Porous liquids: synthesis and application

doi:10.16085/j.issn.1000-6613.2020-1963

Abstract

Abstract:

Porous liquids are an emerging class of liquid material with permanent pores that combine the excellent properties of porous materials with the fluidity of liquids. The permanently porous structures of pore generators can be made from inorganic building blocks or from a combination of organic ligands and inorganic nodes or from organic building blocks. According to the structure of pore generators, this review focused on recent advancements on the use of inorganic hollow nanomaterials, metal organic framework and porous cages as pore generators of porous liquids. This new research direction toward porous liquids chemistry was still in its early stages, which faced many challenges but had great application potential. Porous liquids had been studied in gas absorption, identification of isomers and synthesis of porous liquid separation membrane now, and they were expected to be used in areas of gas capture and separation, catalysis and synthesis membrane material etc.

Key words: porous liquid, inorganic nanomaterial, metal organic frameworks (MOFs), porous cage, separation

摘要：

多孔液体是一类具有永久孔隙的新兴液体材料，它将多孔材料优异的性能和液体的流动性结合在一起。具有永久空腔的造孔器（pore generator），可以完全由无机砌块单元、有机配体和无机节点的组合单元或有机砌块单元构成。本文根据造孔器的结构综述了使用无机纳米材料、金属有机框架和多孔笼合成多孔液体的最新研究进展。文章指出作为新的研究领域，多孔液体化学正处于起步阶段，虽然面临着诸多挑战，但应用潜力巨大。目前在气体吸附、异构体识别、多孔液体膜的合成等方面都有研究，有望在气体捕捉和分离、催化、膜材料制备等领域得到应用。

关键词: 多孔液体, 无机纳米材料, 金属有机框架, 多孔笼, 分离

CLC Number:

O641.3

XIONG Xinkun, SONG Hua, YUAN Binbin, WANG Yuanyuan, ZHANG Haohan, CHEN Yanguang, YUAN Dandan. Porous liquids: synthesis and application[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4346-4359.

熊鑫坤, 宋华, 苑彬彬, 王园园, 张浩瀚, 陈彦广, 苑丹丹. 多孔液体：合成与应用[J]. 化工进展, 2021, 40(8): 4346-4359.

