Materials Advances最新文献

{"title":"Mass transfer kinetics of Cr(vi) adsorption on a green mussel shell-polyethersulfone membrane","authors":"Mohamad Ali Fulazzaky, Nur Atikah Abdul Salim, Mohd Hafiz Puteh, Tiffany Messer, Mohd Hafiz Dzarfan Othman, Ahmad Fauzi Ismail, Juhana Jaafar and Mukhlis A. Rahman","doi":"10.1039/D4MA01068J","DOIUrl":"https://doi.org/10.1039/D4MA01068J","url":null,"abstract":"<p >Cr(<small>VI</small>) is toxic to human health and aquatic life, requiring removal from contaminated water. Green mussel shells incorporated into a polyethersulfone (GMSPES) membrane were designed to create a flat sheet adsorptive membrane crossflow treatment permeator (FSAMCFTP) to remove Cr(<small>VI</small>) from a synthetic solution (SS). The physicochemical properties of the GMSPES membrane were verified using a scanning electron microscope, atomic force microscope, and water contact angle goniometer. The adsorption capacities of GMSPES0.5, GMSPES1.0 and GMSPES1.5 were found to be as high as 13.41, 15.24 and 10.84 mg g<small>⁻¹</small>, respectively. The numerical simulation of data using generalized Fulazzaky equations enabled the prediction of the mechanisms and kinetics of external, internal and global mass transfers for the adsorption of Cr(<small>VI</small>) on the GMSPES membrane. Comparison of external and internal mass transfers facilitated the determination of mass transfer resistance, with the internal mass transfer rate beginning at 0.16 h, while the external mass transfer rate dominated for 3.00 h of the experiment. The verification of Cr(<small>VI</small>) adsorption by the GMSPES membrane with different GMS/PES ratios provides a comprehensive understanding of the FSAMCFTP process, contributing to the advancement of adsorptive membrane technology.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1695-1709"},"PeriodicalIF":5.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01068j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of low-shrinkage eco-friendly composite materials for the DLP 3D printing technique","authors":"Wei-Chun Lin, Jui-Fu Tang, Chia-Cheng Cheng, Chia-Chien Kuo and Wei-Hsuan Hung","doi":"10.1039/D4MA00722K","DOIUrl":"https://doi.org/10.1039/D4MA00722K","url":null,"abstract":"<p >3D printing technology has emerged as a production method in the past ten years and has attracted great attention in the market. Among various printing systems, digital light processing (DLP) 3D printing has extremely high planar resolution with a smooth sample surface, which is the best advantage of this technology. However, this 3D printing technology currently has three major challenges that urgently need to be improved: (1) the sample has dimensional shrinkage defects after secondary light curing; (2) the mechanical properties of the printed product have a serious tendency to decrease after secondary curing; and (3) the choice of printing materials used lacks diversification. The aforementioned defects will seriously affect the yield of printed products in high-precision manufacturing. In this research, eco-friendly carbon black has been added to the photosensitive resin of DLP to form composites. The mechanical properties of the material, thermogravimetric analysis, material viscosity, surface morphology and size shrinkage were investigated. In the tensile test, the area after the yield point is also significantly prolonged, which indicates better toughness of the composite resins. Adding recycled carbon black to the material can also enhance the heat resistance and thermal stability of the resin without increasing the solution viscosity. The newly synthesized composite resin demonstrated an improved hardness without severe size shrinkage after the post UV curing process, and also provided a new solution to the issue of abandoned tires.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 6","pages":" 1889-1898"},"PeriodicalIF":5.