon dioxide and silylboranes. Angew. Chem. Int. Ed. Engl., 2012, 51(46), 11487-11490.
[http://dx.doi.org/10.1002/anie.201207148] [PMID: 23042673]
[74]
Huang, W.B.; Ren, F.Y.; Wang, M.W.; Qiu, L.Q.; Chen, K.H.; He, L.N. Bin; Ren, F.Y.; Wang, M.W.; Qiu, L.Q.; Chen, K.H.; He, L.N. Cu(II)-catalyzed phosphonocarboxylative cyclization reaction of propargylic amines and phosphine oxide with CO2. J. Org. Chem., 2020, 85(21), 14109-14120.
[http://dx.doi.org/10.1021/acs.joc.0c02172] [PMID: 33118350]
[75]
Miao, B.; Li, S.; Li, G.; Ma, S. Cyclic anti-azacarboxylation of 2-alkynylanilines with carbon dioxide. Org. Lett., 2016, 18(11), 2556-2559.
[http://dx.doi.org/10.1021/acs.orglett.6b00884] [PMID: 27214662]
[76]
Kirillov, E.; Carpentier, J.F.; Bunel, E.; Friedrich, J.A.G. Carboxylic acid derivatives via catalytic carboxylation of unsaturated hydrocarbons: whether the nature of a reductant may determine the mechanism of CO2 incorporation? Dalton Trans., 2015, 44(37), 16212-16223.
[http://dx.doi.org/10.1039/C5DT02350E] [PMID: 26243336]
[77]
Yamazaki, K.; Moteki, T.; Ogura, M. Carbonate synthesis from carbon dioxide and cyclic ethers over methylated nitrogen-substituted mesoporous silica. Mol. Catal., 2018, 454, 38-43.
[http://dx.doi.org/10.1016/j.mcat.2018.05.014]
[78]
Modak, A.; Ghosh, A.; Bhaumik, A.; Chowdhury, B. CO2 hydrogenation over functional nanoporous polymers and metal-organic frameworks. Adv. Colloid Interface Sci., 2021, 290102349
[http://dx.doi.org/10.1016/j.cis.2020.102349] [PMID: 33780826]
[79]
Zhou, C.G.; Yu, S.A.; Ma, K.; Liang, B.; Tang, S.Y.; Liu, C.J.; Yue, H.R. Amine-functionalized mesoporous monolithic adsorbents for post-combustion carbon dioxide capture. Chem. Eng. J., 2021, 413127675
[http://dx.doi.org/10.1016/j.cej.2020.127675]

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Request history8.2.27PHP Version420msRequest Duration28MBMemory UsageGET article/{article_id}/{param?}Route
  • warninglog[15:39:09] LOG.warning: Optional parameter $article_id declared before required parameter $request i...
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  • Application (295ms)time
  • 1 x Application (70.23%)
    295ms
    1 x Booting (29.77%)
    125ms
    14 templates were rendered
    • articlearticle.blade.php#?blade
    • includes.article_top_bannerarticle_top_banner.blade.php#?blade
    • includes.article_referencearticle_reference.blade.php#?blade
    • export_citation_formexport_citation_form.blade.php#?blade
    • includes.article_bottom_bannerarticle_bottom_banner.blade.php#?blade
    • includes.inc_related_journalsinc_related_journals.blade.php#?blade
    • includes.inc_related_ebooksinc_related_ebooks.blade.php#?blade
    • includes.journal_rightmenujournal_rightmenu.blade.php#?blade
    • includes.journal_right_bannerjournal_right_banner.blade.php#?blade
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    uri
    GET article/{article_id}/{param?}
    middleware
    web, check_user_access
    controller
    App\Http\Controllers\ArticleController@GetArticleDetails
    namespace
    App\Http\Controllers
    where
    as
    article
    file
    app/Http/Controllers/ArticleController.php:1974-2510
    36 statements were executed, 4 of which were duplicates, 32 unique. Show only duplicated199ms
    • Connection Establishedalphaeurekaselec_live_10_06_2022UserAccessCheck.php#24
      Backtrace
      • 9. middleware::check_user_access:24
      • 10. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 11. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 12. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 13. vendor/laravel/framework/src/Illuminate/Foundation/Http/Middleware/VerifyCsrfToken.php:88
    • INSERT INTO visitor_ip_address (ip_address,visitor_agent,visitor_count, created_on,updated_on) VALUES ('316600437','',1,1740497949,1740497949) ON DUPLICATE KEY UPDATE visitor_count=visitor_count + 1, updated_on=1740497949
      1.89msalphaeurekaselec_live_10_06_2022UserAccessCheck.php#24
      Backtrace
      • 11. middleware::check_user_access:24