Figures/Tables 2

References 76

77	HOSONO N, KITAGAWA S.Modular design of porous soft materials via self-organization of metal-organic cages[J]. Acc. Chem. Res., 2018, 51(10): 2437-2446.
78	CRAIG G A, LARPENT P, KUSAKA S, et al. Switchable gate-opening effect in metal-organic polyhedra assemblies through solution processing[J]. Chemical Science, 2018, 9(31): 6463-6469.
79	VARDHAN H, YUSUBOV M, VERPOORT F. Self-assembled metal-organic polyhedra: an overview of various applications[J]. Coord. Chem. Rev., 2016, 306: 171-194.
80	JUNG M, KIM H, BAEK K, et al. Synthetic ion channel based on metal-organic polyhedra.[J]. Angew. Chem. Int. Ed., 2008, 47(31): 5755-5757.
81	DENG Z, YING W, GONG K, et al. Facilitate gas transport through metal-organic polyhedra constructed porous liquid membrane[J]. Small, 2020, 16: 1907016.
82	MOW R E, LIPTON A S, SHULDA S, et al. Colloidal three-dimensional covalent organic frameworks and their application as porous liquids[J]. Journal of Materials Chemistry A, 2020, 8: 23455-23462
83	KEARSEY R J, ALSTON BEN M, BRIGGS M E, et al. Accelerated robotic discovery of type II porous liquids[J]. Chemical Science, 2019, 10(41): 9454-9465.
84	JIE K, ONISHI N, SCHOTT J A, et al. Transforming porous organic cages into porous ionic liquids via a supramolecular complexation strategy[J]. Angew. Chem. Int. Ed., 2020, 59(6): 2268-2272.
85	MA L, HAYNES C J E, GROMMET A B, et al. Coordination cages as permanently porous ionic liquids[J]. Nature Chemistry, 2020, 12(3): 270-275.
86	FRAUX G, BOUTIN A, FUCHS A H, et al. On the use of the IAST method for gas separation studies in porous materials with gate-opening behavior[J]. Adsorption, 2018, 24(3): 233-241.
87	EGLESTON B D, LUZYANIN K V, BRAND M C, et al. Controlling gas selectivity in molecular porous liquids by tuning the cage window size[J]. Angew. Chem. Int. Ed., 2020, 59(19): 7362-7366.
88	LIU B, SHEKHAH O, ARSLAN H K, et al. Enantiopure metal-organic framework thin films: oriented SURMOF growth and enantioselective adsorption[J]. Angew. Chem. Int. Ed., 2012, 51(3): 807-810.
1	O’REILLY N, GIRI N, JAMES S L. Porous liquids[J]. Chemistry-A European Journal, 2007, 13(11): 3020-3025.
2	GIRI N, PÓPOLO M G DEL, MELAUGH G, et al. Liquids with permanent porosity[J]. Nature, 2015, 527(7577): 216-220.
89	BAKER R W, LOW B T.Gas separation membrane materials: a perspective[J]. Macromolecules, 2014, 47: 6999-7013.
90	DECHNIK J, GASCON J, DOOANA C J, et al. Mixed-matrix membranes[J]. Angew. Chem. Int. Ed., 2017, 56(32): 9292-9310.
91	SEOANE B, CORONAS J, GASCON I, et al. Metal-organic framework based mixed matrix membranes: a solution for highly efficient CO₂ capture?[J]. Chem. Soc. Rev., 2015, 44(8): 2421-2454.
3	ZHANG J, CHAI S H, QIAO Z A, et al. Porous liquids: a promising class of media for gas separation[J]. Angew. Chem. Int. Ed., 2015, 54(3): 932-936.
4	FERMANDES N J, WALLIN T J, VAIA R A, et al. Nanoscale ionic materials[J]. Chem. Mater., 2014, 26(1): 84-96.
5	RODRIGUEZ R, HERRERA R, ARCHER L A, et al. Nanoscale ionic materials[J]. Adv. Mater., 2008, 20(22): 4353-4358.
6	BOURLINOS A B, HERRERA R, CHALKIAS N, et al. Surface-functionalized nanoparticles with liquid-like behavior[J]. Adv. Mater., 2005, 17(2): 234-237.
7	BOURLINOS A B, RAY CHOWDHURY S, HERRERA R, et al. Functionalized nanostructures with liquid-like behavior: expanding the gallery of available nanostructures[J]. Adv. Funct. Mater., 2005, 15(8): 1285-1290.
92	ADAMS R, CARSON C, WARD J, et al. Metal organic framework mixed matrix membranes for gas separations[J]. Microporous and Mesoporous Materials, 2010, 131(1): 13-20.
8	WARREN S C, BANHOLZER M J, SLAUGHTER L S, et al. Generalized route to metal nanoparticles with liquid behavior[J]. J. Am. Chem. Soc., 2006, 128(37): 12074-12075.
