Article
Chemistry, Applied
Silvia Escayola, Jordi Poater, Miguel Ramos, Jesus Antonio Luque-Urrutia, Josep Duran, Silvia Simon, Miquel Sola, Luigi Cavallo, Steven P. Nolan, Albert Poater
Summary: The functionalization of alkynes by Au (N-heterocyclic carbene, NHC) complexes through hydrophenoxylation reaction is a topic of discussion for mono and dual metal catalysis. This study examined a synthetic motif that mimics a framework with two gold units and tested its role in hydrophenoxylation/hydroalkoxylation reactions using DFT calculations. Different chain lengths were explored in terms of coordinating the alkyne to the cationic NHC-gold(I) center.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Review
Chemistry, Physical
Oscar F. Gonzalez-Belman, Artur Brotons-Rufes, Michele Tomasini, Laura Falivene, Lucia Caporaso, Jose Oscar C. Jimenez-Halla, Albert Poater
Summary: Poly(vinyl ethers) are valuable compounds in the coating industry with properties like high viscosity, soft adhesiveness, saponification resistance, and solubility in water and organic solvents. Synthesizing vinyl ether monomers remains a challenge, but the addition of alcohols to alkynes catalyzed by transition metals has shown promise, with gold-NHC catalysts being particularly effective. Recent studies on the hydrophenoxylation reaction have revealed the rate-determining steps and sensitivity to sterical hindrance from the NHC ligands.
Article
Chemistry, Multidisciplinary
Si Chen, Xiaohui Huang, Dieter Schild, Di Wang, Christian Kuebel, Silke Behrens
Summary: Intermetallic Pd-In nanoparticles were synthesized in ionic liquids using a novel and facile approach. The structure of the nanoparticles obtained under different reaction conditions was confirmed. These stabilized nanoparticles showed high activity and selectivity as catalysts. This research provides insights for the synthesis of intermetallic nanoparticles and the design of bimetallic catalysts.
Article
Chemistry, Multidisciplinary
Li-Xia Fan, Lin Chen, Hua-Yu Zhang, Wen-Hao Xu, Xiu-Li Wang, Shimei Xu, Yu-Zhong Wang
Summary: This study proposes a novel in situ chemical upcycling strategy for plastic waste using a customized diphenylacetylene monomer. By inserting diphenylacetylene reactive monomers into the macromolecular chain of polyethylene terephthalate (PET) plastics/fibers, the upcycled PET plastics exhibit reverse enhanced UV resistance and mechanical strength.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Katarina Stefkova, Matthew J. Heard, Ayan Dasgupta, Rebecca L. Melen
Summary: Triarylboranes have garnered significant attention as catalysts for C-C bond forming reactions due to their remarkable catalytic activities. In this study, the B(C6F5)(3) catalyzed cyclopropenation of arylacetylenes using donor-acceptor diazoesters has been successfully developed, resulting in the synthesis of a wide variety of functionalized cyclopropenes in good to excellent yields.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Victor J. Mayerhofer, Martina Lippolis, Christopher J. Teskey
Summary: A mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones and imines is reported. Applications of this straightforward approach include the efficient synthesis of drug molecules and site-selective late-stage functionalisation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tatyana N. Moshkina, Emiliya V. Nosova, Galina N. Lipunova, Ekaterina F. Zhilina, Pavel A. Slepukhin, Igor L. Nikonov, Valery N. Charushin
Summary: A series of novel derivatives were synthesized and their fluorescence properties as well as the ability to detect Fe3+ cations were investigated.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Juan Jose Tarrio, Berta Fernandez, Emilio Quinoa, Felix Freire
Summary: There is a significant correlation between the size of non-symmetric poly(diphenylacetylene)s (PDPAs) and their electronic circular dichroism (ECD) spectra. Consequently, polymers and oligomers of PDPAs with the same screw sense excess exhibit reverse ECD spectra. This is attributed to the intricate nature of ECD spectra, which primarily rely on the degree of polymerization (DP).
