Journal of Membrane Science Letters最新文献

{"title":"Revisiting experimental techniques and theoretical models for estimating the solubility parameter of rubbery and glassy polymer membranes","authors":"Matthew T. Webb ,&nbsp;Lucas C. Condes ,&nbsp;William J. Box ,&nbsp;Harold G. Ly ,&nbsp;Sepideh Razavi ,&nbsp;Michele Galizia","doi":"10.1016/j.memlet.2023.100060","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100060","url":null,"abstract":"<div><p>Estimation and correlation of the Hildebrand solubility parameter (<span><math><mi>δ</mi></math></span>) of polymers and small molecules is a common practice in membrane material science and is accomplished by experimental and numerical routes. In this paper, we revisit, update, and compare both routes to enhance the accuracy in the determination of <span><math><mi>δ</mi></math></span>. Best practices for the experimental determination of polymer solubility parameters are provided, and the viability of Dynamic Light Scattering (DLS) was demonstrated as an alternative to conventional time- and material-consuming techniques, such as Ubbelohde viscometry and swelling measurements. Glassy and rubbery polymers, including high fractional free volume (FFV) microporous polymers such as PIM-1 and poly(1-trimethylsilyl-1-propyne) (PTMSP), are among the samples included in this study with great relevance to membrane science. In an attempt to enhance the accuracy of numerical estimate of polymer solubility parameters via the group contribution method, we provide updated group contribution parameters, along with their uncertainty, according to the technique recently reported by Smith et al. These updated group contribution parameters result in a mean absolute relative error of 9.0% in predicting the solubility parameter on a test set of 40 polymers, which is on par with the average 10% error reported previously. We also show, using machine learning techniques, that augmenting the group contribution model with extra parameters or non-linear relationships does not improve its accuracy. Results of the updated group contribution technique and dynamic light scattering measurements were compared to experimental viscometry on four test polymers, and the difference between the three techniques is compared.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100060"},"PeriodicalIF":0.0,"publicationDate":"2023-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49717346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Positively charged thin-film composite hollow fiber nanofiltration membrane via interfacial polymerization and branch polyethyleneimine modification for Mg2+/Li+ separation","authors":"Enlin Wang ,&nbsp;Shaoxiao Liu ,&nbsp;Liyang Liu ,&nbsp;Lihui Han ,&nbsp;Baowei Su","doi":"10.1016/j.memlet.2023.100061","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100061","url":null,"abstract":"<div><p>It is a vital technical challenge to extract lithium from salt-lake brine which has very high Mg²⁺ / Li⁺ mass ratio via green and low-cost methods, as these two cations have quite similar ionic hydration radius. Positively charged nanofiltration membranes can separate Li⁺ and Mg²⁺ through Donnan exclusion. In this work, a kind of hollow fiber nanofiltration membrane with positively charged skin layer was successfully fabricated via interfacial polymerization followed by a surface modification with branched polyethyleneimine (BPEI). The resultant membrane has a large number of amine groups, and thus shows positively charged surface with high rejection for divalent cation ions via Donnan exclusion. This gives it very high selectivity for the separation of Li⁺ ions from salt-lake brine. Under optimized conditions, it achieves a water permeance of up to 126.2 L m^-2 h^-1 MPa⁻¹ at a transmembrane pressure difference of 4 bar, and a MgCl₂ rejection of 94.6% with 2000 mg L^-1 aqueous MgCl₂ solution as feed. Meanwhile, it achieves a Mg²⁺ / Li⁺ selectivity of nearly 24 for MgCl₂ and LiCl salt mixture solution with an overall concentration of 2000 mg L^-1 and a Mg²⁺ / Li⁺ mass ratio of 150 : 1 as feed, which is high as compared with most of the literature, demonstrating its potential in the practical application of Mg²⁺ and Li⁺ separation.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100061"},"PeriodicalIF":0.0,"publicationDate":"2023-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49717343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lithium recovery from brines by lithium membrane flow capacitive deionization (Li-MFCDI) – A proof of concept","authors":"H.M. Saif,&nbsp;J.G. Crespo,&nbsp;S. Pawlowski","doi":"10.1016/j.memlet.2023.100059","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100059","url":null,"abstract":"<div><p>The demand of lithium for electric vehicles and energy storage devices is increasing rapidly, thus new sources of lithium (such as seawater and natural or industrial brines), as well as sustainable methods for its recovery, will need to be explored/developed soon. This work presents a novel electromembrane process, called Lithium Membrane Flow Capacitive Deionization (Li-MFCDI), which was tested to recover lithium from a synthetic geothermal brine containing