9	BOURLINOS A B, RAMAN K, HERRERA R, et al. A liquid derivative of 12-tungstophosphoric acid with unusually high conductivity[J]. J. Am. Chem. Soc., 2004, 126(47): 15358-15359.
10	BOURLINOS A B, GEORGAKILAS V, TZITZIOS V, et al. Functionalized carbon nanotubes: synthesis of meltable and amphiphilic derivatives[J]. Small, 2006, 2(10): 1188-1191.
11	BOURLINOS A B, STASSINOPOULOS A, ANGLOS D, et al. Functionalized ZnO nanoparticles with liquidlike behavior and their photoluminescence properties[J]. Small, 2006, 2(4): 513-516.
12	生丽莎, 陈振乾. 静电辅助多孔液体的制备及特性研究[J]. 化工学报, 2019, 70(3): 1163-1170.
	SHENG Lisha, CHEN Zhenqian. Preparation and characterization of electrostatic-assisted porous liquid[J]. CIESC Journal, 2019, 70(3): 1163-1170.
13	SHENG L, CHEN Z, WANG Y. Molecular dynamics simulations of stability and fluidity of porous liquids[J]. Appl. Surf. Sci., 2021, 536: 147951.
14	YIN J, ZHANG J, FU W, et al. Theoretical prediction of the SO₂ absorption by hollow silica based porous ionic liquids[J]. J. Mol. Graphics Modell., 2021, 103: 107788.
15	SCHILLING T, MILLER M A, SCHOOT P VAN DER. Percolation in suspensions of hard nanoparticles: from spheres to needles[J]. EPL (Europhysics Letters), 2015, 111(5): 56004.
16	KUMAR R, DHASAIYAN P, NAVEENKUMAR P M, et al. A solvent-free porous liquid comprising hollow nanorod-polymer surfactant conjugates[J]. Nanoscale Advances, 2019, 1(10): 4067-4075.
17	FENG S, LI W, SHI Q, et al. Synthesis of nitrogen-doped hollow carbon nanospheres for CO₂ capture[J]. Chem. Commun., 2014, 50(3): 329-331.
18	LIU J, QIAO S Z, LIU H, et al. Extension of the stöber method to the preparation of monodisperse resorcinol-formaldehyde resin polymer and carbon spheres[J]. Angew. Chem. Int. Ed., 2011, 50(26): 5947-5951.
19	LIU R, MAHURIN S M, LI C, et al. Dopamine as a carbon source: the controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites[J]. Angew. Chem. Int. Ed., 2011, 50(30): 6799-6802.
20	LI P, SCHOTT J A, ZHANG J, et al. Electrostatic-assisted liquefaction of porous carbons[J]. Angew. Chem. Int. Ed., 2017, 56(47): 14958-14962.
21	MOLINER M, MARTÍNEZ C, CORMA A. Multipore zeolites: synthesis and catalytic applications[J]. Angew. Chem. Int. Ed., 2015, 54(12): 3560-3579.
22	BERECIARTUA P J, CANTIN Á, CORMA A, et al. Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene[J]. Science, 2017, 358(6366): 1068-1071.
23	LIU L, DÍAZ U, ARENAL R, et al. Correction: corrigendum: generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D[J]. Nature Materials, 2017, 16(12): 1272.
24	FENG G, CHENG P, YAN W, et al. Accelerated crystallization of zeolites via hydroxyl free radicals[J]. Science, 2016, 351(6278): 1188-1191.
25	WANG N, SUN Q, BAI R, et al. In Situ confinement of ultrasmall Pd clusters within nanosized silicalite-1 zeolite for highly efficient catalysis of hydrogen generation[J]. J. Am. Chem. Soc., 2016, 138(24): 7484-7487.
26	LIU J, WANG N, YU Y, et al. Carbon dots in zeolites: a new class of thermally activated delayed fluorescence materials with ultralong lifetimes[J]. Science Advances, 2017, 3(5): e1603171.
27	SHEN K, QIAN W, WANG N, et al. Centrifugation-free and high yield synthesis of nanosized H-ZSM-5 and its structure-guided aromatization of methanol to 1, 2, 4-trimethylbenzene[J]. Journal of Materials Chemistry A, 2014, 2(46): 19797-19808.
28	CUNDY C S, COX P A. The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time[J]. Chem. Rev., 2003, 103(3): 663-702.
29	LI P, CHEN H, SCHOTT J A, et al. Porous liquid zeolites: hydrogen bonding-stabilized H-ZSM-5 in branched ionic liquids[J]. Nanoscale, 2019, 11(4): 1515-1519.
