Progress in Polymer Science最新文献

{"title":"Thermodynamic and kinetic understanding for managing the controllability of interfacial polymerization","authors":"Chang Liu ,&nbsp;Cheng-Ye Zhu ,&nbsp;Chao Zhang ,&nbsp;Hao-Cheng Yang ,&nbsp;Zhi-Kang Xu","doi":"10.1016/j.progpolymsci.2024.101815","DOIUrl":"https://doi.org/10.1016/j.progpolymsci.2024.101815","url":null,"abstract":"<div><p>Interfacial polymerization serves as a revolutionary technique to create polymer membranes such as polyamides, polyesters, and covalent organic frameworks, holding exceptional promise in numerous scenarios from liquid and gas separation to energy conversion and harvesting. Despite significant achievements, the fundamental principles of interfacial polymerization have been rarely discussed systemically, particularly from the perspective of thermodynamics, kinetics, and their combinations. This knowledge gap results in the lack of rational design and tailoring of interfacial polymerization. This review aims to revisit interfacial polymerization, integrating thermodynamics and kinetics to bridge the remained knowledge gap. We dissect the process into distinct physicochemical stages, including monomer dissolution, molecular diffusion, chemical reactions, and phase separation. Each stage is examined using thermodynamic and kinetic theories, underlining recent strides in refining process control. Furthermore, the review confronts the unresolved theoretical aspects of interfacial polymerization and the challenges inherent in mastering its controllability. We conclude by offering insights into how a controlled approach to interfacial polymerization could substantially transform the landscape of state-of-the-art polymer membranes.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"152 ","pages":"Article 101815"},"PeriodicalIF":27.1,"publicationDate":"2024-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140535756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sustainability of self-healing polymers: A holistic perspective towards circularity in polymer networks","authors":"Kenneth Cerdan ,&nbsp;Marlies Thys ,&nbsp;Aleix Costa Cornellà ,&nbsp;Fatma Demir ,&nbsp;Sophie Norvez ,&nbsp;Richard Vendamme ,&nbsp;Niko Van den Brande ,&nbsp;Peter Van Puyvelde ,&nbsp;Joost Brancart","doi":"10.1016/j.progpolymsci.2024.101816","DOIUrl":"https://doi.org/10.1016/j.progpolymsci.2024.101816","url":null,"abstract":"<div><p>Permanent polymer networks present an important sustainability challenge. Irreversible covalent crosslinks impart these materials excellent mechanical properties, thermal and chemical resistance, yet also render them difficult to repair and to recycle. Self-healing mechanisms can extend the lifetime of thermosets and elastomers, improving their durability and making their lifecycle more sustainable. In addition to the lifetime extension, this paper reviews the sustainability of self-healing polymers from a holistic point of view. The entire lifecycle of self-healing polymers is critically assessed with reference to the green chemistry principles and sustainable development. The relation between the self-healing chemistries and the sustainability aspects of each of the phases of the lifecycle are discussed, starting from the feedstocks, monomer functionalisation and polymer synthesis, to processing and manufacturing as well as end-of-life considerations, <em>i.e.</em> recycling or (bio)degradation. The review provides a toolbox for the development of more sustainable thermosets, elastomers and their composites. It is of utmost importance to consider the entire lifecycle of self-healing materials, derived products and – by extension – any material or product. The self-healing ability and often related recyclability should primarily reduce the amount of new materials that are necessary to fulfill societal needs, by extending the lifetime of products and maximizing reprocessing into new products. Increasing healing efficiency and the number of healing cycles improves the overall environmental impact relative to the extended service lifetime. Renewable resources derived from biomass, recycling processes or waste streams should be the first choice to create new self-healing polymers. Finally, biodegradability can be considered as a complementary end-of-life scenario upon accidental loss of self-healing polymer to the environment, provided that the biodegradation does not start under the prospected use conditions of the self-healing polymers and products, but can be postponed until contact with stimuli present in the environment.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"152 ","pages":"Article 101816"},"PeriodicalIF":27.1,"publicationDate":"2024-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0079670024000339/pdfft?md5=12e01ae1603b967556f936ccb6dc9ec8&pid=1-s2.0-S0079670024000339-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140352000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent developments in indacenodithiophene and indacenodithienothiophene-based donor-acceptor conjugated polymers: From design to device performance in organic electronics","authors":"Wissem Khelifi,&nbsp;Christine K. Luscombe","doi":"10.1016/j.progpolymsci.2024.101804","DOIUrl":"10.1016/j.progpolymsci.2024.101804","url":null,"abstract":"<div><p>Polymeric semiconductors based on donor-acceptor (D-A) conjugated polymers have emerged as a promising class of materials for various applications due to their excellent solution processability, low cost, and intrinsic flexibility. The