a much higher mass concentration of sodium than lithium (more than 650 times). Specifically, a ceramic lithium-selective membrane was integrated into a flow capacitive deionization (FCDI) cell, which was specifically designed, and 3D printed, to allow simultaneous charging and regeneration of the employed flow electrodes. Despite the extremely high Na⁺/Li⁺ mass ratio in the feed stream, 99.98% of the sodium was rejected and the process selectivity for lithium over other monovalent cations was 141 ± 5.85 for Li⁺/Na⁺ and 46 ± 1.46 for Li⁺/K⁺. The Li-MFCDI process exhibited a stable behaviour over a 7-day test period, and the estimated energy consumption was 16.70 ± 1.63 kWh/kg of Li⁺ recovered in the draw solution. These results demonstrate promising potential of the Li-MFCDI for the sustainable lithium recovery from saline streams.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100059"},"PeriodicalIF":0.0,"publicationDate":"2023-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49717178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Green chemistry-based fabrication of hollow fiber and flat sheet polyimide membranes for CO2/CH4 separation","authors":"George V. Theodorakopoulos,&nbsp;Dionysios S. Karousos,&nbsp;Charitomeni M. Veziri,&nbsp;Evangelos P. Kouvelos,&nbsp;Andreas A. Sapalidis,&nbsp;Evangelos P. Favvas","doi":"10.1016/j.memlet.2023.100057","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100057","url":null,"abstract":"<div><p>In this work, the successful fabrication of polymeric hollow fiber (HF) and flat sheet (FS) membranes was examined by employing γ-butyrolactone (GBL)-a green and environmentally friendly solvent- for the polymer's dissolution following the principles of green chemistry and sustainability regarding the membrane preparation. In addition, the ternary phase diagram of the P84/GBL/water was constructed and the viscosity of dope solution was measured for different concentrations and temperatures. Their morphological characteristics of the prepared polyimide membranes were investigated through SEM analysis. CO₂/CH₄ separation measurements under continuous flow were performed to evaluate the efficiency of the membranes for a binary 10/90 vol.% CO₂/CH₄ gas mixture. The developed green HF and FS membranes exhibited comparable, and in some cases even superior, performance compared to membranes prepared using the conventional and highly toxic NMP solvent, making them highly promising candidates for CO₂/CH₄ separation, with a real mixture separation factor of ∼58.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100057"},"PeriodicalIF":0.0,"publicationDate":"2023-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49735003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scalable synthesis of ultrathin MoS2 membranes for dye desalination","authors":"Rodrigo Schneider ,&nbsp;Ameya Manoj Tandel ,&nbsp;Erda Deng ,&nbsp;Daniel S. Correa ,&nbsp;Haiqing Lin","doi":"10.1016/j.memlet.2023.100058","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100058","url":null,"abstract":"<div><p>Molybdenum disulfide (MoS₂) has been fabricated into thin-film composite (TFC) membranes for dye desalination due to its excellent underwater stability and tunable interlay spacing. However, it remains challenging to synthesize thin layers of MoS₂ with high water permeance and high dye rejection due to the difficulty in fabricating large crystalline sheets or exfoliation. Herein, we report a scalable method coupling bottom-up hydrothermal synthesis and top-down ultrasonic exfoliation to obtain well-dispersed MoS₂ nanosheets and a vacuum filtration method to prepare ultrathin membranes (thickness: 30 – 60 nm) for dye desalination. The MoS₂ nanosheets and membranes are thoroughly characterized for their chemistries and nanostructures. The membrane with 60-nm MoS₂ exhibits water permeance of 32 LMH/bar, Na₂SO₄ rejection of 2.3%, and Direct Red-80 rejection of 99.0%. The MoS₂ membranes exhibit dye desalination performance superior to state-of-the-art commercial polyamide membranes and many leading membranes based on two-dimensional materials.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100058"},"PeriodicalIF":0.0,"publicationDate":"2023-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49735002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-situ rapid construction of aliphatic amine combined polyamide seawater reverse osmosis membrane for efficient boron removal","authors":"Can Li ,&nbsp;Gwo Sung Lai ,&nbsp;Yali Zhao ,&nbsp;Rong Wang","doi":"10.1016/j.memlet.2023.100056","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100056","url":null,"abstract":"<div><p>Polyamide (PA) reverse osmosis membranes are commonly employed in seawater desalination owing to their effective salt rejection and water permeability; however, the elimination of small and neutral boron molecules from seawater remains a significant hurdle in energy-efficient and cost-effective desalination processes. In this work, a seawater reverse osmosis (SWRO) membrane with powerful boron removal competence was designed by adopting an <em>in-situ</em> rapid integration protocol, which utilized aliphatic amines as hydrophobic barriers