30	SHAN W, FULVIO P F, KONG L, et al. New class of type Ⅲ porous liquids: a promising platform for rational adjustment of gas sorption behavio[J]. ACS Applied Materials & Interfaces, 2018, 10(1): 32-36.
31	YANG J, LI J, WANG W, et al. Adsorption of CO₂, CH₄, and N₂ on 8-, 10-, and 12-membered ring hydrophobic microporous high-silica zeolites: DDR, silicalite-1, and beta[J]. Industrial & Engineering Chemistry Research, 2013, 52(50): 17856-17864.
32	ZHANG S Y, ZHANG X, LI H, et al. Dual-functionalized metal-organic frameworks constructed from hexatopic ligand for selective CO₂ adsorption[J]. Inorg. Chem., 2015, 54(5): 2310-2314.
33	BANERJEE D, CAIRNS A J, LIU J, et al. Potential of metal-organic frameworks for separation of xenon and krypton[J]. Acc. Chem. Res., 2015, 48(2): 211-219.
34	ZHANG M, CHEN Y P, BOSCH M, et al. Symmetry-guided synthesis of highly porous metal-organic frameworks with fluorite topology[J]. Angew. Chem. Int. Ed., 2014, 53(3): 815-818.
35	ZHAO X, WANG Y, LI D S, et al. Metal-organic frameworks for separation[J]. Adv. Mater., 2018, 30(37): 1705189.
36	LIN R B, XIANG S, XING H, et al. Exploration of porous metal-organic frameworks for gas separation and purification[J]. Coord. Chem. Rev., 2019, 378: 87-103.
37	SHI Z L, ZHANG Y B. Renaissance of the methane adsorbents[J]. Isr. J. Chem., 2018, 58(9/10): 985-994.
38	LI H, WANG K, SUN Y, et al. Recent advances in gas storage and separation using metal-organic frameworks[J]. Mater. Today, 2018, 21(2): 108-121.
39	HASELL T, MIKLITZ M, STEPHENSON A, et al. Porous organic cages for sulfur hexafluoride separation[J]. J. Am. Chem. Soc., 2016, 138(5): 1653-1659.
40	ALEZI D, BELMABKHOUT Y, SUYETIN M, et al. MOF crystal chemistry paving the way to gas storage needs: aluminum-based soc-MOF for CH₄, O₂, and CO₂ storage[J]. J. Am. Chem. Soc., 2015, 137(41): 13308-13318.
41	ABANADES LAZARO I, FORGAN R S. Application of zirconium MOFs in drug delivery and biomedicine[J]. Coord. Chem. Rev., 2019, 380: 230-259.
42	HORCAJADA P, SERRE C, VALLET-REGI M, et al. Metal-organic frameworks as efficient materials for drug delivery[J]. Angew. Chem. Int. Ed., 2006, 45(36): 5974-5978.
43	ZHU B, XIA D, ZOU R. Metal-organic frameworks and their derivatives as bifunctional electrocatalysts[J]. Coord. Chem. Rev., 2018, 376: 430-448.
44	DHAKSHINAMOORTHY A, LI Z, GARCIA H. Catalysis and photocatalysis by metal organic frameworks[J]. Chem. Soc. Rev., 2018, 47(22): 8134-8172.
45	ROGGE S M J, BAVYKINA A, HAJEK J, et al. Metal-organic and covalent organic frameworks as single-site catalysts[J]. Chem. Soc. Rev., 2017, 46(11): 3134-3184.
46	GASCON J, CORMA A, KAPTEIJN F, et al. Metal organic framework catalysis: quo vadis?[J]. ACS Catalysis, 2014, 4(2): 361-378.
47	FANG Y, MA Y, ZHENG M, et al. Metal-organic frameworks for solar energy conversion by photoredox catalysis[J]. Coord. Chem. Rev., 2018, 373: 83-115.
48	BON V. Metal-organic frameworks for energy-related applications[J]. Current Opinion in Green and Sustainable Chemistry, 2017, 4: 44-49.
49	WALLER P J, GÁNDARA F, YAGHI O M. Chemistry of covalent organic frameworks[J]. Acc. Chem. Res., 2015, 48(12): 3053-3063.
50	HAN S S, FURUKAWA H, YAGHI O M, et al. Covalent organic frameworks as exceptional hydrogen storage materials[J]. J. Am. Chem. Soc., 2008, 130(35): 11580-11581.
51	FANG Q, WANG J, GU S, et al. 3D porous crystalline polyimide covalent organic frameworks for drug delivery[J]. J. Am. Chem. Soc., 2015, 137(26): 8352-8355.
52	HUGHES B K, BRAUNECKER W A, BOBELA D C, et al. Covalently bound nitroxyl radicals in an organic framework[J]. The Journal of Physical Chemistry Letters, 2016, 7(18): 3660-3665.