use of the indacenodithiophene (IDT) unit as a building block has received significant attention due to its unique pentacyclic ring structure and exceptional photophysical and electronic properties. This review focuses on the latest progress in the field of IDT-based polymers. We discuss the versatility of IDT as a structural molecular engineering tool, along with the use of various electron-deficient acceptors as comonomers and modifications to the IDT structure unit. These advancements have led to improved device performance, particularly in organic electronics applications such as photodetectors, solar cells, field-effect transistors, and thermoelectric devices. In summary, this review serves as a valuable reference for researchers who are interested in creating high-performance polymeric semiconductors using the IDT building block for a range of optoelectronic devices.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"151 ","pages":"Article 101804"},"PeriodicalIF":27.1,"publicationDate":"2024-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0079670024000212/pdfft?md5=076ed1946fdd1b155301e4543590baca&pid=1-s2.0-S0079670024000212-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140000842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sustainable polyurethanes: toward new cutting-edge opportunities","authors":"Aliénor Delavarde ,&nbsp;Gaelle Savin ,&nbsp;Paul Derkenne ,&nbsp;Marine Boursier ,&nbsp;Roberto Morales-Cerrada ,&nbsp;Benjamin Nottelet ,&nbsp;Julien Pinaud ,&nbsp;Sylvain Caillol","doi":"10.1016/j.progpolymsci.2024.101805","DOIUrl":"10.1016/j.progpolymsci.2024.101805","url":null,"abstract":"<div><p>Polyurethanes (PU) are ranked amongst the 6^th most manufactured worldwide polymers and are widely used in a variety of applications due to the diversity of properties they offer. Nevertheless, PUs are raising questions around environmental, legislative, health, and recycling concerns. In this context, due to the high isocyanate toxicity, blocked isocyanates, waterborne PU systems, and non-isocyanate polyurethane (NIPU) were introduced to prevent isocyanate handling risks. Moreover, sustainable feedstocks stood out to synthetize greener PU. In particular, bio-based polyfunctional short alcohol and isocyanate compounds have emerged to design fully bio-based PU materials with targeted chemical and mechanical properties. Finally, the large amounts of PU that have been placed on the market are now leading to environmental issues regarding its accumulation in the environment. Several methods have thus been recently developed to facilitate their end-of-life management and recyclability.</p><p>This review provides a complete overview on the most recent advances on PUs synthesis with focus on the replacement of toxic isocyanates and petroleum-based resources, the use of greener processes, and their recycling methods. After a quick summary on PUs history and worldwide situation, different bio-based alcohols and isocyanates introduced on academic and industrial sides, and the corresponding PU are outlined. Furthermore, different synthesis pathways to produce NIPUs are discussed. Finally, the enzymatic and chemical recycling of PUs are outlined.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"151 ","pages":"Article 101805"},"PeriodicalIF":27.1,"publicationDate":"2024-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0079670024000224/pdfft?md5=9811ca39bbf90c57c1e7427b45cd25d4&pid=1-s2.0-S0079670024000224-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139937508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural engineering of polyurethanes for biomedical applications","authors":"Haoran Wang,&nbsp;Tong Li,&nbsp;Jia Li,&nbsp;Ruohong Zhao,&nbsp;Ao Ding,&nbsp;Fu-Jian Xu","doi":"10.1016/j.progpolymsci.2024.101803","DOIUrl":"10.1016/j.progpolymsci.2024.101803","url":null,"abstract":"<div><p>Polyurethane, a synthetic polymer distinguished by its urethane (carbamate, -NHCOO-) and/or urea (-NHCONH-) linkages, has been applied in various industries since its discovery in 1937 by Bayer and colleagues. The successful <em>in vivo</em> use of segmented multiblock thermoplastic polyurethane in 1967 marked the beginning of its development for biomedical applications. Over the past few decades, research on polyurethane biomaterials has evolved from focusing on biostable to biodegradable forms, exploring multifunctionality and application in areas like functional medical devices, tissue engineering scaffolds, drug delivery systems, etc.</p><p>This review aims to summarize the recent advancements in engineering polyurethane structures for biomedical applications, presenting the main methods utilized in their preparation, biological functions, and their main biomedical applications. In addition, we proposed four general strategies for engineering polyurethane structures in the biomedical field, offering a structured methodology for researchers and engineers engaged in polyurethane biomaterials work. Concluding the review, we spotlight future development directions, emphasizing multifunctional programmable polyurethane, peptide-mimicking polyurethane, and poly (hydroxyl urethane).