      • 12. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 14. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 15. vendor/laravel/framework/src/Illuminate/Foundation/Http/Middleware/VerifyCsrfToken.php:88
    • INSERT INTO visitor_ip_address_detail (ip_address,visitor_url,visitor_count, created_on,updated_on) VALUES ('316600437','/article/119229',1,1740497949,1740497949)
      1.6msalphaeurekaselec_live_10_06_2022UserAccessCheck.php#27
      Backtrace
      • 11. middleware::check_user_access:27
      • 12. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 14. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 15. vendor/laravel/framework/src/Illuminate/Foundation/Http/Middleware/VerifyCsrfToken.php:88
    • (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_journal_volume_trail WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_journal_volume_corporate WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_journal_volume_token WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_ebook_volume_trail WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_ebook_volume_corporate WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_ebook_volume_token WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_issue_trail WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_issue_corporate WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_issue_token WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_article_trail WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_article_corporate WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_article_token WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_chapter_trail WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_chapter_corporate WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_chapter_token WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_disease_corporate WHERE to_ip >= 316600437 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 316600437) limit 1
      14.94msalphaeurekaselec_live_10_06_2022UserAccess.php#784
      Bindings
      • 0: 316600437
      • 1: 316600437
      • 2: 316600437
      • 3: 316600437
      • 4: 316600437
      • 5: 316600437
      • 6: 316600437
      • 7: 316600437
      • 8: 316600437
      • 9: 316600437
      • 10: 316600437
      • 11: 316600437
      • 12: 316600437
      • 13: 316600437
      • 14: 316600437
      • 15: 316600437
      Backtrace
      • 14. app/Models/UserAccess/UserAccess.php:784
      • 15. middleware::check_user_access:114
      • 16. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 18. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
    • SELECT at.type_name, p.copyright, p.publisher_location,m.month,y.year, a.publish_on, a.nid article_nid,a.article_id, a.pmid, a.issue_id, a.title, a.abstract,a.podcast,a.altmetric_score,a.altmetric_url,a.kudos_url, a.page_count, a.first_page, a.elocator, a.last_page, i.publication_date, a.file_name, a.file_path, a.doi, a.is_epub,a.epub_type, a.volume_id, a.is_uploaded, a.editor_choice, a.is_epub, j.image_file_name, a.article_no, a.art_type AS article_type, a.supplementary_filename,a.html_filename,a.prc_filename,a.epub_filename, a.graph_abs_lg_filename, a.graph_abs_sm_filename, a.oa_image_lg_filename, a.oa_image_sm_filename, j.journal_banner,a.animated_abstract,a.erratum_in,a.erratum_for, (CASE WHEN a.issue_id =0 THEN j.epub_price ELSE j.price END) AS sell_price, j.epub_price, j.nid AS jour_nid, j.title AS journal_title, j.issn, j.eissn,j.journal_id, j.subtitle AS jour_subtitle, v.volume_id,v.volume_name AS volume, v.year_id, i.title AS issue, i.month_id ,i.type issue_type, j.subtitle,j.formerly_title, ac.subtitle AS epub_title,a.crossmark_enabled,a.text_mining_urls,a.license_urls,a.created, a.receivedate, a.revisedate, a.acceptdate,js.js_title FROM article a LEFT JOIN article_section ac ON a.is_epub = ac.art_sec_id LEFT JOIN journal_section js ON a.js_id = js.js_id LEFT JOIN article_type at ON a.art_type = at.art_type_id LEFT JOIN issue i ON a.issue_id = i.issue_id LEFT JOIN month m ON m.id = i.month_id LEFT JOIN volume v ON v.volume_id = a.volume_id INNER JOIN year y ON y.id = v.year_id INNER JOIN journal j ON j.journal_id = a.journal_id INNER JOIN publisher p ON p.publisher_id = j.publisher_id WHERE a.article_id=119229
