99-98-9Relevant academic research and scientific papers
Developments in Dynamic Covalent Chemistries from the Reaction of Thiols with Hexahydrotriazines
Wojtecki, Rudy J.,Jones, Gavin O.,Yuen, Alexander Y.,Chin, Willy,Boday, Dylan J.,Nelson, Alshakim,García, Jeannette M.,Yang, Yi Yan,Hedrick, James L.
, p. 14248 - 14251 (2015)
Dynamic covalent chemistries have garnered significant attention for their potential to revolutionize technologies in the material fields (engineering, biomedical, and sensors) and synthetic design strategies as they provide access to stimuli responsiveness and adaptive behaviors. However, only a limited number of molecular motifs have been known to display this dynamic behavior under mild conditions. Here, we identified a dynamic covalent motif - thioaminals - that is produced from the reaction of hexahydrotriazines (HTs) with thiols. Furthermore, we report on the synthesis of a new family of step-growth polymers based on this motif. The condensation efficiently proceeds to quantitative yields within a short time frame and offers versatility in functional group tolerance; thus, it can be exploited to synthesize both small molecule thioaminals as well as high molecular weight polymers from the step-growth polymerization of HTs with dithiols. Careful evaluation of substituted HTs and organic thiols supported by DFT calculations led to a chemically diverse library of polymers based on this motif. Finally, dynamic substitution reactions were employed toward the facile preparation of functional oligomers and macromolecules. This dynamic covalent motif is particularly attractive for a range of applications that include material design and drug delivery due to the economic feasibility of synthesis.
Naphthalimide-Based Azo-Functionalized Supramolecular Vesicle in Hypoxia-Responsive Drug Delivery
Sarkar, Deblina,Chowdhury, Monalisa,Das, Prasanta Kumar
, p. 3480 - 3492 (2022/03/27)
Supramolecular materials that respond to external triggers are being extensively utilized in developing spatiotemporal control in biomedical applications ranging from drug delivery to diagnostics. The present article describes the development of self-assembled vesicles in 1:9 (v/v), tetrahydrofuran (THF)-water by naphthalimide-based azo moiety containing amphiphile (NI-Azo) where azo moiety would act as the stimuli-responsive junction. The self-assembly of NI-Azo took place through H-type of aggregation. Microscopic and spectroscopic analyses confirmed the formation of supramolecular vesicles with a dimension of 200-250 nm. Azo (-N=N-) moiety is known to get reduced to amine derivatives in the presence of the azoreductase enzyme, which is overexpressed in the hypoxic microenvironment. The absorbance intensity of this characteristic azo (-N=N-) moiety of NI-Azo (1:9 (v/v), THF-water) at 458 nm got diminished in the presence of both extracellular and intracellular bacterial azoreductase extracted from Escherichia coli bacteria. The same observation was noted in the presence of sodium dithionite (mimic of azoreductase), indicating that azoreductase/sodium dithionite induced azo bond cleavage of NI-Azo, which was confirmed by matrix-assisted laser desorption ionization time-of-flight spectrometric data of the corresponding aromatic amine fragments. The anticancer drug, curcumin, was encapsulated inside NI-Azo vesicles that successfully killed B16F10 cells (cancer cells) in CoCl2-induced hypoxic environment owing to the azoreductase-responsive release of drug. The cancer cell killing efficiency by curcumin-loaded NI-Azo vesicles in the hypoxic condition was 2.15-fold higher than that of the normoxic environment and 2.4-fold higher compared to that of native curcumin in the hypoxic condition. Notably, cancer cell killing efficiency of curcumin-loaded NI-Azo vesicles was 4.5- and 1.9-fold higher than that of noncancerous NIH3T3 cells in normoxic and hypoxic environments, respectively. Cell killing was found to be primarily through the early apoptotic pathway.