</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"151 ","pages":"Article 101803"},"PeriodicalIF":27.1,"publicationDate":"2024-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139875942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chiral macromolecules and supramolecular assemblies: Synthesis, properties and applications","authors":"Mingyue Zhang ,&nbsp;Minju Kim ,&nbsp;Woosung Choi ,&nbsp;Jinyoung Choi ,&nbsp;Dong Ha Kim ,&nbsp;Yijiang Liu ,&nbsp;Zhiqun Lin","doi":"10.1016/j.progpolymsci.2024.101800","DOIUrl":"10.1016/j.progpolymsci.2024.101800","url":null,"abstract":"<div><p>Chirality, an inherent characteristic observed throughout nature, plays a pivotal role across a wide range of scales, from subatomic to galactic, and holds significance in myriad scientific fields, including chemistry, biology, and nanotechnology. Since the discovery of molecular chirality in 1848, there have been monumental advances, especially in the realm of chiral macromolecules and chiral supramolecular assemblies. This progress, primarily propelled by innovations in polymer science and supramolecular chemistry, has opened up numerous applications, spanning enantioselective sensing, catalysis, optics, and biomedicine. Both chiral macromolecules, synthesized either from chiral or achiral components, and chiral supramolecular assemblies, often manifest enhanced chiroptical responses and other intriguing chiral-related characteristics. However, challenges remain, particularly in precisely characterizing and understanding the governing factors and dynamics of these complex systems, as well as in synthesizing novel chiral macromolecules and chiral supramolecular assemblies that can efficiently interact with circularly polarized light. This review offers a comprehensive overview of the most recent advances in the synthesis, properties, characterization, and applications of chiral macromolecules and chiral supramolecular assemblies. In addition, it provides an insightful perspective on the current challenges and the future direction of research in this rapidly evolving field.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"151 ","pages":"Article 101800"},"PeriodicalIF":27.1,"publicationDate":"2024-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139891315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifunctional naturally derived bioadhesives: From strategic molecular design toward advanced biomedical applications","authors":"Mahshid Kharaziha ,&nbsp;Thomas Scheibel ,&nbsp;Sahar Salehi","doi":"10.1016/j.progpolymsci.2024.101792","DOIUrl":"10.1016/j.progpolymsci.2024.101792","url":null,"abstract":"<div><p>In the last decades, adhesives derived from natural resources (i.e., bioadhesives) have emerged as promising alternative to the standard wound closure devices, including sutures, clips, and strips, owing to relatively easy and rapid application, minimal tissue damage, fast hemostasis, and ability to decrease the risk of infection. Various synthetic and natural materials have been utilized as bioadhesives. These materials find extensive applications in various biomedical fields, ranging from simple wound sealing to controlled drug delivery, tissue regeneration, and noninvasive therapy. Considering the weak underwater adhesion, degradability, and biological performances of synthetic adhesives, naturally derived-based adhesives are more attractive. The first generation of these bioadhesives provided primarily only one function. Moreover, they had issues including long curing time, slow adhesion, high degradation rate, low mechanical properties, and the risk of transferring contamination to the wound. Various chemically and genetically engineered strategies have been applied to advance their multifunctionality. The synergy of bonding chemistry, topography, and mechanics of dissipation in their structure supports the improved adhesion and controlled degradation rate. Various naturally derived bioadhesives are developed that cover subjects from innovative biomaterial synthesis or functionalization and cutting-edge manufacturing processes. However, to fulfill all the criteria of an ideal bioadhesive for clinical applications, more efforts should be devoted to investigating the surface characteristics of target tissues and the long-term relationship between the physiochemical properties of natural polymers and cohesion and adhesion mechanisms, as well as adhesive functionality. This review outlines the recent progress on naturally-derived bioadhesives, including proteins and polysaccharides, focusing on designing approaches based on chemically and genetically engineering strategies, development, and applications. Furthermore, the challenges of current studies are summarized to show future perspectives for developing bioengineered and high-performance naturally-derived bioadhesives for clinical use.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"150 ","pages":"Article 101792"},"PeriodicalIF":27.1,"publicationDate":"2024-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0079670024000091/pdfft?md5=a4d05abdf25efab9a2679f8e716a6bf3&pid=1-s2.0-S0079670024000091-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139568130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rigorous recognition mode analysis of molecularly imprinted polymers—Rational design, challenges, and opportunities","authors":"Yanxia Liu ,&nbsp;Lulu Wang ,&nbsp;Haitao Li ,&nbsp;Lin Zhao ,&nbsp;Yanfu Ma ,&nbsp;Yagang Zhang ,&nbsp;Jian Liu ,&nbsp;Yen Wei","doi":"10.1016/j.progpolymsci.2024.101790","DOIUrl":"10.1016/j.progpolymsci.2024.101790","url":null,"abstract":"<div><p>Supramolecular chemistry<span><span> now presents an elaborate „enabling tool“ that offers exciting opportunities for novel functional material<span> design. One of the areas to benefit from recent advances in supramolecular chemistry is the field of molecularly