      1.51msalphaeurekaselec_live_10_06_2022Article.php#408
      Backtrace
      • 11. app/Models/Article.php:408
      • 12. app/Http/Controllers/ArticleController.php:2515
      • 13. app/Http/Controllers/ArticleController.php:2035
      • 14. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 15. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select * from `journal` where `journal_id` = 19 limit 1
      900μsalphaeurekaselec_live_10_06_2022Journal.php#64
      Bindings
      • 0: 19
      Backtrace
      • 14. app/Models/Journal.php:64
      • 15. app/Http/Controllers/ArticleController.php:2516
      • 16. app/Http/Controllers/ArticleController.php:2035
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select count(*) as aggregate from (select j.nid as journal_nid,j.flyer_link,j.title ,j.issn,j.eissn,j.keyword, j.journal_id as journal_id, j.subtitle, j.image_file_name,j.description,j.journal_insight_url,j.doi from `subject_journal` as `sj` inner join `journal` as `j` on `j`.`journal_id` = `sj`.`journal_id` where j.journal_status=1 and subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and sj.journal_id!=19 group by `j`.`nid`) as `aggregate_table`
      700μsalphaeurekaselec_live_10_06_2022Subject.php#200
      Backtrace
      • 16. app/Models/Subject.php:200
      • 17. app/Http/Controllers/ArticleController.php:2517
      • 18. app/Http/Controllers/ArticleController.php:2035
      • 19. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 20. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select j.nid as journal_nid,j.flyer_link,j.title ,j.issn,j.eissn,j.keyword, j.journal_id as journal_id, j.subtitle, j.image_file_name,j.description,j.journal_insight_url,j.doi from `subject_journal` as `sj` inner join `journal` as `j` on `j`.`journal_id` = `sj`.`journal_id` where j.journal_status=1 and subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and sj.journal_id!=19 group by `j`.`nid` order by `j`.`journal_id` asc limit 10 offset 0
      620μsalphaeurekaselec_live_10_06_2022Subject.php#200
      Backtrace
      • 14. app/Models/Subject.php:200
      • 15. app/Http/Controllers/ArticleController.php:2517
      • 16. app/Http/Controllers/ArticleController.php:2035
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select count(*) as aggregate from (select v.nid as volume_id,e.nid,e.title,v.issn,v.eissn,v.isbn,v.eisbn,e.ebook_id, v.image_file_name,v.file_path,v.flyer_link,v.ebook_volume_id, v.volume_name,v.doi,v.year_id,v.introduction from `subject_ebook` as `se` inner join `ebook` as `e` on `e`.`ebook_id` = `se`.`ebook_id` inner join `ebook_volume` as `v` on `v`.`ebook_id` = `se`.`ebook_id` inner join `year` as `y` on `y`.`id` = `v`.`year_id` where subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and v.ebook_status='1' and y.year > 2020 group by `v`.`nid`) as `aggregate_table`
      51.66msalphaeurekaselec_live_10_06_2022Subject.php#220
      Backtrace
      • 16. app/Models/Subject.php:220
      • 17. app/Http/Controllers/ArticleController.php:2518
      • 18. app/Http/Controllers/ArticleController.php:2035
      • 19. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 20. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select v.nid as volume_id,e.nid,e.title,v.issn,v.eissn,v.isbn,v.eisbn,e.ebook_id, v.image_file_name,v.file_path,v.flyer_link,v.ebook_volume_id, v.volume_name,v.doi,v.year_id,v.introduction from `subject_ebook` as `se` inner join `ebook` as `e` on `e`.`ebook_id` = `se`.`ebook_id` inner join `ebook_volume` as `v` on `v`.`ebook_id` = `se`.`ebook_id` inner join `year` as `y` on `y`.`id` = `v`.`year_id` where subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and v.ebook_status='1' and y.year > 2020 group by `v`.`nid` order by `v`.`ebook_volume_id` desc limit 10 offset 0
      4.61msalphaeurekaselec_live_10_06_2022Subject.php#220
      Backtrace
      • 14. app/Models/Subject.php:220