53	FANG Q, GU S, ZHENG J, et al. 3D microporous base-functionalized covalent organic frameworks for size-selective catalysis[J]. Angew. Chem. Int. Ed., 2014, 53(11): 2878-2882.
54	CAHIR J, TSANG M Y, LAI B, et al. Type 3 porous liquids based on non-ionic liquid phases-a broad and tailorable platform of selective, fluid gas sorbents[J]. Chemical Science, 2020, 11(8): 2077-2084.
55	BENNETT T D, TAN J C, YUE Y, et al. Hybrid glasses from strong and fragile metal-organic framework liquids[J]. Nature Communications, 2015, 6(1): 8079.
56	BENNTETT T D, YUE Y, LI P, et al. Melt-quenched glasses of metal-organic frameworks[J]. J. Am. Chem. Soc., 2016, 138(10): 3484-3492.
57	ZHOU C, LONGLEY L, KRAJNC A, et al. Metal-organic framework glasses with permanent accessible porosity[J]. Nat. Commun., 2018, 9(1): 5042.
58	QIAO A, BENNETT T D, TAO H, et al. A metal-organic framework with ultrahigh glass-forming ability[J]. Science Advances, 2018, 4(3): 6827.
59	WIDMER R N, LAMPRONTI G I, ANZELLINI S, et al. Pressure promoted low-temperature melting of metal-organic frameworks[J]. Nature Materials, 2019, 18(4): 370-376.
60	HUANG X C, LIN Y Y, ZHANG J P, et al. Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies[J]. Angew. Chem. Int. Ed., 2006, 45(10): 1557-1559.
61	BANERJEE R, PHAN A, WANG B, et al. High-throughput synthesis of zeolitic imidazolate frameworks and application to CO₂ capture[J]. Science, 2008, 319(5865): 939-943.
62	PARK K S, NI Z, COTE A P, et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks[J]. Proceedings of the National Academy of Sciences, 2006, 103(27): 10186-10191.
63	SINGH S K, SAVOY A W. Ionic liquids synthesis and applications: an overview[J]. J. Mol. Liq., 2020, 297: 112038.
64	WELTON T. Room-temperature ionic liquids. Solvents for synthesis and catalysis[J]. Chem. Rev., 1999, 99(8): 2071-2084.
65	ROGERS R D, SEDDON K R. Ionic liquids—solvents of the future?[J]. Science, 2003, 302(5646): 792-793.
66	FUJIE K, KITAGAWA H. Ionic liquid transported into metal-organic frameworks[J]. Coord. Chem. Rev., 2016, 307: 382-390.
67	LIU S, LIU J, HOU X, et al. Porous liquid: a stable ZIF-8 colloid in ionic liquid with permanent porosity[J]. Langmuir, 2018, 34(12): 3654-3660.
68	COSTA GOMES M, PISON L, ČERVINKA C, et al. Porous ionic liquids or liquid metal-organic frameworks?[J]. Angew. Chem. Int. Ed., 2018, 57(37): 11909-11912.
69	KNEBEL A, BAVYKINA A, DATTA S J, et al. Solution processable metal-organic frameworks for mixed matrix membranes using porous liquids[J]. Nature Materials, 2020, 19: 1346-1353.
70	HE S, CHEN L, CUI J, et al. General way to construct micro-and mesoporous metal-organic framework-based porous liquids[J]. J. Am. Chem. Soc., 2019, 141(50): 19708-19714.
71	HE S, WANG H, ZHANG C, et al. A generalizable method for the construction of MOF@polymer functional composites through surface-initiated atom transfer radical polymerization[J]. Chemical Science, 2019, 10(6): 1816-1822.
72	FÉREY G, MELLOT-DRAZNIEKS C, Serre C, et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science, 2005, 309(5743): 2040-2042.
73	HUGGINS M L. Some properties of solutions of long-chain compounds[J]. The Journal of Physical Chemistry, 1942, 46(1): 151-158.
74	FLORY P J. Thermodynamics of high polymer solutions[J]. The Journal of Chemical Physics, 1942, 10(1): 51-61.
75	ZHAO X, AN S, DAI J, et al. Transforming surface-modified metal organic framework powder into room temperature porous liquids via an electrical balance strategy[J]. New J. Chem., 2020, 44(29): 12715-12722.
76	CARNÉ-SÁNCHEZ A, CRAIG G A, LARPENT P, et al. Self-assembly of metal-organic polyhedra into supramolecular polymers with intrinsic microporosity[J]. Nature Communications, 2018, 9(1): 2506.