by bonding the residual chloride groups upon the membrane surface and as molecular plugs by embedding in the PA networks. Consequently, it resulted in a notable improvement in the rejection of neutral boron molecules due to enhanced steric hindrance caused by immobilized amine plugs and synergistically tunned hydrophobic interactions. The permeability coefficient of boron decreased from 4.8 to 0.9 L m⁻² h⁻¹, and the boron rejection increased from 80.7 to 90.5% under the modification conditions with the optimal type and concentration of amines, while displaying a NaCl rejection of 99.8% and an acceptable water permeability of 0.55 L m⁻² h⁻¹ bar⁻¹. Meanwhile, the alteration of membrane chemical compositions and structure properties was kept to a minimum. This study offers intuitive insights into the critical roles played by the aliphatic amines in the selective layer of the membrane for the removal of neutral boron molecules and salts, thereby enabling the fabrication of highly selective SWRO membranes, which may have significant implications for more efficient membrane-based seawater desalination and boron removal.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100056"},"PeriodicalIF":0.0,"publicationDate":"2023-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49716957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Opportunities for isoporous membranes in the manufacture of genomic medicines","authors":"Ke Meng ,&nbsp;Thomas F. Johnson ,&nbsp;Alberto Alvarez-Fernandez ,&nbsp;Stefan Guldin ,&nbsp;Daniel G. Bracewell","doi":"10.1016/j.memlet.2023.100052","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100052","url":null,"abstract":"<div><p>Viral and non-viral vectors have revolutionised in the last 5 years the approaches to tackling pandemics, cancers and genetic diseases. The intrinsic properties of these vectors present new separation challenges to their manufacture in terms of both the process-related impurities to be removed and the complex labile nature of the target products. These characteristics make them susceptible to heterogeneity and the formation of product-related impurities.</p><p>Conventional polyethersulfone membrane filters used for sterile filtration and ultrafiltration of viral vectors and lipid nanoparticles can display limited selectivity and cause product losses. To address these challenges, novel membrane materials and fabrication techniques to overcome the boundary of selectivity-permeability performance have become of interest. Isoporous membranes with well-defined pore size and pore dispersity at the nano-scale show promising separation performance but have only been demonstrated at small scales to date.</p><p>This review summarises the decision process for the development of new membrane candidates for vector manufacturing in genomic medicine, including membranes fabricated by lithography, track-etched membranes, anodic aluminium oxide (AAO) membranes and self-assembled block copolymer membranes. By comparing these membranes to existing commercially available products, the possible advantages presented by novel materials and fabrication approaches are identified.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100052"},"PeriodicalIF":0.0,"publicationDate":"2023-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49717249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of surfactant structure on MPD diffusion for interfacial polymerization","authors":"Shahriar Habib,&nbsp;Bryn E. Larson,&nbsp;Steven T. Weinman","doi":"10.1016/j.memlet.2023.100055","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100055","url":null,"abstract":"<div><p>Polyamide membranes made with surfactant-assisted interfacial polymerization (IP) have demonstrated the potential for excellent membrane performance. The presence of surfactants accelerates amine diffusion into the organic phase causing a more complete IP reaction. Even though surfactant-assisted IP has been used in polyamide membranes, the structure-property relationship of the surfactants on amine transport into the organic phase has not been explored in a systematic manner. In this work, MPD diffusion from a membrane support into <em>n</em>-dodecane in the presence of seven different surfactants, which were anionic, cationic, and non-ionic, was evaluated. When the surfactants were used at different concentrations, the MPD concentration was increased in the presence of anionic (48–80%), cationic (32–75%) and non-ionic (26%) surfactants. The MPD concentration was increased in the presence of anionic (by 48–72%), cationic (by 32–75%), and non-ionic surfactants (by 26%) at 15–60 s contact time. For further understanding, the interfacial tension in <em>n</em>-dodecane for the surfactants was measured, however, it did not correlate with our data. This study provides a better understanding of MPD diffusion in the presence of different types of surfactants during RO membrane synthesis, which will help us to engineer membranes with better permeability and selectivity.