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma00722k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3D hierarchical rare-earth metal composite nanofiber membranes for highly durable and efficient photodegradations of organic pollutants†","authors":"Aditya Rianjanu, Sephia Amanda Muhtar, Hannah Faye M. Austria, Tarmizi Taher, Noto Susanto Gultom, Wibawa Hendra Saputera, Hutomo Suryo Wasisto, Fatwa F. Abdi, Wei-Song Hung and Januar Widakdo","doi":"10.1039/D4MA01144A","DOIUrl":"https://doi.org/10.1039/D4MA01144A","url":null,"abstract":"<p >The use of powdered photocatalysts in wastewater treatment presents several challenges, such as difficulties in recovery, aggregation during use, and poor reusability, which limit their effectiveness in large-scale environmental applications. To address these issues, we developed sustainable and reusable photocatalytic membranes comprising three-dimensional (3D) hierarchical lanthanum-doped rare-earth metal oxide nanorods integrated onto polyacrylonitrile/polyvinylidene fluoride (PAN/PVDF) nanofibers (La-doped RE-NFs). These hybrid composite membranes were fabricated by combining electrospinning and hydrothermal synthesis methods. The La-doped RE-NFs not only possess a high surface-area-to-volume ratio but also demonstrate superior photocatalytic efficiency for removing common target organic pollutants in water (<em>i.e.</em>, Congo red (CR), methyl orange (MO), methylene blue (MB), and tetracycline (TC)). Here, the formation of the CeCO<small>₃</small>F phase has contributed to the enhanced photocatalytic performance. From the kinetic analysis of the photocatalytic degradation, the rate constant (<em>k</em>) of La-doped RE-NFs in the MB removal test is 4.3 times higher than that of their undoped counterparts. Moreover, these proposed membranes exhibit excellent reusability, with only a ∼5% reduction in degradation efficiency after five consecutive cycles. These findings highlight the potential of La-doped RE-NFs as a highly efficient and reusable photocatalytic membrane material for environmental applications, particularly in water treatment systems.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1755-1768"},"PeriodicalIF":5.2,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01144a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"PDMS-based flexible and conductive composite films containing modified PEDOT:PSS coated channels as a potential neural conduit†","authors":"Orhan Gokalp Buyukuysal, Busra Kilic, Cagatay Karaaslan, Dincer Gokcen, Cem Bayram and Halil Murat Aydin","doi":"10.1039/D4MA01205D","DOIUrl":"https://doi.org/10.1039/D4MA01205D","url":null,"abstract":"<p >Neurological injuries cause the nervous system to malfunction, significantly impacting living standards. Conductive polymers aim to ensure the continuity of nervous system activities and their treatments through specially designed materials. Their soft structure, ability to combine with other polymers, load transfer capacity and biochemical composition enable them to be used in living tissues. Within the scope of this study, conductive and flexible composite films based on PEDOT:PSS aqueous dispersion (PPAD) (poly(3,4-ethylene dioxide thiophene):poly(styrene sulfonate)) were synthesized and combined in different proportions using bis(trifluoromethane)sulfonimide lithium (LiTFSI) salt as a chemical additive. Films were formed by pouring the PDMS polymer into a mold with a special electronic design printed with a 3D printer. Afterwards, the film channels were coated with modified PPAD and PPAD-LiTFSI by dip-coating and spin-coating methods and 1.1 mm thick composite films with channels 0.4 mm wide, 62.8 mm long and 0.1 mm deep were obtained. Several modifications including ion exchange, lyophilization, redispersion, and ethylene glycol (EG) addition have been applied to dispersions. As a consequence, particle size distribution, zeta potential, pH of dispersions, film conductivities and film biocompatibilities were modified as desired. Additionally, lyophilization and redispersion processes have been shown to mostly preserve material properties and extend the shelf life. Furthermore, analyses applied to normal materials were also conducted on samples kept for 12 months (12M), and the effects of time on the materials under different storage conditions were compared. Moreover, as a result of conductivity measurements, it was seen that the PPAD-RAL-EG had a conductivity of 4.67561 S m<small>⁻¹</small> and was among the values that can be used in nerve tissue. Finally, we investigated the <em>in vitro</em> cell culture behaviour of the films using MTT analysis, LDH analysis, ethidium bromide calcein staining and alamar blue assay with the L929 and SH-SY5Y cell lines. The composite films were found to be biocompatible. In conclusion, the shelf life of PEDOT:PSS has been extended, allowing it to be used when necessary, and a composite production and modification method that has the potential to be used in peripheral nerve injuries has been introduced to the literature.