      • 15. app/Http/Controllers/ArticleController.php:2518
      • 16. app/Http/Controllers/ArticleController.php:2035
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select * from `keywords` where `article_id` = '119229'
      990μsalphaeurekaselec_live_10_06_2022Keywords.php#43
      Bindings
      • 0: 119229
      Backtrace
      • 13. app/Models/Keywords.php:43
      • 14. app/Http/Controllers/ArticleController.php:2519
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select * from `article_citation` where `article_id` = '119229'
      6.83msalphaeurekaselec_live_10_06_2022Article.php#1570
      Bindings
      • 0: 119229
      Backtrace
      • 13. app/Models/Article.php:1570
      • 14. app/Http/Controllers/ArticleController.php:2520
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select CONCAT_WS(' ',au.first_name, ' ', ifnull(au.initials,''), ' ', au.last_name) as authors, CONCAT(au.last_name, IFNULL(CONCAT(' ', au.initials), ''), ' ', au.first_name) AS authorsRIS, CONCAT_WS(' ',au.last_name, ' ', ifnull(au.initials,''), ' ', au.first_name) as authorsCiteAs, CONCAT_WS(' ',au.first_name, IFNULL(CONCAT(' ', au.initials), ''), IFNULL(CONCAT(' ', au.last_name), '')) as authorsmodal , `au`.*, `af`.`ror_id`, `af`.`institution`, `af`.`department`, `af`.`country`, `af`.`city`, `af`.`address`, (GROUP_CONCAT(TRIM(BOTH ', ' FROM CONCAT(ifnull(concat(af.institution,','),''), ifnull(concat(af.department,','),''), ifnull(concat(af.address,','),''), ifnull(concat(af.city,','),''), ifnull(concat(af.country,','),''), ifnull(concat(af.postal_code,','),''), ifnull(concat(af.phone,','),''), ifnull(concat(af.fax,','),''))) SEPARATOR '|')) as `author_affiliation`, (GROUP_CONCAT(TRIM(BOTH ', ' FROM CONCAT(ifnull(concat(af.web_view,','),''))) SEPARATOR '|')) as `web_view` from `author` as `au` left join `author_affiliation` as `af` on `au`.`author_id` = `af`.`author_id` where `au`.`article_id` = '119229' group by `au`.`author_id` order by `au`.`article_id` asc, `au`.`sequence` asc
      1.56msalphaeurekaselec_live_10_06_2022Author.php#86
      Bindings
      • 0: 119229
      Backtrace
      • 13. app/Models/Author.php:86
      • 14. app/Http/Controllers/ArticleController.php:2533
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select `bo`.* from `bundle_offer` as `bo` where `bo`.`bundle_status` = 'A' order by `bo`.`bundle_id` desc
      350μsalphaeurekaselec_live_10_06_2022BundleOffer.php#57
      Bindings
      • 0: A
      Backtrace
      • 13. app/Models/BundleOffer.php:57
      • 14. app/Http/Controllers/ArticleController.php:2535
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select `subtitle` from `journal` where `continues_publication_journal` = 1
      730μsalphaeurekaselec_live_10_06_2022Article.php#1960
      Bindings
      • 0: 1
      Backtrace
      • 13. app/Models/Article.php:1960
      • 14. app/Http/Controllers/ArticleController.php:2062
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • Select j.subtitle, v.volume_id as volume_id,v.year_id,y.year as year,v.volume_name, v.total_no_of_issues, i.issue_id as issue_id,i.title as issue, i.publication_date as issue_pub_date from journal j join volume v on j.journal_id = v.journal_id join issue i on v.volume_id = i.volume_id join article a on a.issue_id = i.issue_id join year y on v.year_id = y.id where j.journal_id = 19 and i.is_uploaded = 1 order by v.volume_name+0 desc, i.title+0 desc limit 1
      51.04msalphaeurekaselec_live_10_06_2022Issue.php#298
      Backtrace
      • 11. app/Models/Issue.php:298
      • 12. app/Http/Controllers/ArticleController.php:2068
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select a.nid,a.publish_on, a.pmid,a.article_id,a.doi,j.journal_id,j.subtitle,v.volume_name,a.volume_id as volume_id, a.issue_id,a.title,first_page, last_page, page_count,abstract,ifnull(is_abstract,"y"),asec.title as article_section,at.type_name as article_type_name, a.article_id as ArticleID ,is_epub,epub_price,epub_type,a.created, y.year from `article` as `a` left join `article_section` as `asec` on `asec`.`art_sec_id` = `a`.`is_epub` left join `article_type` as `at` on `at`.`art_type_id` = `a`.`art_type` left join `journal` as `j` on `j`.`journal_id` = `a`.`journal_id` inner join `volume` as `v` on `a`.`volume_id` = `v`.`volume_id` inner join `year` as `y` on `v`.`year_id` = `y`.`id` where a.article_status != "W" and a.is_epub = 1 and a.journal_id = 19 and a.is_uploaded = 1 group by `a`.`article_id` order by `a`.`publish_on` desc