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Shujin Hou, Lili Xu, Xing Ding, Regina M. Kluge, Theophilus Kobina Sarpey, Richard W. Haid, Batyr Garlyyev, Soumya Mukherjee, Julien Warnan, Max Koch, Shengli Zhang, Weijin Li, Aliaksandr S. Bandarenka, Roland A. Fischer
Summary: Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. The nature of alkali metal cations has been found to have a profound impact on the oxygen evolution activity of SURMOF derived electrocatalysts based on NiFe(OOH). The effects of cation-dependent electric double layer properties on activity were studied using a laser-induced current transient technique. Electrolyte composition can be used to maximize the performance of SURMOF derivatives in electrochemical water splitting.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Danijela Lunic, Enrico Bergamaschi, Christopher J. Teskey
Summary: Light, in combination with transition metal catalysis, can modify catalyst function in a non-invasive manner, often switching on or accelerating reactions that do not occur in the dark. While it is less common, the ability to completely change reactivity or selectivity between different reaction outcomes is also possible with these systems. These non-natural, photo-switchable systems provide key mechanistic insights that enhance our understanding and stimulate the development of new catalytic activities, potentially impacting fields such as polymer chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ying-Qi Zhang, Yang-Bo Chen, Ji-Ren Liu, Shao-Qi Wu, Xin-Yang Fan, Zhi-Xin Zhang, Xin Hong, Long-Wu Ye
Summary: The use of chiral Bronsted acids in catalytic asymmetric synthesis enables the direct activation of alkynes, leading to the construction of valuable spirocyclic enones and 2H-pyrroles with high yields and excellent enantioselectivity. This activation mode is expected to be widely applicable in catalytic asymmetric reactions involving ynamides and related heteroatom-substituted alkynes.
Review
Orthopedics
Theodore T. T. Manson, Murillo Adrados, Jeremy M. M. Gililland, Bilal M. M. Mahmood, Linsen T. T. Samuel, Joseph T. T. Moskal
Summary: Dual mobility (DM) is a widely used option for total hip replacement, which features a small inner head within a larger outer polyethylene head. It aims to increase stability and range of motion in the hip joint. However, long-term data, especially for modular DM implants, is lacking, and potential issues include accelerated polyethylene wear, intraprosthetic dislocation, and modular backside fretting corrosion.
JOURNAL OF BONE AND JOINT SURGERY-AMERICAN VOLUME
(2023)
Article
Chemistry, Organic
Milos Petkovic, Milos Jovanovic, Predrag Jovanovic, Milena Simic, Gordana Tasic, Vladimir Savic
Summary: Pyrrole derivatives with C(2)-aryl substituents are an important and widespread class of heterocyclic compounds. A novel approach combining the dual role of arylating agent as nitrogen protecting group and involved in the arylation step has been developed for the direct arylation synthesis of C(2)-arylpyrroles. The deprotection as a final stage is carried out simultaneously utilizing amines as reacting components, leading to mild conditions and exclusive C(2) selectivity.
SYNTHESIS-STUTTGART
(2022)
Article
Multidisciplinary Sciences
Paul White, Samuel F. Haysom, Matthew G. Iadanza, Anna J. Higgins, Jonathan M. Machin, James M. Whitehouse, Jim E. Horne, Bob Schiffrin, Charlotte Carpenter-Platt, Antonio N. Calabrese, Kelly M. Storek, Steven T. Rutherford, David J. Brockwell, Neil A. Ranson, Sheena E. Radford
Summary: The study elucidates the roles of BAM structure and lipid dynamics in OMP folding, showing that both factors are crucial for efficient OMP assembly.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Jennifer Poelker, Dieter Schaarschmidt, Josef Bernauer, Matteo Villa, Axel Jacobi von Wangelin
Summary: This article introduces a catalytic hydrogenation of amines using a bimetallic Li/Al dihydride catalyst. The research demonstrates that the preparation of this catalyst is relatively simple.