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1647-1666"},"PeriodicalIF":5.2,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01205d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel biocompatible multifunctional porous magnetic nanoclusters for the targeted delivery of lenvatinib towards hepatocellular carcinoma†","authors":"Saba Sohail, Alam Zeb, Ali H. Alamri, Adel Al Fatease, Ahmed A. Lahiq, Nabil K. Alruwaili, Salman Khan and Fakhar ud Din","doi":"10.1039/D4MA01101E","DOIUrl":"https://doi.org/10.1039/D4MA01101E","url":null,"abstract":"<p >Hepatocellular carcinoma (HCC) is a very aggressive and deadly disease with a complicated tumor microenvironment (TME). Recently, lenvatinib (LEN) has shown effectiveness in the clinical treatment of HCC, but its limited solubility and serious adverse reactions must not be overlooked. Herein, we developed novel pluronic F127-decorated citric acid-capped, LEN-loaded porous magnetic nanoclusters (PF127/CA/LEN@pMNCs) for effective tumor targeting and toxicity reduction. PF127/CA/LEN@pMNCs were statistically optimized and characterized based on their particle size, polydispersity index (PDI), zeta potential, and entrapment efficiency (%EE). Additionally, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) analyses were performed. Furthermore, advanced characterization techniques such as vibrating sample magnetometry (VSM), Brunauer–Emmett–Teller (BET) method, thermal gravimetric analysis (TGA) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) were employed. In addition to these, <em>in vitro</em> release, hemolytic assay, lactate dehydrogenase (LDH) assay, cell viability and magnetic hyperthermia (MH) analyses of PF127/CA/LEN@pMNCs were performed. Cytotoxicity assay of PF127/CA/LEN@pMNCs under magnetic hyperthermia (MH) exposure conditions was also performed using H22 and Hep3B cells. The successful production of PF127/CA/LEN@pMNCs was confirmed by FTIR spectroscopy and TGA analysis. The optimized PF127/CA/LEN@pMNCs demonstrated 160 nm particle size, −22.80 mV zeta potential, 98% EE, 8.9% loading capacity, hemocompatibility, superparamagnetism, and a prolonged retention time. The iron content of nanoclusters was found to be between 55.78% and 83.91%. Moreover, PF127/CA/LEN@pMNCs exhibited pH responsiveness, and they significantly (<em>p</em> &lt; 0.05) reduced the cell viability of H22 and Hep3B cells. The specific absorption rate of PF127/CA/LEN@pMNCs was 10.79 W g<small>⁻¹</small> at 10 mg mL<small>⁻¹</small>, indicating their potential for MH. Additionally, significantly (<em>p</em> &lt; 0.05) improved cytotoxicity of PF127/CA/LEN@pMNCs was confirmed against H22 and Hep3B cells under the influence of MH. Collectively, this novel research offers valuable insights into harnessing the diverse potentials of combining existing pharmaceuticals with metallic nanomedicine to effectively treat the intractable liver cancer.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1769-1787"},"PeriodicalIF":5.2,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01101e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Type I and type II superconductivity in a quasi-2D Dirac metal†","authors":"Chris J. Lygouras, Junyi Zhang, Jonah Gautreau, Mathew Pula, Sudarshan Sharma, Shiyuan Gao, Tanya Berry, Thomas Halloran, Peter Orban, Gael Grissonnanche, Juan R. Chamorro, Taketora Mikuri, Dilip K. Bhoi, Maxime A. Siegler, Kenneth J.T. Livi, Yoshiya Uwatoko, Satoru Nakatsuji, B. J. Ramshaw, Yi Li, Graeme M. Luke, Collin L. Broholm and Tyrel M. McQueen","doi":"10.1039/D5MA00022J","DOIUrl":"https://doi.org/10.1039/D5MA00022J","url":null,"abstract":"<p >We explore bulk superconducting phase in single crystals of the Dirac material LaCuSb<small>₂</small> prepared by the self-flux method. Magnetization, muon spin relaxation measurements, and density functional theory, show the Dirac nodal line Fermi surfaces give rise to type-II superconductivity for magnetic fields applied along the <strong><em>a</em></strong>-axis, and type-I superconductivity for fields along the <strong><em>c</em></strong>-axis. Both chemical and hydrostatic pressure drastically suppress the superconducting transition. We find multiband superconductivity evidenced by a precipitous drop in the electronic specific heat capacity and high-pressure susceptibility for <em>T</em>* &lt; <em>T</em><small>_c</small>/3. Our work demonstrates dirty-limit, weak-coupling multiband superconductivity in LaCuSb<small>₂</small>, and highlights the role of Dirac fermions on its anisotropic character.