Molecular Systems Design & Engineering最新文献

{"title":"Investigation of novel indoline azo disperse dyes: synthesis, DFT simulation, and dyeing performance on PET and PA fabrics†","authors":"Xiyu Song, Mingda Li, Chuang Dai, Jingyi Li, Yu Wang, Aiqin Hou and Hongfei Qian","doi":"10.1039/D3ME00187C","DOIUrl":"10.1039/D3ME00187C","url":null,"abstract":"<p >The feasibilities of the chemical reactions of indoline were analyzed with density functional theory (DFT) simulation. A series of azo disperse dyes using indoline as a coupling component were synthesized, namely D1–D6. The synthesized dyes were investigated by UV-visible, FT-IR, <small>¹</small>H-NMR and MS spectroscopies. DFT simulation was applied to analyze the spectrometric properties of designed dyes. The dyeing of polyethylene terephthalate (PET) and nylon (PA) fabrics were assessed and compared. The synthesized indoline azo disperse dyes exhibited a yellow to red hue on the PET and PA fabrics. Deep shades were achieved with increased dye concentrations for D1 and D2 for the PET and PA fabrics. Excellent rubbing fastness and good sublimation fastness were achieved. Interrelations between dye structures and dyeing performance on the PET and PA fabrics were investigated using DFT calculations.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 5","pages":" 500-506"},"PeriodicalIF":3.6,"publicationDate":"2024-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139927479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactive degradable linear poly(aminoamide)s: synthesis, post-polymerization modifications and layer-by-layer coating†","authors":"Sulbha Kumari and Subrata Chattopadhyay","doi":"10.1039/D4ME00003J","DOIUrl":"10.1039/D4ME00003J","url":null,"abstract":"<p >The design of reactive biodegradable polymers and materials is an extremely important topic of research. This work presents the synthesis of a highly reactive and degradable poly(aminoamide) containing indole functional group in each repeating unit. The presence of indole functional groups allows for easy post-modification of such poly(aminoamide), enabling the synthesis of a library of functional poly(aminoamide)s <em>via</em> triazolinedione (TAD)–indole click reactions. Furthermore, the use of bifunctional TAD molecules facilitates the crosslinking of such poly(aminoamide), where the degree of crosslinking directly influencing the surface area of the resulting materials. The thermoreversible characteristics of such crosslinked material was also investigated. Additionally, such indole decorated poly(aminoamide) was used as an excellent platform for layer-by-layer coatings and surface functionalization. Degradation studies reveals that both the linear and crosslinked poly(aminoamide)s can be degraded in alkaline solution, where the crosslinked materials degrade faster compared to the linear analogues.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 5","pages":" 490-499"},"PeriodicalIF":3.6,"publicationDate":"2024-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139927490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Adsorption variations on the Ni(111) surface: electron density diversity from oxygen-containing functional groups†","authors":"Changwei Liu, Congtao Wen, Zekai Zhang, Yuxin Chen, Huachao Yang, Jia-hui Li, Cheng Lian and Honglai Liu","doi":"10.1039/D3ME00168G","DOIUrl":"10.1039/D3ME00168G","url":null,"abstract":"<p >In the catalytic hydrodeoxygenation (HDO) upgrading process of biomass pyrolysis, adsorption behavior plays a crucial role in subsequent reaction processes. A comprehensive understanding of the interfacial behavior is essential for advancing novel biomaterials and commercial bio-oil. We initially establish their precise orientation on the Ni(111) surface and identify the preferential binding site by calculating the binding energy of eight model components (<em>n</em>-butanol, acetic acid, methyl acetate, <em>n</em>-hexanal, toluene, catechol, guaiacol, and 3-methyl-1,2-cyclopentanone). Differences in the electrostatic potential of functional groups and their interactions with the surface lead to surface electrostatic potential distributions, with compounds containing aldehyde functionality demonstrating increased reactivity. To account for competitive adsorption behavior among multiple molecules, ReaxFF-MD simulations were conducted to investigate the adsorption of guaiacol molecules. The inclusion of acetic acid enhances the polarization effect and non-uniformity, indicating competitive adsorption between guaiacol and acetic acid molecules. The chair conformation of acetic acid was demonstrated to be more reasonable from a kinetic perspective, leading to a stronger surface charge induction effect compared to guaiacol. Additionally, this non-uniform distribution is closely correlated with the characteristic bond activations of adsorbed active molecules, serving as a driving force to enhance further hydrogenation and deoxygenation activities of the molecules.