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100055"},"PeriodicalIF":0.0,"publicationDate":"2023-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49717239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Epoxide-based TFC membranes with tunable performance in the tight nanofiltration range","authors":"Rhea Verbeke ,&nbsp;Douglas M. Davenport ,&nbsp;Caroline Bogaerts ,&nbsp;Samuel Eyley ,&nbsp;Wim Thielemans ,&nbsp;Ivo F.J. Vankelecom","doi":"10.1016/j.memlet.2023.100054","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100054","url":null,"abstract":"<div><p>Membrane technology offers promise as a breakthrough separation technology in many applications, but is frequently limited by the chemical stability of currently available membrane materials. Recently developed membranes utilizing epoxide-based chemistry have shown great potential as intrinsically stable thin-film composite membranes in water-based applications. However, as these membranes are in their infancy, many synthesis parameters are still to be explored. In this study, the versatility of epoxide chemistry is exploited to demonstrate its potential to serve as a new platform for membrane synthesis, even beyond the field of aqueous applications. It is proven here how the membrane performance can be tailored in a controllable way between 20 – 85% NaCl rejection with a water permeance between 0.5 – 3 L m⁻² h⁻¹ bar⁻¹ by simply selecting epoxide monomers and initiators of different size and functionality. A systematic increase in water permeance and salt passage was observed for epoxide monomers that exhibit a lower functionality and a lower number of aromatic groups, while a threshold nucleophilicity and aliphatic chain length of the initiator are required to obtain a salt-selective layer. This work demonstrates the possibility to easily and predictably tune membrane performance in the tight nanofiltration range, while simultaneously achieving a better understanding of the synthesis-structure-performance relationship of this new class of promising membranes.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100054"},"PeriodicalIF":0.0,"publicationDate":"2023-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49717243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mixed-linker MOF-303 membranes for pervaporation","authors":"Fang-Hsuan Hu ,&nbsp;Li-Tang Chi ,&nbsp;Guan-Bo Syu ,&nbsp;Tsyr-Yan Yu ,&nbsp;Ming-Pei Lin ,&nbsp;Jiun-Jen Chen ,&nbsp;Wen-Yueh Yu ,&nbsp;Dun-Yen Kang","doi":"10.1016/j.memlet.2023.100053","DOIUrl":"https://doi.org/10.1016/j.memlet.2023.100053","url":null,"abstract":"<div><p>Metal-organic frameworks (MOFs) hold great promise as porous materials for pervaporation applications. However, the exploration of MOF membranes in this field is still in its early stages. One of the main challenges is the relatively low mass flux and stability of pure MOF membranes compared to other materials used in pervaporation. In this study, we propose a novel approach to enhance the separation performance of MOF membranes for water and ethanol separation. Our strategy involves incorporating the 2,5-thiophenedicarboxylic acid (TDC) linker into the MOF-303 structure, partially replacing the 3,5-pyrazoledicarboxylic acid (PDC) linker. The goal is to increase the aperture size of the microporous channels in the pristine MOF-303 membrane, thereby improving the mass flux. X-ray diffraction characterization, combined with Rietveld refinement, confirmed that the partial substitution of PDC with TDC resulted in an increased pore-limiting diameter (PLD) of MOF-303. For instance, the pristine MOF-303 exhibited a PLD of 5.78 Å, while MOF-303(70/30) with 70% TDC replacement displayed a PLD of 6.02 Å. To fabricate the mixed-linker MOF-303 membranes, we utilized a seeded growth method, which yielded membranes with dense layers, as confirmed by scanning electron microscopy and air permeation characterization. The prepared membranes were subjected to pervaporation tests to evaluate their performance in separating 90 wt.% ethanol at 60 °C. The pristine MOF-303 membrane exhibited notable separation capabilities, with an average flux of 0.071 kg·m⁻²·hr⁻¹ and a water/ethanol separation factor of 5371. Surpassing the unmodified MOF-303, the mixed-linker MOF-303(50/50) membrane demonstrated improved mass flux and water/ethanol separation factor. Specifically, the MOF-303(50/50) membrane displayed an average flux of 0.092 kg·m⁻²·hr⁻¹ and a water/ethanol separation factor of 8500. Importantly, the unmodified MOF-303 membrane exhibited instability during prolonged pervaporation operation, whereas the mixed-linker MOF-303(50/50) membrane effectively addressed this issue. Further analysis using <em>in situ</em> Fourier transform infrared spectroscopy and water adsorption characterization revealed that MOF-303(50/50) possessed a strong affinity for water, comparable to the pristine MOF-303. Overall, our study highlights the potential of the mixed-linker approach to optimize the separation performance and stability of MOF-based membranes for pervaporation application.</p></div>","PeriodicalId":100805,"journal":{"name":"Journal of Membrane Science Letters","volume":"3 2","pages":"Article 100053"},"PeriodicalIF":0.0,"publicationDate":"2023-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49735102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}