[1]	HE Meijin. Application and development trend of molecular management in separation technology in petrochemical field [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 260-266.
[2]	CUI Shoucheng, XU Hongbo, PENG Nan. Simulation analysis of two MOFs materials for O₂/He adsorption separation [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 382-390.
[3]	LI Shilin, HU Jingze, WANG Yilin, WANG Qingji, SHAO Lei. Research progress in separation and extraction of high value components by electrodialysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 420-429.
[4]	GUO Qiang, ZHAO Wenkai, XIAO Yonghou. Numerical simulation of enhancing fluid perturbation to improve separation of dimethyl sulfide/nitrogen via pressure swing adsorption [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 64-72.
[5]	LIAO Zhixin, LUO Tao, WANG Hong, KONG Jiajun, SHEN Haiping, GUAN Cuishi, WANG Cuihong, SHE Yucheng. Application and progress of solvent deasphalting technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4573-4586.
[6]	PAN Yichang, ZHOU Rongfei, XING Weihong. Advanced microporous membranes for efficient separation of same-carbon-number hydrocarbon mixtures: State-of-the-art and challenges [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3926-3942.
[7]	ZHOU Longda, ZHAO Lixin, XU Baorui, ZHANG Shuang, LIU Lin. Advances in electrostatic-cyclonic coupling enhanced multiphase media separation research [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3443-3456.
[8]	CHEN Xiangli, LI Qianqian, ZHANG Tian, LI Biao, LI Kangkang. Research progress on self-healing oil/water separation membranes [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3600-3610.
[9]	LOU Baohui, WU Xianhao, ZHANG Chi, CHEN Zhen, FENG Xiangdong. Advances in nanofluid for CO₂ absorption and separation [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3802-3815.
[10]	ZHOU Lei, SUN Xiaoyan, TAO Shaohui, CHEN Yushi, XIANG Shuguang. Development and application of refinery short-cut column model [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2819-2827.
[11]	WU Heping, CAO Ning, XU Yuanyuan, CAO Yunbo, LI Yudong, YANG Qiang, LU Hao. Rapid separation of hydrofluoric acid and alkylated oil [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2845-2853.
[12]	SONG Minhang, ZHAO Lixin, XU Baorui, LIU Lin, ZHANG Shuang. Research progress of cyclone-enhanced separation based on disperse phase rearrangement at the inlet [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2219-2232.
[13]	ZHAO Yao, ZHOU Zhihui, WU Hongdan, HU Chuanzhi, ZHANG Guochun, WU Ruipeng. Response surface analysis and optimization of membrane permeation vaporization by Silicalite-1 molecular sieve [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2586-2594.
[14]	PANG Nanjiong, WANG Xiaoling, LIAO Xuepin, SHI Bi. Separation of boron isotopes by collagen fibers-immobilized black wattle tannin [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2616-2625.
[15]	LIU Nian, CHEN Kui, WU Bin, JI Lijun, WU Yanyang, HAN Jinling. Preparation of yolk-shell mesoporous magnetic carbon microspheres and its efficient adsorption of erythromycin [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2724-2732.