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Juliane Heitkaemper, Sergio Posada-Perez, Silvia Escayola, Miquel Sola, Johannes Kaestner, Albert Poater
Summary: For decades, efforts have been made to reduce the amount of metal reagents used in the synthesis of secondary alcohols. In 2021, Newman and collaborators pioneered a synthesis method using metals as catalytic engines rather than reactants. This paper presents a description of the process using Density Functional Theory calculations and attempts to shed light on the mechanism behind the attainment of secondary alcohols, emphasizing the debate on whether the catalytically active species is Ni(0) or if they take shortcuts following the course of Ni(II). Effective Orbital analyses provide a clear picture. Furthermore, this paper provides insight into both the nature of the ligands of the metal catalyst and the role of the base.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Artur Brotons-Rufes, Naeimeh Bahri-Laleh, Albert Poater
Summary: Ruthenium-NHC based catalysts with chelated iminium ligand were studied using Density Functional Theory calculations to understand the reaction mechanism of dicyclopentadiene polymerization at different temperatures. The importance of geometrical and electronic features, as well as non-covalent interactions, especially H-bonds, were investigated. This computational study aims to facilitate future research on new generations of latent initiators for olefin metathesis polymerization using Non-Covalent Interaction plots as a characterization tool for H-bonds.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Gibu George, Sergio Posada-Perez, Albert Poater, Miguel Sola
Summary: Aqueous lithium-ion batteries are promising large-scale energy storage technology due to their low-cost and environmentally friendly nature. However, the interaction between water and electrodes leads to fast degradation of the batteries. In this study, density functional theory simulations were used to investigate the behavior of Li1-xMn2O4 as a cathode material for aqueous batteries. The results reveal that a partially lithiated (011) surface can produce O2 at low overpotential, while a (001) termination can facilitate the presence of O and OOH intermediates at 1.23 V without generating O2. The study highlights the pros and cons of using Li1-xMn2O4 as a cathode material and the importance of surface termination in aqueous electrolytes.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Mostafa Ahmadi, Lucas Loeser, Gerard Pareras, Albert Poater, Kay Saalwaechter, Sebastian Seiffert
Summary: The properties of polymer networks are influenced by the presence of connectivity defects like loops and dangling ends. Transient polymer networks based on metallo-supramolecular polymer networks and hindrance can self-sort to develop networks with fewer defects. By using heteroleptic complexes and adjusting the coordination geometry preference, we can control the self-sorting process and reduce the formation of primary loops and dangling ends. Our results show that copper(I) can adopt the desired geometry requirements and create a network with the least number of defects.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Benon P. Maliszewski, Tahani A. C. A. Bayrakdar, Perrine Lambert, Lama Hamdouna, Xavier Trivelli, Luigi Cavallo, Albert Poater, Marek Belis, Olivier Lafon, Kristof Van Hecke, Dominic Ormerod, Catherine S. J. Cazin, Fady Nahra, Steven P. Nolan
Summary: In this study, the catalytic activity of a series of platinum(II) pre-catalysts with N-heterocyclic carbene (NHC) ligands in the alkene hydrosilylation reaction is reported. The structural and electronic properties of these catalysts are fully characterized using X-ray diffraction analysis and nuclear magnetic resonance spectroscopy (NMR). A structure-activity relationship within this group of pre-catalysts is established, and mechanistic insights into the catalyst activation step are provided. One of the complexes shows exceptional catalytic performance, achieving a turnover number (TON) of 970,000 and a turnover frequency (TOF) of 40,417 h(-1) at 1 ppm catalyst loading. Furthermore, a solvent-free and open-to-air alkene hydrosilylation protocol with efficient platinum removal (reducing residual Pt from 582 ppm to 5.8 ppm) is disclosed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Roger Monreal-Corona, Miquel Sola, Anna Pla-Quintana, Albert Poater
Summary: The mechanism for the stereospecific synthesis of cyclobutanes is revealed using density functional theory (DFT) calculations. The rate-determining step involves the release of N2 from the 1,1-diazene intermediate to form an open-shell singlet 1,4-biradical. The formation of the stereo-retentive product is explained by the barrierless collapse of this open-shell singlet 1,4-biradical. The methodology could potentially be used for the synthesis of [2]-ladderanes and bicyclic cyclobutanes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Mostafa Ahmadi, Albert Poater, Sebastian Seiffert
Summary: Advances in self-sorting mechanisms have led to the development of well-defined supra-molecular coordination complexes (SCCs) with unprecedented geometries. However, these advances have been rarely applied to the design of metallo-supramolecular polymer networks (MSPNs). To address this gap, steric hindrance was used as a self-sorting mechanism to construct MSPNs based on the formation of heteroleptic complexes. These results open up a promising interface between polymer science and coordination chemistry.
