Advances in the Synthesis and Application of 1,3,4-Thiadiazole Ring-containing Polymers
LI Chao1, MA Chengzhang1, HUANG Shaojun2, MIN Chungang2, HUANG Qiuling2, SUN Xiaodong2
1 School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093; 2 Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093
Abstract: As a new type of functional aromatic heterocyclic polymers, 1,3,4-thiadiazole ring-containing polymers have attracted a great deal of attention in recent years due to their unique energy storage, electrocatalytic activity and electron-rich properties. In the past two decades, the uninterrupted research over 1,3,4-thiadiazole ring-containing polymers has been mainly focused on the electrochemical synthesis and structural characterization of these polymers as well as their applications in cathode materials for rechar-geable lithium batteries, biochemical sensors, clinical diagnosis and pharmacology and other related fields.
Electrochemical synthesis method is favorable to the preparation of self-supporting membrane with controllable thickness and easy modification for electrodes, but nevertheless presents many defects such as electrolyte contamination, high cost and unsuitability for large-scale production. Some researchers have made attempts to synthesize 1,3,4-thiadiazole ring-containing polymers via chemical oxidative polymerization, though merely obtained some complexes or coordination polymers except 2,5-dimercapto-1,3,4-thia-diazole polymers, yet the environmental friendly and large-scale synthesis methodology represent the general trend. There are scanty means available for the structural characterization of 1,3,4-thiadiazole ring-containing polymers because of the solubility limitation, and the main characterization methods are X-ray photoelectron spectroscopy and infrared or Raman spectroscopy. The features of high energy density and high specific capacity have recommended 2,5-dimercapto-1,3,4-thiadiazole polymers to global researchers in seeking for the secondary lithium battery cathode materials, but they also suffer some weaknesses such as slow charge-discharge rate and rapid decline in the capacitance. Besides, the sensors constructed based on 1,3,4-thiadiazole ring-containing polymer modified electrodes have displayed potential for highly sensitive and highly selective detection of a rich variety of bio-related molecules, but the stability of these electrodes needs improvement.
Among all 1,3,4-thiadiazole ring-containing polymers, poly-2-amino-1,3,4-thiadiazole (PAT), poly-5-amino-1,3,4-thiadiazole-2-thiol or poly-5-amino-2-mercapto-1,3,4-thiadiazole (PAMT) and poly-2,5-dimercapto-1,3,4-thiadiazole (PBT) have been synthesized through electrochemical method, while PBT has also been synthesized via a chemical oxidative synthesis method under green conditions, offering a reference for the synthesis of other 1,3,4-thiadiazole ring-containing polymers. Furthermore, our group also has successfully synthesized PAT, PAMT and poly-2-mercapto-1,3,4-thiadiazole (PTT) through chemical oxidative polymerization. So far, with respect to cathode material for secondary lithium ion battery, the PBT with a theoretical specific capacity of up to 362 mAh/g has been the most studied. Researchers have combined PBT with conductive polymers such as polypyrrole, polyaniline or water-soluble sulfonated graphene to further enhance the specific capacity and the stability of the electrode and accelerate the charge-discharge process. Meanwhile impressive strides have been made in fabricating the biochemical sensors based on 1,3,4-thiadiazole ring-containing polymers modified electrodes for the purpose of detection and content measurement of active ingredients in natural pro-ducts, drugs or metabolites in blood and body fluids of human/mammals or in the drug injections, the pesticide residues in Chinese herbal medicine or food, and heavy metal ions in aqueous solutions. Combining 1,3,4-thiadiazole ring-containing polymer with perf-luorosulfonic acid binder and multi-walled carbon nanotubes would facilitate to reduce polymer loss, thus enhancing the stability of the electrode and prolonging the service life.
This review mainly concerns the worldwide research over 1,3,4-thiadiazole ring-containing polymers. It introduces the synthesis, structure characterization and application of 1,3,4-thiadiazole ring-containing polymers, and discusses the problems confronting the 1,3,4-thiadiazole ring-containing polymers and their application prospects. It is expected to provide a reference for the preparation technology and function extension of this species of polymers.
李超, 马成章, 黄绍军, 闵春刚, 黄秋玲, 孙晓东. 含1,3,4-噻二唑环聚合物的合成及应用研究进展[J]. 《材料导报》期刊社, 2018, 32(11): 1891-1902.
LI Chao, MA Chengzhang, HUANG Shaojun, MIN Chungang, HUANG Qiuling, SUN Xiaodong. Advances in the Synthesis and Application of 1,3,4-Thiadiazole Ring-containing Polymers. Materials Reports, 2018, 32(11): 1891-1902.