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1685-1694"},"PeriodicalIF":5.2,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d5ma00022j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxygen partial pressure effects on nickel oxide thin films and NiO/Si diode performance","authors":"Thi Kim Hang Pham, Bao Quan Tran, Khac Binh Nguyen, Ngoc Yen Nhi Pham, Thi Hai Yen Nguyen, An Hoang-Thuy Nguyen, Ngoc Phuong Nguyen, Hai Dang Ngo and Hoai Phuong Pham","doi":"10.1039/D4MA01113A","DOIUrl":"https://doi.org/10.1039/D4MA01113A","url":null,"abstract":"<p >In this work, nickel oxide thin films were grown on glass and n-type Si substrates using RF-magnetron sputtering in an oxygen-rich environment. The effects of elevated oxygen on the optical properties, electrical properties, ionic states, compositional analysis, surface morphology, and crystal structure are investigated. The X-ray diffraction data, which also demonstrate the presence of two phases in all samples: NiO and Ni<small>₂</small>O<small>₃</small>, indicate that the highly crystalline Ni<small>₂</small>O<small>₃</small> phase in the nickel oxide thin film structure has a (002) growth orientation. According to X-ray photoelectron spectroscopy, the ratio of Ni<small>³⁺</small> (Ni<small>₂</small>O<small>₃</small> phase) to Ni<small>²⁺</small> (NiO) states increases as the oxygen concentration increases. In the nickel oxide thin films, the ratio of Ni<small>³⁺</small> states is substantially higher than that of Ni<small>²⁺</small> states. The optical band gap is around 3.4 eV, as determined from UV-Vis transmission spectroscopy, and the average transmittance of nickel oxide thin films exceeds 50% in the visible spectrum. The nickel oxide thin films demonstrate a substantial carrier concentration between 2.33 × 10<small>¹⁹</small> and 7.46 × 10<small>¹⁹</small> cm<small>⁻³</small>, with a minimum resistivity of 0.28 Ω cm. Furthermore, the p–n heterojunctions of the p-nickel oxide/n-silicon substrates revealed the optimal diode characteristic parameters at a 30% oxygen gas ratio. The results have been promising for further industrial development and fabrication of diodes.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1719-1725"},"PeriodicalIF":5.2,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01113a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of the oxidation level of the graphene oxide substrate on in situ growth of COF-300†","authors":"Ying Quan, Yizhou Yang, Qinfu Liu and Karl Börjesson","doi":"10.1039/D4MA01088D","DOIUrl":"https://doi.org/10.1039/D4MA01088D","url":null,"abstract":"<p >The synthesis of covalent organic framework (COF) based hybrid materials is highly important for society as it provides materials with a large variety of beneficial properties. However, the COFs in graphene–COF and reduced graphene oxide (rGO)–COF hybrids are mostly two-dimensional (2D) due to the challenge in the design and synthesis of three-dimensional (3D) COFs. rGO-3D COF composites were here synthesized using several different graphene oxide (GO) substrates <em>via</em> a simple ventilation-vial protocol. These composites, as well as the starting materials of GO, were characterized by XRD, Raman spectroscopy, XPS, FT-IR, TG, SEM and EDS. The mechanism of <em>in situ</em> growth of COF-300 on graphene is proposed, where the oxygen-containing functional groups on GO are assumed to play a leading role in anchoring COF-300. Interestingly, a change in the morphology of COF-300 particles on the GO substrate was observed. It is found that GO acts as not only the substrate but also a structure-directing agent for modulating the morphology of COF-300. The high oxidation level and the large interlayer distance of GO are beneficial for growing COF-300 with smaller length, higher loading and more uniform distribution. This finding opens an avenue to control the morphology of COFs just by regulating the GO substrate. This work also covers GO prepared from natural coaly graphite, which promotes the high-value utilization of natural coaly graphite resources.