Article
Chemistry, Physical
Samahe Sadjadi, Neda Abedian-Dehaghani, Majid M. Heravi, Xuemin Zhong, Peng Yuan, Josep Duran, Albert Poater, Naeimeh Bahri-Laleh
Summary: Halloysite nanoclay was used as a natural support for an acidic ionic liquid immobilization. The resulting catalyst exhibited improved Bronsted acidity and high recyclability. It effectively promoted the conversion of various carbohydrates to a valuable product under mild reaction conditions.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sergio Posada-Perez, Anna Vidal-Lopez, Miquel Sola, Albert Poater
Summary: In this study, the performance of Cu, Ag, and Au single-atom particles dispersed on a two-dimensional carbon nitride support for CO2 reduction reaction was explored. It was found that the deposition of single metal atoms enhances the catalytic activity of the system, with the first proton-electron transfer being favored in terms of energy. However, strong binding energies were found for CO adsorption on Cu and Au single atoms, leading to the favorable competitive H2 generation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Sylwia Ostrowska, Pierre Arnaut, David J. Liptrot, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis, isolation, and full characterization of a new copper complex [Cu(IPr)(OC(H)(CF3)(2))] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) are reported. This copper(I) complex is a versatile synthon capable of activating various X-H bonds including C-H, N-H, and S-H bonds. [Cu(IPr)(OC(H)(CF3)(2))] was investigated as a pre-catalyst in several catalytic reactions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Tharinee Theerathanagorn, Anna Vidal-Lopez, Aleix Comas-Vives, Albert Poater, Valerio D'Elia
Summary: The study demonstrates that water-soluble organocatalysts can efficiently synthesize cyclic carbonates from CO2 and various epoxides in water-organic biphasic systems. The addition of simple inorganic salts accelerates the reaction rates and seawater is particularly effective as the aqueous layer. Control experiments and DFT calculations provide insights into the heterogeneous catalytic process at the interface between water droplets and the epoxide phase.
Article
Polymer Science
Mohammadreza Mehdizadeh, Fereshteh Karkhaneh, Mehdi Nekoomanesh, Samahe Sadjadi, Mehrsa Emami, HamidReza Teimoury, Mehrdad Salimi, Miquel Sola, Albert Poater, Naeimeh Bahri-Laleh, Sergio Posada-Perez
Summary: The influence of ethanol content in adducts on the catalytic behavior of Ziegler-Natta catalysts in propylene homo- and copolymerizations was investigated. The results showed that higher ethanol content in the adducts led to increased catalyst activity, particularly in homopolymerization reactions in the absence of H2. Additionally, the catalyst with the highest ethanol content produced a copolymer with lower isotacticity index and more uniform distribution of comonomer. These findings highlight the importance of controlling ethanol content in catalyst/support during the preparation process. Molecular simulation was also utilized to explain the iso-specificity of the polypropylene produced by the synthesized catalysts.
Article
Chemistry, Physical
Mostafa Ahmadi, Cora Sprenger, Gerard Pareras, Albert Poater, Sebastian Seiffert
Summary: Nature utilizes spontaneous self-organization of supramolecular bonds to create complex matter capable of adaptation and self-healing. In this study, the self-sorting of unlike ligands in a mixed ligand system was used to form stimuli-responsive polymer networks with various geometries. By studying the coordination preferences of different metal ions, the researchers achieved the formation of heteroleptic complexes in polymer networks, resulting in enhanced strength and stability compared to individual components. The findings offer new opportunities for the development of topology-switching polymer networks.