1 Feng Z Z, Nuli Y N, Yang J. Conductive sulfur-containing material/polyaniline composite for cathode material of rechargeable magne-sium batteries[J].Acta Physico-Chimica Sinica,2007,23(3):327(in Chinese). 冯真真,努丽燕娜,杨军.导电含硫材料/聚苯胺复合物作为镁二次电池的正极材料[J].物理化学学报,2007,23(3):327. 2 Pope J M, Sato T, Shoji E, et al. Organosulfur/conducting polymer composite cathodes Ⅱ. Spectroscopic determination of the protonation and oxidation states of 2,5-dimercapto-1,3,4-thiadiazole[J].Journal of the Electrochemical Society,2002,149(7):A939. 3 Gao J, Lowe M A, Conte S, et al. Poly(2,5-dimercapto-1,3,4-thiadiazole) as a cathode for rechargeable lithium batteries with drama-tically improved performance[J].Chemistry-A European Journal,2012,18(27):8521. 4 Yu L, Wang X H, Li J, et al. Soluble 2,5-dimercapto-1,3,4-thia-diazole/poly(o-toluidine) electroactive composite[J].Journal of the Electrochemical Society,1999,146(5):1712. 5 Kalimuthu P, John S A. Modification of electrodes with nanostructured functionalized thiadiazole polymer film and its application to the determination of ascorbic acid[J].Electrochimica Acta,2009,55(1):183. 6 He J B, Qi F, Wang Y, et al. Solid carbon paste-based amperometric sensor with electropolymerized film of 2-amino-5-mercapto-1,3,4-thiadiazole[J].Sensors and Actuators B-Chemical,2010,145(1):480. 7 Kalimuthu P, John S A. Selective electrochemical sensor for folic acid at physio-logical pH using ultrathin electropolymerized film of functionalized thiadiazole modified glassy carbon electrode[J].Biosensors & Bioelectronics,2009,24(12):3575. 8 Muti M, Gencdag K, Nacak F M, et al. Electrochemical polymerized 5-amino-2-mercapto-1,3,4-thiadiazole modified single use sensors for detection of quercetin[J].Colloids and Surfaces B-Biointerfaces,2013,106:181. 9 Aydogdu G, Gunendi G, Zeybek D K, et al. A novel electrochemical DNA biosensor based on poly-(5-amino-2-mercapto-1,3,4-thia-diazole) modified glassy carbon electrode for the determination of nitrofurantoin[J].Sensors and Actuators B—Chemical,2014,197(3):211. 10 Kalimuthu P, John S A. Simultaneous determination of epinephrine, uric acid and xanthine in the presence of ascorbic acid using an ultrathin polymer film of 5-amino-1,3,4-thiadiazole-2-thiol modified electrode[J].Analytica Chimica Acta,2009,647(1):97. 11 Kalimuthu P, John S A. Electropolymerized film of functionalized thiadiazole on glassy carbon electrode for the simultaneous determination of ascorbic acid, dopamine and uric acid[J].Bioelectrochemistry,2009,77(1):13. 12 Kalimuthu P, John S A. Nanostructured electropolymerized film of 5-amino-2-mercapto-1,3,4-thiadiazole on glassy carbon electrode for the selective determination of L-cysteine[J].Electrochemistry Communications,2009,11(2):367. 13 Tan X, Li C, Feng Y, et al. Electrochemical determination of me-thyl parathion using poly-(2-amino-5-mercapto-1,3,4-thiadiazole) nano-film modified electrode[J].Nanoscience and Nanotechnology Letters,2013,5(7):818. 14 Varghese A, Chitravathi S, Munichandraiah N. Electrocatalytic oxidation and determination of morin at a poly(2,5-dimercapto-1,3,4-thiadiazole) modified carbon fiber paper electrode[J].Journal of the Electrochemical Society,2016,163(8):B471. 15 Zhao C, Liu H, Wang L. Simultaneous determination of Pb(Ⅱ) and Cd(Ⅱ) using an electrode modified with electropolymerized thia-diazole film[J].Analytical Methods,2012,4(11):3586. 16 Lü Q F, Huang M R, Li X G. Synthesis and heavy-metal-ion sorption of pure sulfophenylenediamine copolymer nanoparticles with intrinsic conductivity and stability[J].Chemistry—A European Journal,2007,13(21):6009. 