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1744-1754"},"PeriodicalIF":5.2,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01088d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Therapeutic systems based on natural gut microbiota modulators: the latest advances in the treatment of inflammatory bowel disease","authors":"Zelin Guan, Peilin Niu, Qichao Tan, Yidong Wang, Shujing Deng, Danyang Wang, Kai Dong, Jianfeng Xing and Cuiyu You","doi":"10.1039/D4MA00896K","DOIUrl":"https://doi.org/10.1039/D4MA00896K","url":null,"abstract":"<p >The gut microbiota plays an indispensable role in maintaining gut health. However, the imbalance of gut microbiota under inflammatory conditions is closely related to the acceleration of inflammatory bowel disease (IBD) progression. Consequently, modulating the gut microbiota is one of the crucial strategies for treating IBD. Naturally sourced phytonutrients, probiotics, prebiotics, gut microbiota metabolites and extracellular vesicles (EVs) exhibit remarkable gut microbiota regulation capabilities through diverse pathways, for instance, exerting anti-inflammatory and antioxidant activities, competing with harmful bacteria for nutrients, selectively promoting the proliferation of beneficial bacteria, regulating immune homeostasis, and so on. Since they are all derived from nature and exhibit excellent gut microbiota modulation capabilities, we define them as “natural gut microbiota modulators” (NGMMs). In recent years, the thriving development of therapeutic systems has illuminated the direction for the advancement of NGMMs. Constructing therapeutic systems based on MGMMs can overcome the challenges they face in treating IBD and significantly enhance their therapeutic efficacy. In this review, We first reviewed the role of gut microbiota in IBD, and then systematically summarized how the therapeutic system based on NGMMs positively influences the intestinal microbiota. Furthermore, we sort out the challenges faced by these therapeutic systems and offer insights into their prospects.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1578-1607"},"PeriodicalIF":5.2,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma00896k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient oxidative coupling of amines to imines under natural sunlight using a benzothiadiazole-based molecular photocatalyst†","authors":"Ajeet Singh, Bidisa Das and Saumi Ray","doi":"10.1039/D4MA00990H","DOIUrl":"https://doi.org/10.1039/D4MA00990H","url":null,"abstract":"<p >Developing a ‘greener’ avenue for organic synthesis is a key challenge, which must focus on energy efficiency as well as sustainability. Harnessing solar energy to chemical energy is an efficient way to utilize renewable energy resources. Herein, we report a D–A-type (donor–acceptor-type) small organic molecular photocatalyst (SOMP) “Ph-BT-Ph” with benzothiadiazole as the primary photoactive unit for oxidative coupling of amines to synthesize imines. Photocatalyst Ph-BT-Ph is synthesized using a Suzuki–Miyaura coupling reaction and thoroughly characterized by <small>¹</small>H-NMR, HRMS, and cyclic voltammetry studies. Photoluminescence and lifetime studies of Ph-BT-Ph show a high excited state reduction potential (−1.37 V <em>vs.</em> Ag/AgCl) and longer lifetime (12.64 ns) which make it suitable for photocatalytic organic transformations. The photocatalytic activity of the catalyst has been evaluated on the direct oxidative coupling reaction of amines to synthesize imines in the presence of natural sunlight and O<small>₂</small> as a green oxidant. Catalyst Ph-BT-Ph exhibits excellent photocatalytic performance under optimal reaction conditions by converting &gt;99% amine to imine with &gt;98% selectivity within 2 hours. This high photocatalytic efficiency has been achieved by purging oxygen only for 2 minutes and without any mechanical energy input (no stirring). Quite a moderate amount of catalyst (0.13 mol%) has been employed which results in a high catalytic turnover frequency of 381 h<small>⁻¹</small>. EPR spectroscopy and theoretical studies are performed to understand the reaction mechanism and to determine the active sites of the catalyst. The Ph-BT-Ph catalyst surpasses the photocatalytic efficiencies of many reported metal-free catalysts for oxidative coupling of amines. Such SOMPs, with easily tunable absorption range and well-defined energy-band positions, offer a new class of metal-free and photoactive catalysts for organic synthesis with outstanding performance under greener reaction conditions.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 5","pages":" 1667-1678"},"PeriodicalIF":5.2,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma00990h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}