623-27-8Relevant articles and documents
A lanthanide-functionalized covalent triazine framework as a physiological molecular thermometer
Abalymov, Anatolii,Abednatanzi, Sara,Bourda, Laurens,Dalapati, Sasanka,Gohari Derakhshandeh, Parviz,Kaczmarek, Anna M.,Liu, Ying-Ya,Meledina, Maria,Skirtach, Andre G.,Van Der Voort, Pascal,Van Hecke, Kristof
, p. 6436 - 6444 (2021)
Crystalline covalent triazine frameworks (CTFs) with intrinsic porosity and high stability are an excellent platform for engineering luminescence properties, as their building blocks and guest ions are all important factors in light emission. Herein, a highly crystalline bipyridine-based CTF (Bipy-CTF) is synthesized under mild conditions. The controlled tethering of lanthanide ions (Ln = Eu3+ and Tb3+) onto Bipy-CTF combined with selective photoexcitation results in a ratiometric luminescent thermometer (LnCTF). This LnCTF thermometer exhibits an excellent linear response in the solid state over a wide range of temperatures (200-340 K), with a temperature uncertainty below 0.2% and very good reusability (up to 98.5% repeatability). Moreover, the suspended material in water shows a temperature sensitivity down to 253 K (-20 °C), which is a very important finding for monitoring the physiological processes within biological and biochemical systems during freezing/defrosting treatment with precise temperature measurements. We also studied and confirmed the low cytotoxicity of the LnCTF towards cells thereby opening prospects for future in vivo applications. This work thus highlights a new application of LnCTF materials as ratiometric luminescent molecular thermometers with excellent sensitivity in the physiological temperature range.
Metal nanoparticles decorated MIL-125-NH2 and MIL-125 for efficient photocatalysis
Qiu, Jianhao,Yang, Lvye,Li, Ming,Yao, Jianfeng
, p. 297 - 306 (2019)
Metal nanoparticles (NPs) decorated MOFs for photocatalysis has drawn enormous attention in the past decade. Here, a series of M/Ti-MOFs (M = Pt and Au, Ti-MOFs = MIL-125-NH2 and MIL-125) has been synthesized through a facile post-synthetic method and the metal NPs highly dispersed on surface of MOFs with major sizes of 3–9 nm. Light absorption edges of scaffolds are crucial in the photocatalytic oxidation of benzyl alcohol over M/MIL-125-NH2 and M/MIL-125. The conversion of benzyl alcohol over Pt/MIL-125-NH2 is 2.4 times and 1.9 times higher than that of pristine MIL-125-NH2 and Au/MIL-125-NH2, respectively. Besides, Pt/MIL-125-NH2 photocatalyst also exhibited good activity for Cr(VI) reduction compared to that of MIL-125-NH2. The enhanced photocatalytic activity of Pt/MIL-125-NH2 is contributed to the rapid transfer of photo-induced electrons and decreased recombination of electron-hole pairs, which is verified by measurements of photocurrent and Electrochemical Impedance Spectroscopy. We hope that this study will provide worthy information for designing metal/MOFs or metal/MOFs-NH2 photocatalysts.
Synthesis of 4-(dibromomethyl)benzenecarbaldehyde and its reactions with N- and O-nucleophiles
Gazizov,Ivanova, S. Yu.,Karimova,Bagauva,Gazizova,Karimova
, p. 191 - 194 (2016)
4-(Dibromomethyl)benzenecarbaldehyde was first synthesized and its preparation method jointly with terephthalic aldehyde was developed. Its reactions with O- and N-nucleophiles were studied: the reaction of this aldehyde with trialkyl orthoformates results in the formation of acetals while reacting with primary amines it forms imines, including those containing an additional acetal group.
Nano–silica functionalized with thiol–based dendrimer as a host for gold nanoparticles: An efficient and reusable catalyst for chemoselective oxidation of alcohols
Haghshenas Kashani, Sara,Landarani-Isfahani, Amir,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
, (2018)
In this paper, we present the synthesis of Au nanoparticles supported on nanosilica thiol based dendrimer, nSTDP. The catalyst was prepared by reduction of HAuCl4 with NaBH4 in the presence of nSTDP. The resulting Aunp–nSTDP materials were characterized by FT–IR and UV–vis spectroscopic methods, SEM, TEM, TGA, XPS and ICP analyses. The characterization of the catalyst showed that Au nanoparticles with the size of 2–6?nm are homogeneously distributed on the nSTDP dendrimer with a catalyst loading of about 0.19?mmol/g of catalyst. The Aunp–nSTDP catalyst was used in the oxidation of alcohols with tert–butyl hydroperoxide (TBHP) as oxidant. The influence of vital reaction parameters such as solvent, oxidant and amount of catalyst on the oxidation of alcohols was investigated. These reactions were best performed in an acetonitrile/water mixture (3:2) in the presence of 0.76?mol% of the catalyst on the basis of the Au content at 80?°C under atmospheric pressure of air to afford the desired products in high yields (80–93% for benzyl alcohols). The Aunp–nSTDP catalyst exhibited a high selectivity toward the corresponding aldehyde and ketone (up to 100%). Reusabiliy and stability tests demonstrated that the Aunp–nSTDP catalyst can be recycled with a negligible loss of its activity. Also this catalytic exhibited a good chemoselectivity in the oxidation of alcohols.