Nickel Boride Catalyzed Reductions of Nitro Compounds and Azides: Nanocellulose-Supported Catalysts in Tandem Reactions
Proietti, Giampiero,Prathap, Kaniraj Jeya,Ye, Xinchen,Olsson, Richard T.,Dinér, Peter
, p. 133 - 146 (2021/11/04)
Nickel boride catalyst prepared in situ from NiCl2 and sodium borohydride allowed, in the presence of an aqueous solution of TEMPO-oxidized nanocellulose (0.01 wt%), the reduction of a wide range of nitroarenes and aliphatic nitro compounds. Here we describe how the modified nanocellulose has a stabilizing effect on the catalyst that enables low loading of the nickel salt pre-catalyst. Ni-B prepared in situ from a methanolic solution was also used to develop a greener and facile reduction of organic azides, offering a substantially lowered catalyst loading with respect to reported methods in the literature. Both aromatic and aliphatic azides were reduced, and the protocol is compatible with a one-pot Boc-protection of the obtained amine yielding the corresponding carbamates. Finally, bacterial crystalline nanocellulose was chosen as a support for the Ni-B catalyst to allow an easy recovery step of the catalyst and its recyclability for new reduction cycles.
Green synthesized AgNPs decorated on Ketjen black for enhanced catalytic dye degradation
Ramaraghavulu, Rajavaram,Rao, V. Koteswara,Devarayapalli,Yoo, Kisoo,Nagajyothi,Shim, Jaesool
, p. 637 - 648 (2020/10/15)
The green synthesis of nanoparticles using plant-based materials as an alternative to chemical and physical routes provides economic and environmental benefits. In the present study, silver nanoparticles (AgNPs) were fabricated using Pseudocydonia sinensis fruit extract. The fabricated NPs were then decorated on commercial Ketjen black-300 (AgNPs@KB-300) and Ketjen black-600 (AgNPs@ KB-600). The synthesized materials were characterized via XRD, FTIR, XPS, SEM-EDX, and HR-TEM studies. The SEM and HR-TEM results revealed that the synthesized AgNPs were spherical and successfully decorated on KB-300 and KB-600. Additionally, the catalytic ability of the synthesized samples during the degradation of methyl orange in the presence of NaBH4 was studied. Notably, the catalytic activity of AgNPs@ KB-600 was higher than that of AgNPs@ KB-300.
Synthesis and characterization of polyaniline/nickel oxide composites for fuel additive and dyes reduction
Jamil, Saba,Ahmad, Zunaira,Ali, Muhammad,Rauf Khan, Shanza,Ali, Sarmed,Amen Hammami, Mohamed,Haroon, Muhammad,Saleh, Tawfik A.,Ramzan Saeed Ashraf Janjua, Muhammad
, (2021/05/13)
Polyaniline (PANI) and Polyaniline/Nickel oxide (PANI/NiO) composites are prepared to use as a potential catalyst, by Chemical oxidation method using ammonium persulfate (NH4)2S2O8)) as an oxidant. Nickel oxide (NiO) nanopartiles are prepared by Sol-gel method. The synthesized products were characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray analysis (EDX), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Diffraction technique (XRD). The prepared PANI/NiO composites are used as additive with different concentrations in diesel to investigate their efficiency as fuel additive. The catalytic properties are studied by using the synthesized products as catalyst for reduction of dyes in aqueous media. Sodium borohydride (NaBH4) is used as reducing agent. Linear relationships are obtained between time and ln(A0/At) for Methyl orange and Methylene blue. Kapp values were obtained for three catalysts showed the increasing trend of reduction for both dyes as, PANI NiO PANI/NiO composites. Experimental data analysis proved PANI/NiO composites to be efficient catalysts and fuel additive as compared to PANI and NiO.
Cyan color-emitting nitrogen-functionalized carbon nanodots (NFCNDs) from Indigofera tinctoria and their catalytic reduction of organic dyes and fluorescent ink applications
Abirami, Natarajan,Arul, Velusamy,Arulmozhi, Rajaram,Kavitha, Ganesan,Vinoth Kumar, Jothi
, p. 27745 - 27756 (2021/08/25)
The present study reports the synthesis of nitrogen-functionalized carbon nanodots (NFCNDs) by a low-cost hydrothermal method using the leaf extract of Indigofera tinctoria as a novel carbon precursor. The synthesized NFCNDs were characterized by diverse spectroscopic techniques. The optical properties of N-CNDs were analyzed by UV-visible and fluorescence spectroscopic studies. The quantum yield (QY) for the prepared NFCNDs was found to be 12.6%. The surface morphology, functional groups, and crystallinity of NFCNDs were evaluated by HR-TEM, FT-IR, XRD and Raman spectroscopic methods, respectively. The Raman results revealed the moderate graphite structure of NFCNDs, and the calculated ID/IG value was 0.49. The spherical appearance of the synthesized NFCNDs was confirmed by HR-TEM, and the calculated size of the NFCNDs was 4 nm. The XRD and SAED pattern results gives an evidence for the amorphous nature of the prepared NFCNDs. The thermal stability of NFCNDs was studied by TGA analysis. The resulting NFCNDs acted as a green nanocatalyst and thus efficiently improved the reducing capability of sodium borohydride (NaBH4) in the catalytic reduction of methylene blue (MB) and methyl orange (MO) dyes. Furthermore, the bright cyan emission characteristics of synthesized NFCNDs were utilized as a labeling agent in anti-counterfeiting applications.