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 5","pages":" 477-489"},"PeriodicalIF":3.6,"publicationDate":"2024-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139927416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3-Perfluoroalkylated fluorescent coumarin dyes: rational molecular design and photophysical properties†","authors":"Ayano Ikemura, Yukiko Karuo, Yuki Uehashi, Tomohiro Agou, Masahiro Ebihara, Yasuhiro Kubota, Toshiyasu Inuzuka, Masaaki Omote and Kazumasa Funabiki","doi":"10.1039/D4ME00006D","DOIUrl":"10.1039/D4ME00006D","url":null,"abstract":"<p >Owing to their excellent fluorescence properties, coumarin derivatives have diverse applications in phototherapy and optoelectronics. Coumarin derivatives with a trifluoromethyl group at the 4-position have been extensively investigated; however, studies on the photophysical properties of fluorescent 3-trifluoromethylated coumarins in solution and in the solid state are rare. Hence, in this study, the photochemical properties of a coumarin derivative incorporating a promising electron-withdrawing fluoroalkyl group at the 3-position in solution and in the crystal form were investigated in detail by absorption and fluorescence spectral measurements, density functional theory and time-dependent density functional theory calculations, and single crystal X-ray structure analysis. The aim was to verify the reasons for its excellent fluorescence emission in solution and in the crystal form. These molecular compounds are expected to have potential applications as coumarin fluorophores in fluorescent emission probes and electronic light-emitting devices.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 4","pages":" 332-344"},"PeriodicalIF":3.6,"publicationDate":"2024-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139769926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancing osteogenic differentiation of mesenchymal stem cells seeded on a polycaprolactone/MoS2 nanofibrous scaffold through electrical stimulation","authors":"Elahe Amiri, Mehrdad Khakbiz, Behnaz Bakhshandeh, Nika Ranjbar and Javad Mohammadnejad","doi":"10.1039/D3ME00135K","DOIUrl":"10.1039/D3ME00135K","url":null,"abstract":"<p >Recent progress in bone tissue engineering (BTE) has introduced alternative treatments for sizable and non-healing bone defects. Electrical stimulation (ES) has recently been shown to influence bone cells and foster processes such as adhesion, migration, proliferation, and differentiation, which can enhance the bone regeneration process. In this study, we synthesized molybdenum disulfide (MoS<small>₂</small>) nanoparticles (NPs) and incorporated them into a polycaprolactone (PCL) polymeric matrix to enhance the electrical conductivity of scaffolds. The PCL/MoS<small>₂</small> nanocomposites were analysed using scanning electron microscopy (SEM), water contact angle measurement, electrical conductivity, and tensile strength assessments. <em>In vitro</em> studies evaluated the adhesion of mesenchymal stem cells (MSCs) and the biocompatibility of the fabricated scaffolds using the MTT assay. Biomineral crystal deposition was determined <em>via in vitro</em> simulated body fluid (SBF) biomineralization, and alizarin red S assays demonstrated enhanced calcium phosphate deposition on the PCL/MoS<small>₂</small> composite scaffold. Additionally, qPCR analysis revealed that exposing MSCs cultured on PCL/MoS<small>₂</small> to ES for two weeks transcriptionally upregulated osteogenic markers (osteocalcin (OC) and alkaline phosphatase (ALP)) in cells. Using either ES or a differentiation medium alone could enhance osteogenesis. However, when both stimuli were applied concurrently, improved levels of osteogenic markers were observed. Our findings suggest that ES plays a significant role in boosting osteogenic differentiation, particularly when combined with MoS<small>₂</small>NPs as an osteogenic enhancer. Therefore, PCL/MoS<small>₂</small> nanofibrous scaffolds can be proposed as suitable candidates for BTE, and ES holds great potential as an effective tool along with commonly used biomaterial scaffolds.