      19.99msalphaeurekaselec_live_10_06_2022Article.php#528
      Backtrace
      • 13. app/Models/Article.php:528
      • 14. app/Http/Controllers/ArticleController.php:2070
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select a.nid,a.publish_on, a.pmid,a.article_id,a.doi,j.journal_id,j.subtitle,v.volume_name,a.volume_id as volume_id, a.issue_id,a.title,first_page, last_page, page_count,abstract,ifnull(is_abstract,"y"),asec.title as article_section,at.type_name as article_type_name, a.article_id as ArticleID ,is_epub,epub_price,epub_type,a.created, y.year from `article` as `a` left join `article_section` as `asec` on `asec`.`art_sec_id` = `a`.`is_epub` left join `article_type` as `at` on `at`.`art_type_id` = `a`.`art_type` left join `journal` as `j` on `j`.`journal_id` = `a`.`journal_id` inner join `volume` as `v` on `a`.`volume_id` = `v`.`volume_id` inner join `year` as `y` on `v`.`year_id` = `y`.`id` where a.article_status != "W" and a.is_epub = 4 and a.journal_id = 19 and a.is_uploaded = 1 group by `a`.`article_id` order by `a`.`publish_on` desc
      18.73msalphaeurekaselec_live_10_06_2022Article.php#528
      Backtrace
      • 13. app/Models/Article.php:528
      • 14. app/Http/Controllers/ArticleController.php:2071
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select pdf, html, epub, prc from `article_metrics` where `article_id` = 119229 limit 1
      320μsalphaeurekaselec_live_10_06_2022Article.php#744
      Bindings
      • 0: 119229
      Backtrace
      • 14. app/Models/Article.php:744
      • 15. app/Http/Controllers/ArticleController.php:2091
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from content_by_diseases where content_id = 119229 and content_type = 'article' order by status desc limit 1
      380μsalphaeurekaselec_live_10_06_2022Article.php#751
      Backtrace
      • 11. app/Models/Article.php:751
      • 12. app/Http/Controllers/ArticleController.php:2094
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `node_meta` where `nid` = 198566 limit 1
      200μsalphaeurekaselec_live_10_06_2022Meta.php#30
      Bindings
      • 0: 198566
      Backtrace
      • 14. app/Models/Meta.php:30
      • 15. app/Http/Controllers/ArticleController.php:2101
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select `bo`.* from `bundle_offer` as `bo` where `bo`.`bundle_status` = 'A' order by `bo`.`bundle_id` desc
      260μsalphaeurekaselec_live_10_06_2022BundleOffer.php#57
      Bindings
      • 0: A
      Backtrace
      • 13. app/Models/BundleOffer.php:57
      • 14. app/Http/Controllers/ArticleController.php:2108
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `tbl_ht_submission` as `h` where `h`.`subtitle` = 'COC' and (h.proposal_closing_date = 0 OR TO_DAYS(FROM_UNIXTIME(h.proposal_closing_date)) >= TO_DAYS(NOW())) order by `h`.`manuscript` asc
      470μsalphaeurekaselec_live_10_06_2022Article.php#2025
      Bindings
      • 0: COC
      Backtrace
      • 13. app/Models/Article.php:2025
      • 14. app/Http/Controllers/ArticleController.php:2112
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select count(*) as total_count, content_type_access_id as access_type from journal_access where content_type_id = '119229' and content_type = 'a' and ( (from_date <= CURDATE() and to_date >= CURDATE() and perpetual= 0) or (from_date is null and to_date is null and perpetual= 1) )
      450μsalphaeurekaselec_live_10_06_2022ContentAccess.php#647
      Backtrace
      • 11. app/Models/ContentAccess.php:647
      • 12. app/Http/Controllers/ArticleController.php:2186