Cu/CuxS-Embedded N,S-Doped Porous Carbon Derived in Situ from a MOF Designed for Efficient Catalysis
Wang, Dongsheng,Fan, Mingyue,He, Tingyu,Zeng, Fanming,Hu, Xiaoli,Li, Chun,Su, Zhongmin
supporting information, p. 11468 - 11476 (2021/06/14)
The reasonable design of the precursor of a carbon-based nanocatalyst is an important pathway to improve catalytic performance. In this study, a simple solvothermal method was used to synthesize [Cu(TPT)(2,5-tdc)] ? 2H2O (Cu-MOF), which contains N and S atoms, in one step. Further in-situ carbonization of the Cu-MOF as the precursor was used to synthesize Cu/CuxS-embedded N,S-doped porous carbon (Cu/CuxS/NSC) composites. The catalytic activities of the prepared Cu/CuxS/NSC were investigated through catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The results show that the designed Cu/CuxS/NSC has exceptional catalytic activity and recycling stability, with a reaction rate constant of 0.0256 s?1, and the conversion rate still exceeds 90 % after 15 cycles. Meanwhile, the efficient catalytic reduction of dyes (CR, MO, MB and RhB) confirmed its versatility. Finally, the active sites of the Cu/CuxS/NSC catalysts were analyzed, and a possible multicomponent synergistic catalytic mechanism was proposed.
Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines
Ben-David, Yehoshoa,Das, Uttam Kumar,Diskin-Posner, Yael,Kar, Sayan,Milstein, David
supporting information, p. 3744 - 3749 (2021/07/09)
We report the first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies. (Figure presented.).
Development of sustainable and efficient nanocatalyst based on polyoxometalate/nickel oxide nanocomposite: A simple and recyclable catalyst for reduction of nitroaromatic compounds
Kurbah, Sunshine Dominic
, p. 1487 - 1495 (2021/04/22)
In this paper, we report the synthesis and characterization of NiO@PolyMo nanocomposite. The newly synthesized nanocomposite was characterized by transmission electronmicroscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and powder X-ray diffraction (XRD). The particle sizes of the NiO@PolyMo nanocatalyst are in the range of 10–20 nm. Powder XRD patterns show that the phase of NiO@PolyMo remains unaltered even after the functionalization of NiO. The lattice fringes of d = 0.20 nm were observed, which correspond to the (111) plane of NiO phase. The newly synthesized material shows excellent catalytic performance and good selectivity for reduction of nitroarenes. The advantages of the present protocols are mild, and can be carried out using water as a solvent, which is an eco-friendly benign.
Photocatalytic reduction of nitroaromatics into anilines using CeO2-TiO2 nanocomposite
Chen, Changdong,Lu, Caiyun,Sun, Chengxin,Wang, Fangfang,Yin, Zhengfeng
, (2021/08/19)
The reduction of nitro compounds into amines is an important approach for synthetic and pharmaceutical chemistry. The reduced compounds are used as synthetic intermediates in the synthesis of therapeutic molecules. In the present work, we have fabricated cerium dioxide decorated TiO2 nanoparticles using a sol-gel-hydrothermal method. The synthesized nanocomposite was effectively reduced various nitro-compounds, specifically aromatic nitro compounds, into amines in visible light. All the nitro compounds screened in the photoreduction reaction showed >90% conversion with >96% selectivity. Chromatographic techniques confirmed the products obtained. The nanocomposite photocatalyst has excellent stability under the experimental condition and exhibited up to five cycles with no loss of metal content. The nanomaterials were characterized using various spectroscopic techniques.