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 6","pages":" 581-596"},"PeriodicalIF":3.6,"publicationDate":"2024-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/me/d3me00135k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139769864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of composition ratio of donor and acceptor moieties in conjugated polymer: optical and electrochemical properties†","authors":"Shahjad and Asit Patra","doi":"10.1039/D3ME00171G","DOIUrl":"10.1039/D3ME00171G","url":null,"abstract":"<p >Designing donor–acceptor polymers by incorporating additional donor or acceptor units in the polymer backbone has attracted significant interest for further tuning of physical and chemical properties for organic electronic applications. In this study, we design and synthesize random donor–acceptor–donor–acceptor (D–A–D–A′, <strong>P1</strong>) and acceptor–donor–acceptor–acceptor (A–D–A′–A, <strong>P2</strong>) polymers using direct heteroarylation polymerization. Polymer <strong>P1</strong> has alternating donor and acceptor units, whereas polymer <strong>P2</strong> has an additional acceptor unit. For comparison purposes with parent polymers, three donor–acceptor polymers (<strong>P3–5</strong>) were synthesized. All polymers <strong>P1–5</strong> were synthesized from three precursor units, 5-fluoro-2,1,3-benzothiadiazole, 5-diethylhexyl-3,6-bis(thiophene-2-yl)pyrrolo[3,4-<em>c</em>]pyrrole-1,4-dione and 3-hexylthiophene, using different compositions and sequences. Structural characterization of polymers <strong>P1–5</strong> was carried out by <small>¹</small>H NMR, GPC and FTIR spectroscopy. The electrochemical, stability and optical properties of polymers <strong>P1–5</strong> were investigated by cyclic voltammetry and UV-vis-NIR absorption spectroscopy. All polymers exhibited narrow optical band gaps. The absorption of these polymers was red-shifted (30–100 nm) in the solid state compared to in a solution. It was observed that copolymers have different optical and electrical properties from their parent donor–acceptor polymers. Therefore, it is an effective method for the synthesis of donor–acceptor polymers with additional donor or acceptor units to tune the properties of the polymers for flexible electronic applications.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 7","pages":" 754-764"},"PeriodicalIF":3.2,"publicationDate":"2024-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139769836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single-atom cobalt encapsulated in carbon nanotubes as an effective catalyst for enhancing sulfur conversion in lithium–sulfur batteries†","authors":"Khalida Abaid Samawi, Ekhlas Abd-Alkuder Salman, Hiba Ali Hasan, HassabAlla M. A. Mahmoud, Sura Mohammad Mohealdeen, G. Abdulkareem-Alsultan, Emilia Abdulmalek and Maadh Fawzi Nassar","doi":"10.1039/D3ME00191A","DOIUrl":"10.1039/D3ME00191A","url":null,"abstract":"<p >The application of single-atom catalysts offers an auspicious resolution to the obstacles introduced by the polysulfide shuttle phenomenon and the sluggish sulfur conversion kinetics in lithium–sulfur batteries (LSBs). This research presents results regarding a sulfur host that demonstrates redox activity and resistance to polymeric sulfur species (PSS). High-curvature carbon nanotubes are utilized in the construction of a single atom CoN<small>₄</small> catalyst through a series of steps including pyrolysis, surface processing, electrostatic adsorption, and polymerization. Undoubtedly, the presence of cobalt (Co) atoms as discrete entities was revealed by X-ray absorption spectroscopy and transmission electron microscopy, as these atoms showed dimensions consistent with the sulfur components on the cathode side. This configuration enables catalytic activity with a remarkable 100% atomic utilization functionality. Furthermore, the DFT calculation of free energy values indicates that the reduction of LiPSs on the carbon nanotube with surface curvature is more advantageous compared to the planar carbon surface. The obtained data suggest that the sulfur cathode, which was fabricated utilizing CoSAC/CNT, demonstrates electrocatalytic capability in the transformation of soluble polysulfides to insoluble Li<small>₂</small>S. As a consequence, the detrimental effects of the polysulfide shuttle effect are mitigated. The recently introduced sulfur host in the LSB exhibits consistent performance over 1000 cycles. It sustains a capacity of 990 mA h g<small>⁻¹</small> at a rate of 1C, with a sulfur loading of 2.0 mg cm<small>⁻²</small>. An impressive area-specific power of 4.1 mA h cm<small>⁻²</small> is achieved with a considerable sulfur loading of 7 mg cm<small>⁻²</small>. This single-atom cobalt catalyst shows significant potential as a next-generation cathode material for LSBs.