A Synergistic Magnetically Retrievable Inorganic-Organic Hybrid Metal Oxide Catalyst for Scalable Selective Oxidation of Alcohols to Aldehydes and Ketones
Mittal, Rupali,Awasthi, Satish Kumar
, p. 4799 - 4813 (2021/09/30)
Herein, we report a synergistic silica coated magnetic Fe3O4 catalyst functionalized with nitrogen rich organic moieties and immobilized with cobalt metal ion (FNP-5) for selective oxidation of alcohols to aldehydes and ketones using tert-butyl hydroperoxide (TBHP) as oxidant. The catalyst was rigorously characterized via several techniques which delineate its core-shell structure, magnetic behavior, phase and crystal structure. The Co(III) acts as the active catalytic center for selective oxidation reaction. The control reactions revealed radical mechanistic pathway assisted by the synergism induced by the inorganic-organic hybrid nature of FNP-5. The other features of current protocol involve neat reaction conditions, high TOF values, scalability of product and low E-factor value (1.92). Moreover, FNP-5 could be effortlessly separated via an external magnet, displays recyclability over eight catalytic cycles and exhibits structural integrity even after rigorous use. Overall, these results manifest the understanding of synergistic architectures as sustainable surrogates for selective oxidation reactions.
Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide
Badani, Purav,Chaturbhuj, Ganesh,Ganwir, Prerna,Misal, Balu,Palav, Amey
supporting information, (2021/06/03)
Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.
Catalytic study of the copper-based magnetic nanocatalyst on the aerobic oxidation of alcohols in water
Dehkordi, S. Saeid Saei,Albadi, Jalal,Jafari, Abbas Ali,Samimi, Heshmat Allah
, p. 2527 - 2538 (2021/03/24)
A copper-based magnetic nanocatalyst has been prepared by co-precipitation method and characterized by FESEM, EDS, TEM, XRD, XRF, ICP–OES, FTIR, and BET analysis. This new nanocatalyst displays a good activity toward the aerobic oxidation of a wide range of alcohols in water. Moreover, it is recyclable up to five following runs by simple filtration without any significant loss of its catalytic activity.
Synthesis of new Zn (II) complexes for photo decomposition of organic dye pollutants, industrial wastewater and photo-oxidation of methyl arenes under visible-light
Ahemed, Jakeer,Bhongiri, Yadagiri,Chetti, Prabhakar,Gade, Ramesh,Kore, Ranjith,Pasha, Jakeer,Pola, Someshwar,Rao D, Venkateshwar
, (2021/07/28)
Synthesis of new Schiff's base Zn-complexes for photo-oxidation of methyl arenes and xylenes are reported under visible light irradiation conditions. All the synthesized new ligands and Zn-complexes are thoroughly characterized with various spectral analyses and confirmed as 1:1 ratio of Zn and ligand with distorted octahedral structure. The bandgap energies of the ligands are higher than its Zn-complexes. These synthesized new Zn(II) complexes are used for the photo-fragmentation of organic dye pollutants, photodegradation of food industrial wastewater and oxidation of methyl arenes which are converted into its respective aldehydes with moderate yields under visible light irradiation. The photooxidation reaction dependency on the intensity of the visible light was also studied. With the increase in the dosage of photocatalyst, the methyl groups are oxidized to get aldehydes and mono acid products, which are also identified from LC-MS data. Finally, [Zn(PPMHT)Cl] is with better efficiency than [Zn(PTHMT)Cl] and [Zn(MIMHPT)Cl] for oxidation of methyl arenes is reported under visible-light-driven conditions.
Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
supporting information, p. 8108 - 8115 (2021/10/29)
The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
Samarium-based Grignard-type addition of organohalides to carbonyl compounds under catalysis of CuI
Liu, Chen,Liu, Yongjun,Qi, Yan,Song, Bin,Wang, Liang,Xiao, Shuhuan
, p. 6169 - 6172 (2021/06/30)
Grignard-type additions were readily achieved under the mediation of CuI (10 mol%) and samarium (2 equiv.) by employing various organohalides,e.g.benzyl, aryl, heterocyclic and aliphatic halides (Cl, Br or I), and diverse carbonyl compounds (e.g.carbonic esters, carboxylic esters, acid anhydrides, acyl chlorides, ketones, aldehydes, propylene epoxides and formamides) to afford alcohols, ketones and aldehydes, respectively, with high efficiency and chemoselectivity, in which the organosamarium intermediate might be involved.