imprinted polymers (MIPs), also known as “synthetic antibodies”. It uses the memory of template molecules to form tailor-made binding sites in the </span></span>polymer matrix<span><span>. This review provides insights from rigorous recognition mode analysis perspectives and highlights evolving approaches in MIPs. First, the principles and recognition mode of molecular imprinting technology are carefully reviewed. The similarities and major differences between MIPs and enzymes are discussed. The internal 3D structure model of MIP is depicted, the origin and consequences of binding site heterogeneity are highlighted, and methods for the optimization of the recognition degree and imprinting efficiency are summarized. The criteria for evaluating imprinting efficacy and the role of chiral recognition in molecular imprinting are discussed. Subsequently, important approaches for the design and synthesis of MIPs a reviewed. Relevant approaches include dye displacement strategy for MIP sensors, multi-functional group recognition, monomolecular imprinting using dendrimers, solvent programmable polymer (SPP) based on </span>restricted rotation, template activated molecular imprinting strategy, molecular imprinting with click chemistry, and evolution of molecular imprinting with computational strategies. Finally, the exciting progress of MIPs for recognition of biomacromolecules such as proteins, bacteria and viruses are discussed. The goal of this review is thus to inspire new applications of MIP materials and to provide a guide for how these applications might become a reality.</span></span></p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"150 ","pages":"Article 101790"},"PeriodicalIF":27.1,"publicationDate":"2024-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139505125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrogels for bioinspired soft robots","authors":"Chang Seo Park ,&nbsp;Yong-Woo Kang ,&nbsp;Hyeonuk Na ,&nbsp;Jeong-Yun Sun","doi":"10.1016/j.progpolymsci.2024.101791","DOIUrl":"10.1016/j.progpolymsci.2024.101791","url":null,"abstract":"<div><p>Amid the ever-advancing landscape of industrial robotics, soft robots in particular have attracted substantial attention due to their remarkable structural adaptability and high efficiency and stability in dynamic environments. Living organisms are, in essence, natural soft robots, composed of diverse and efficient soft organs, each precisely performing assigned functions as a result of a long-term evolution. Fundamental components of organisms, such as material, designs, and working mechanisms, have been a paradigmatic model for the development of soft robots. Recently, these researches have been boosted with the advancement in hydrogel, a synthetic material that closely resembles the constituents of living organisms. The distinctive features of hydrogel - softness, stimuli-responsiveness, biocompatibility, ionicity, and transparency - have enabled the reproduction of nature-inspired strategies, significantly contributing to the progress in soft robots. In this review, we discuss how these properties have been exploited in various applications in soft robots to emulate blueprints found in nature. Moreover, we provide insightful perspectives on overcoming obstacles and research directions, offering a glimpse into future of soft robots.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"150 ","pages":"Article 101791"},"PeriodicalIF":27.1,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139504737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Conjugated microporous polymers for advanced chemical sensing applications","authors":"Weisi He,&nbsp;Ju Duan,&nbsp;He Liu,&nbsp;Cheng Qian,&nbsp;Meifang Zhu,&nbsp;Weiyi Zhang,&nbsp;Yaozu Liao","doi":"10.1016/j.progpolymsci.2023.101770","DOIUrl":"10.1016/j.progpolymsci.2023.101770","url":null,"abstract":"<div><p><span>Exploring advanced chemical sensing applications using porous materials is of critical importance for emerging industries such as Internet of Things, carbon neutrality, new energy resources, </span><em>etc.</em><span><span><span> Conjugated microporous polymers (CMPs), being well-renowned for their extended π-π conjugations, tunable </span>pore structures<span>, tailored chemical components, and high surface areas, have attracted increasing interests for chemical sensing applications. Here, recent milestones in the sensing applications of CMPs are presented, with an emphasis on the synthetic routes, structural requirements or parameters that dominate their sensing properties and functionalities. This review focuses on multiple chemical sensing devices including: i) fluorescent sensors, ii) electrochemical sensors, iii) colorimetric sensors, iv) resistive sensors, and v) versatile sensors. The key application areas of these CMPs-based sensors for detecting multiple matters including industrial exhausts, explosives, </span></span>metal cations, halogen species, micropollutants, organic hazards, biological matters, and multiple. species, </span><em>etc.</em>, are highlighted. The in-depth understanding of the sensing mechanisms and structure-property-function relationships of CMPs are also provided. Finally, a perspective on the future research directions and challenges of CMPs-based sensors is presented.</p></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"148 ","pages":"Article 101770"},"PeriodicalIF":27.1,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138635620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}