Article
Chemistry, Physical
Zi-Ye Liu, Qian-Yu Wang, Ji-Ming Hu
Summary: In this study, a layered carbon dot composite catalyst (NiFe LDH@CDs) was prepared using a one-step coprecipitation method, without the need for heating or hydrothermal treatment. The CD-functionalized catalyst facilitated rapid charge transfer and accelerated the oxygen evolution reaction. Additionally, the heterojunction structure formed between NiFe LDH and CDs efficiently suppressed photoelectron-hole recombination.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Rohit Kumar, Ankit Kumar Srivastava, Palaniyappan Nagarasu, Vedichi Madhu, Ekambaram Balaraman
Summary: We designed and synthesized a NN-CoII bidentate complex and used it for the amination of alcohols under mild and solventless conditions. The complex exhibited good reactivity towards both primary and sterically hindered secondary alcohols, providing high yields of amines. The pyrazole moiety in the ligand played a crucial role in the reaction. Furthermore, we demonstrated the reusability of the complex as a homogeneous cobalt catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shivanand Chettri, Liang-Ting Wu, Sagarmani Rasaily, Debesh Sharma, Bikram Gurung, Rajani Dewan, Sudarsan Tamang, Jyh-Chiang Jiang, Anand Pariyar
Summary: Replicating the enzymatic surface microenvironment in vitro is challenging, but constructing an analogous model could facilitate our understanding of surface effects and aid in developing an efficient bioinspired catalytic system. In this study, five unique Cu2O morphologies were generated, and the surface morphology variations were found to be a consequence of differences in the exposure of low-index facets. The reactivity of Cu2O was found to be influenced by the proportion of {110} planes, with r-Cu2O exhibiting the highest reactivity.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Yong Tang, Jianhao Qiu, Dingliang Dai, Guanglu Xia, Lu Zhang, Jianfeng Yao
Summary: Defect engineering has been shown to improve the photocatalytic performance. This study investigated the use of defect-rich UiO-66-NH2 wrapped by ZnIn2S4 as a catalyst for photocatalytic H2O2 production. The defects in UiO-66-NH2 enhanced O-2 adsorption and charge separation, leading to higher H2O2 yield. The insights from this work can advance the research in defect engineering of MOFs and photocatalytic H2O2 synthesis.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Ruiyang Qu, Shuxin Mao, Jana Weiss, Vita A. Kondratenko, Evgenii V. Kondratenko, Stephan Bartling, Haifeng Qi, Annette-Enrica Surkus, Kathrin Junge, Matthias Beller
Summary: The hydrogenation of amides, a challenging reaction usually performed at high temperatures, has been achieved under milder conditions using a new Pt-MoOx/TiO2 catalyst. This catalyst system enables the selective hydrogenation of various amides and imides.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Xiaoran Niu, Ao Wang, Lei Tong, Lei Wang, Yuan Kong, Chenliang Su, Hai-Wei Liang
Summary: This study introduces a novel intermetallic PdCu3 catalyst supported on defective nanodiamond-graphene (ND@G), which exhibits high selectivity (95%) and remarkable activity (turnover frequency: 2940 h(-1)), six times higher than that of the commercial Lindlar catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Review
Chemistry, Physical
Zhiyuan Zheng, Yiming Yue, Hongying Zhuo, Qinggang Liu, Yanqiang Huang
Summary: This review presents the recent research advances on single-atom catalysis for deep reduction of CO2. Detailed introductions and summaries were classified into three categories based on proton-coupled multi-electron transfer approaches: strengthening metal-support interaction, rational design and regulation of coordination environment, and development of SACs with multi-atom active sites. The challenges and future research directions in the field of SACs for CO2 reduction are also proposed.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shiv Kumar, Paramita Datta, Anup Bhunia, Swadhin K. Mandal
Summary: This article reports a transition-metal-free process for in situ denitrogenation of tosylhydrazones, resulting in the production of various sulfones. The authors used a phenalenyl-based odd alternant hydrocarbon as a photoredox catalyst, which acted as a potent oxidant to facilitate the denitrogenation reaction. The method showed wide functional-group tolerance and high yields, making it suitable for late-stage modification of natural products.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
L. A. Luque-Alvarez, J. Gonzalez-Arias, F. Romero-Sarria, T. R. Reina, L. F. Bobadilla, J. A. Odriozola
Summary: Currently, the production of acetic acid through the carbonylation reaction of methanol has limitations, leading to the exploration of alternative methods using heterogeneous catalysts. This study investigates the methanol carbonylation reaction over a Cu-H-MOR catalyst and proposes a reaction mechanism based on the catalytic behavior and performance of the catalyst. The results provide insights into the reaction mechanism and the involvement of acid and redox centers.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