17 Li X G, Lü Q F, Huang M R. Self-stabilized nanoparticles of intrinsically conducting copolymers from 5-sulfonic-2-anisidine[J].Small,2008,4(8):1201. 18 Suen M C, Yeh C W, Jou C H. catena-Poly[(μ-2-amino-1,3,4-thiadiazole-κ2N3∶N4) di-μ-chlorido-cadmium][J].Acta Crystallographica,2011,E67:m1082. 19 El-Shekeil A G, Al-Maydama H M, Al-Shuja’a O M. The synthesis, characterization, and DC electrical conductivity of poly[di(2,5-dimercapto-1,3,4-thiadiazole)-metal] complexes[J].Journal of Applied Polymer Science,2007,106(4):2427. 20 Sun J S, Zhang R F, Wang D Q. catena-Poly[[trimethyltin(IV)]-μ-[5-(2-thienyl- methyleneamino)-1,3,4-thiadiazole-2-thiolato-κ2N4∶S2]][J].Acta Crystallographica,2007,E63:m418. 21 Qin J H, Wang J G, Hu P Z. catena-Poly[[[bis[2,2′-(propane-1,3-diyl-dithio) bis(1,3,4-thiadiazole)-κN4]-copper(Ⅱ)]-bis[μ-2,2′-(propane-1,3-diyl-dithio)bis(1,3,4-thiadiazole)-κ2N4∶N4′]]bis(perchlorate)][J].Acta Crystallographica,2009,E65:m349. 22 Qin J H, Wang J G, Hu P Z. Crystal structure of ethanolatopenta {2,2′-[1,2-propanedithio-bis(1,3,4-thiadiazole)]} dicopper(Ⅱ) tetrakisperchlorate,[Cu2(C2H5OH)(C7H8N4S4)5][ClO4]4[J].Zeitschrift für Kristallographie—New Crystal Structures,2010,225(2):339. 23 Tiwari M, Gupta S, Prakash R. One pot synthesis of coordination polymer 2,5-dimercapto-1,3,4-thiadiazole-gold and its application in voltammetric sensing of resorcinol[J].RSC Advances,2014,4(49):25675. 24 Shouji E, Oyama N. Examination of the cleavage and formation of the disulfide bond in poly[dithio-2,5-(1,3,4-thiadiazole) by redox reaction[J].Journal of Electroanalytical Chemistry,1996,410(2):229. 25 Jin L, Wang G, Li X, et al. Poly(2,5-dimercapto-1,3,4-thia-diazole)/sulfonated graphene composite as cathode material for rechargeable lithium batteries[J].Journal of Applied Electrochemistry,2011,41(4):377. 26 He X, Su Z, Xie Q, et al. Differential pulse anodic stripping voltammetric determination of Cd and Pb at a bismuth glassy carbon electrode modified with Nafion, poly(2,5-dimercapto-1,3,4-thiadiazole) and multiwalled carbon nanotubes[J].Microchimica Acta,2011,173(1-2):95. 27 黄绍军,马成章,李超,等.一种聚2-巯基-1,3,4-噻二唑纳米颗粒及其合成方法和用途:中国,201710067737.9[P].2017. 28 黄绍军,李超,马成章,等.聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法:中国,201611071101.3[P].2016. 29 黄绍军,马成章,杜萍,等.化学氧化聚合制备聚2-氨基-1,3,4-噻二唑纳米纤维的方法:中国,201610258933.X[P].2016. 30 Xu J, Hou J, Zhang S, et al. Electrochemical polymerization of fluoranthene and characterization of its polymers[J].Journal of Phy-sical Chemistry B,2006,110(6):2643. 31 Dias J R. Electronic and structural properties of biazulene, terazulene, and polyazulene isomers[J].Journal of Physical Organic Chemistry,2007,20(6):395. 32 Liu M L, Visco S J, De Jonghe L C. Novel solid redox polymerization electrodes—All-solid-state, thin-film, rechargeable lithium batteries[J].Journal of the Electrochemical Society,1991,138(7):1891. 33 Liu M L, Visco S J, De Jonghe L C. Novel solid redox polymerization electrodes—Electrochemical properties[J].Journal of the Electrochemical Society,1991,138(7):1896. 34 Kiya Y, Iwata A, Sarukawa T, et al. Poly[dithio-2,5-(1,3,4-thia-diazole)] (PDMcT)-poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for high-energy lithium/lithium-ion rechargeable batteries[J].Journal of Power Sources,2007,173(1):522. 35 Dalmolin C, Biaggio S R, Rocha-Filho R C, et al. Reticulated vit-reous carbon/polypyrrole composites as electrodes for lithium batte-ries: Preparation, electrochemical characterization and charge-discharge performance[J].Synthetic Metals,2010,160(1-2):173. 36 Davoglio R A, Biaggio S R, Rocha-Filho R C, et al. Bilayered nanofilm of polypyrrole and poly(DMcT) for high-performance battery cathodes[J].Journal of Power Sources,2010,195(9):2924. 