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select count(*) as total_count, content_type_access_id as access_type from journal_access where content_type_id = '11126' and content_type = 'i' and ( (from_date <= CURDATE() and to_date >= CURDATE() and perpetual= 0) or (from_date is null and to_date is null and perpetual= 1) )
      400μsalphaeurekaselec_live_10_06_2022ContentAccess.php#647
      Backtrace
      • 11. app/Models/ContentAccess.php:647
      • 12. app/Http/Controllers/ArticleController.php:2207
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select count(*) as total_count, content_type_access_id as access_type from journal_access where content_type_id = '3226' and content_type = 'v' and ( (from_date <= CURDATE() and to_date >= CURDATE() and perpetual= 0) or (from_date is null and to_date is null and perpetual= 1) )
      370μsalphaeurekaselec_live_10_06_2022ContentAccess.php#647
      Backtrace
      • 11. app/Models/ContentAccess.php:647
      • 12. app/Http/Controllers/ArticleController.php:2231
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"volume" as access_level,"" as issue_id,"" as article_id from `user_access_journal_volume_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.volume_id = 3226) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"volume" as access_level,"" as issue_id,"" as article_id from `user_access_journal_volume_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.volume_id = 3226) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"volume" as access_level,"" as issue_id,"" as article_id from `user_access_journal_volume_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.volume_id = 3226)
      7.6msalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ArticleController.php:2272
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"issue" as access_level,j.issue_id,"" as article_id from `user_access_issue_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.issue_id = 11126) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"issue" as access_level,j.issue_id,"" as article_id from `user_access_issue_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.issue_id = 11126) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"issue" as access_level,j.issue_id,"" as article_id from `user_access_issue_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.issue_id = 11126)
      840μsalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ArticleController.php:2297
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"article" as access_level, j.issue_id, j.article_id from `user_access_article_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.article_id = 119229) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"article" as access_level, j.issue_id, j.article_id from `user_access_article_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.article_id = 119229) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"article" as access_level, j.issue_id, j.article_id from `user_access_article_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 316600437 and j.to_ip >=316600437 )) and ((j.from_date <= 1740497949 and j.to_date >= 1740497949 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.article_id = 119229)
      830μsalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ArticleController.php:2329
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `article` where `first_page` < '60' and is_uploaded = 1 and issue_id = 11126 order by cast(first_page as SIGNED) desc limit 1
      590μsalphaeurekaselec_live_10_06_2022Article.php#1819
      Bindings
      • 0: 60
      Backtrace
      • 14. app/Models/Article.php:1819
      • 15. app/Http/Controllers/ArticleController.php:2470
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `article` where `last_page` > '70' and is_uploaded = 1 and issue_id = 11126 order by cast(first_page as SIGNED) asc limit 1
      630μsalphaeurekaselec_live_10_06_2022Article.php#1831
      Bindings
      • 0: 70
      Backtrace
      • 14. app/Models/Article.php:1831
      • 15. app/Http/Controllers/ArticleController.php:2472
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select `language_id` from `multilanguage` where `short_code` = 'en'