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 5","pages":" 464-476"},"PeriodicalIF":3.6,"publicationDate":"2024-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139769942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical design of imprinted albumin against foodborne toxins†","authors":"Polina M. Ilicheva, Elena S. Fedotova, Kirill Yu. Presnyakov, Vyacheslav S. Grinev, Pavel S. Pidenko and Natalia A. Burmistrova","doi":"10.1039/D3ME00179B","DOIUrl":"10.1039/D3ME00179B","url":null,"abstract":"<p >Creation of imprinted proteins (IPs) as a synthetic alternative to natural recognition systems is an important task for chemical engineering. However, the knowledge available on the theoretical study of IPs as recognition systems is limited. In this study, combined molecular docking and molecular dynamics methods were applied for the first time to study the albumin-based IPs against foodborne toxins. Changes in protein structure and intermolecular interactions between protein and foodborne toxin molecules were evaluated. Based on these theoretical computations, insights into the rational design for IPs were submitted. This approach is extremely promising for demonstrating the IP formation mechanism, identifying their properties, and introducing new concepts of IP creation based on controlling the synthesis conditions.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 5","pages":" 456-463"},"PeriodicalIF":3.6,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139769943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Two-state nanocomposite based on symmetric diblock copolymer and planar nanoparticles: mesoscopic simulation†","authors":"Maxim Malyshev, Daria Guseva and Pavel Komarov","doi":"10.1039/D3ME00176H","DOIUrl":"10.1039/D3ME00176H","url":null,"abstract":"<p >We study a coarse-grained model of a nanocomposite consisting of a symmetric AB diblock copolymer and a planar nanoparticle (NP) using dissipative particle dynamics. The NP size exceeds the period of the lamellar domains formed by microphase separation of the copolymer blocks. The model predicts that the NP has two stable orientations due to its anisotropic nature and the difference between the NP size and the period of the matrix domains. In the case of good or poor compatibility of the NP with both copolymer blocks, the NP plane is oriented perpendicular to the plane of the matrix domains. In the case of selective interaction with the copolymer, the NP will be incorporated into the domain formed by the blocks with which it has the greatest compatibility. The appearance of the orientational ordering effect is explained by the imbalance in the distribution of copolymer blocks along the NP surface in the early stages of the microphase separation. This result allows us to consider this system as a two-state nanocomposite. It is also observed that the introduction of the NP reduces the incompatibility threshold of the copolymer blocks above which microphase separation occurs. We hope that the reported effect will be useful for the design of smart nanomaterials with switchable properties.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 4","pages":" 409-422"},"PeriodicalIF":3.6,"publicationDate":"2024-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139689698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Designing biphenanthridine-based singlet fission materials using computational chemistry†","authors":"Keighlynn A. Veilleux, Georg Schreckenbach and David E. Herbert","doi":"10.1039/D3ME00181D","DOIUrl":"10.1039/D3ME00181D","url":null,"abstract":"<p >Singlet fission has the potential to significantly improve the efficiency of photovoltaic devices by harnessing high-energy sunlight to double the photocurrent that can be generated in standard semiconductors. The challenge is identifying materials capable of undergoing this process efficiently. Herein, we present the results of a systematic search for novel intermolecular singlet fission materials based on the recently synthesized 6,6′-biphenanthridine (biphe) framework utilizing a straightforward computational approach. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) were employed to study the photophysics of various structural analogues of biphe. These analogues were generated <em>in silico</em> by utilizing an extensive range of transformations, including planarization, protonation, symmetric and asymmetric alkylation, electron-donating and electron-withdrawing group substitution, <em>N</em>-oxide substitution, and symmetric and asymmetric π-extension and contraction. Analysis of the effects of these structural modifications on the energies of the lowest singlet and triplet excited states revealed that (2,2′,10,10′-tetra-<em>N</em>-oxide) planar biphe has an <em>E</em>(S<small>₁</small>)/<em>E</em>(T<small>₁</small>) ratio of 2.12 and an <em>E</em>(T<small>₂</small>)/<em>E</em>(T<small>₁</small>) of 2.05, suggesting its potential for intermolecular singlet fission. Additionally, <em>N</em>-methylated biphe emerged as a promising contender for thermally activated delayed fluorescence. The effects of solvation are also discussed.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 4","pages":" 423-435"},"PeriodicalIF":3.6,"publicationDate":"2024-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139664199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}