37 Oyama N, Tatsuma T, Sato T, et al. Dimercaptan-polyaniline composite electrodes for lithium batteries with high energy density[J].Nature,1995,373:598. 38 Tatsuma T, Matsui H, Shouji E, et al. Reversible electron transfer reaction between polyaniline and thiol/disulfide couples[J].Journal of Physical Chemistry,1996,100(33):14016. 39 Cosnier S, Holzinger M. Electrosynthesized polymers for biosensing[J].Chemical Society Reviews,2011,40(5):2146. 40 Chitravathi S, Swamy B E K, Mamatha G P, et al. Electrochemical behavior of poly (naphthol green B)-film modified carbon paste electrode and its application for the determination of dopamine and uric acid[J].Journal of Electroanalytical Chemistry,2012,667(1):66. 41 Shankar S S, Swamy B E K, Chandrashekar B N, et al. Sodium do-decyl benzene sulfate modified carbon paste electrode as an electrochemical sensor for the simultaneous analysis of dopamine, ascorbic acid and uric acid: A voltammetric study[J].Journal of Molecular Liquids,2012,177(8):32. 42 Mahanthesha K R, Swamy B E K, Chandra U, et al. Sodium dodecyl sulphate/polyglycine/phthalamide/carbon paste electrode based voltammetric sensors for detection of dopamine in the presence of ascorbic acid and uric acid[J].Chemical Sensors,2014,4(10):1. 43 Revin S B, John S A. Electropolymerization of 3-amino-5-mercapto-1,2,4-triazole on glassy carbon electrode and its electrocatalytic activity towards uric acid[J].Electrochimica Acta,2011,56(24):8934. 44 Xue Y, Sheng Z, Zhao H, et al. Electrochemical synthesis and cha-racterization of a novel thiazole-based copolymer and its application in biosensor[J].Electrochimica Acta,2012,59(4):256. 45 Zhang L, Wang L. Poly(2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole) film modified electrode for the simultaneous determinations of dopamine, uric acid and nitrite[J].Journal of Solid State Electrochemistry,2013,17(3):691. 46 Li X G, Ma X L, Huang M R. Biosensors based on polyphenylene-diamine loaded with noble metal nanoparticles[J].Chinese Journal of Analytical Chemistry,2008,36(2):253(in Chinese). 李新贵,马小立,黄美荣.基于担载贵金属纳米粒子聚苯二胺的生物传感器[J].分析化学,2008,36(2):253. 47 Huang M R, Ding Y B, Li X G, et al. Synthesis of semiconducting polymer microparticles as solid ionophore with abundant complexing sites for long-life Pb(II) sensors[J].ACS Applied Materials & Interfaces,2014,6(24):22096. 48 Li X G, Ma X L, Huang M R. The application of poly(o-phenylenediamine) in sensors[J].Chemical Sensors,2008,28(1):15(in Chinese). 李新贵,马小立,黄美荣.聚邻苯二胺在传感器中的应用[J].化学传感器,2008,28(1):15. 49 Patil P S, Haram N S, Pal R R, et al. Synthesis, spectroscopy, and electrochemical investigation of new conjugated polymers containing thiophene and 1,3,4-thiadiazole in the main chain[J].Journal of Applied Polymer Science,2012,125(3):1882. 50 Chang K, Liu Z, Chen H, et al. Conjugated polymer dots for ultra-stable full-color fluorescence patterning[J].Small,2014,10(21):4270. 51 Dias N L, Caetano L, do Carmo D R, et al. Preparation of a silica gel modified with 2-amino-1,3,4-thiadiazole for adsorption of metal ions and electroanalytical application[J].Journal of the Brazilian Chemical Society,2006,17(3):473. 52 Tzvetkova P, Vassileva P, Nickolov R. Modified silica gel with 5-amino-1,3,4-thiadiazole-2-thiol for heavy metal ions removal[J].Journal of Porous Materials,2010,17(4):459. 53 Olkhovyk O, Jaroniec M. Ordered mesoporous silicas with 2,5-di-mercapto-1,3,4- thiadiazole ligand: High capacity adsorbents for mercury ions[J].Adsorption,2005,11:205.
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2018, Vol. 32 