      230μsalphaeurekaselec_live_10_06_2022ArticleController.php#2497
      Bindings
      • 0: en
      Backtrace
      • 14. app/Http/Controllers/ArticleController.php:2497
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:206
    • select `source_lang_label`, `target_lang_label` from `multilanguage_labels` where `target_lang_id` = 1
      320μsalphaeurekaselec_live_10_06_2022MultiLanguage.php#23
      Bindings
      • 0: 1
      Backtrace
      • 13. app/Models/MultiLanguage.php:23
      • 14. app/Http/Controllers/ArticleController.php:2498
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select `id` from `multilanguage_article` where `article_id` = 119229 limit 1
      3.88msalphaeurekaselec_live_10_06_2022ArticleController.php#2506
      Bindings
      • 0: 119229
      Backtrace
      • 16. app/Http/Controllers/ArticleController.php:2506
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 19. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
      • 20. vendor/laravel/framework/src/Illuminate/Routing/Route.php:206
    • select b.banner_link, b.banner_name, b.banner_script, b.banner_remarks, b.banner_file_name, b.banner_placement, bd.content_type, bd.content_id from `tbl_banner` as `b` inner join `tbl_banner_detail` as `bd` on `bd`.`banner_id` = `b`.`banner_id` inner join `users` as `u` on `u`.`id` = `b`.`updated_by` inner join `journal` as `j` on `j`.`journal_id` = `bd`.`content_id` where `b`.`banner_journal` = 1 and `bd`.`content_type` = 'J' and `bd`.`content_id` = 19 and `b`.`banner_from_date` <= 1740497949 and `b`.`banner_to_date` >= 1740497949 and `b`.`banner_status` = 'A' order by `b`.`banner_id` desc
      1.2msalphaeurekaselec_live_10_06_2022Banner.php#95
      Bindings
      • 0: 1
      • 1: J
      • 2: 19
      • 3: 1740497949
      • 4: 1740497949
      • 5: A
      Backtrace
      • 13. app/Models/Banner.php:95
      • 14. app/Http/helpers.php:404
      • 17. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 18. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    • select b.banner_link, b.banner_name, b.banner_script, b.banner_remarks, b.banner_file_name, b.banner_placement, bd.content_type, bd.content_id from `tbl_banner` as `b` inner join `tbl_banner_detail` as `bd` on `bd`.`banner_id` = `b`.`banner_id` inner join `users` as `u` on `u`.`id` = `b`.`updated_by` inner join `journal` as `j` on `j`.`journal_id` = `bd`.`content_id` where `b`.`banner_journal` = 1 and `bd`.`content_type` = 'J' and `bd`.`content_id` = 19 and `b`.`banner_from_date` <= 1740497949 and `b`.`banner_to_date` >= 1740497949 and `b`.`banner_status` = 'A' order by `b`.`banner_id` desc
      1.48msalphaeurekaselec_live_10_06_2022Banner.php#95
      Bindings
      • 0: 1
      • 1: J
      • 2: 19
      • 3: 1740497949
      • 4: 1740497949
      • 5: A
      Backtrace
      • 13. app/Models/Banner.php:95
      • 14. app/Http/helpers.php:404
      • 17. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 18. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    • select count(*) as aggregate from `uc_cart_products` where cart_id='1aa235dd104e98de88e041839a21fa47'
      300μsalphaeurekaselec_live_10_06_2022Cart.php#271
      Backtrace
      • 15. app/Models/Cart.php:271
      • 16. view::layouts._header:260
      • 18. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 20. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    App\Models\MultiLanguage
    1MultiLanguage.php#?
        _token
        uswozyx5TnMw0RqHxo1WsUfOStrKLEP2H4ibOxeL
        uc_cart_id
        1aa235dd104e98de88e041839a21fa47
        _previous
        array:1 [ "url" => "http://alpha.eurekaselect.com/article/119229" ]
        _flash
        array:2 [ "old" => [] "new" => [] ]
        PHPDEBUGBAR_STACK_DATA
        []
        path_info
        /article/119229
        status_code
        200
        
        status_text
        OK
        format
        html
        content_type
        text/html; charset=UTF-8
        request_query
        []
        
        request_request
        []
        
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