Synergistic performance of a new bimetallic complex supported on magnetic nanoparticles for Sonogashira and C-N coupling reactions.

This paper describes the synthesis of a novel Cu-Ni bimetallic system comprising of magnetic nanoparticles, as the core, and 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (4-ABPT), as a conjugated bridge, between nickel and copper species. With low Cu and Ni loading (0.06 mol% Ni, 0.08 mol% Cu), the resulting Fe3O4@SiO2@4-ABPT/Cu-Ni showed to be a highly efficient catalyst for the Sonogashira and C-N cross-coupling reactions. The developed catalyst was well characterized by FT-IR, XRD, EDX-mapping, FE-SEM, TEM, ICP, VSM, TGA/DTG/DTA, LSV, and XPS techniques. Fe3O4@SiO2@4-ABPT/Cu-Ni nanocatalyst was compatible with a wide range of amines and aryl halides in the Sonogashira and C-N cross-coupling reactions and offered desired coupling products in high to excellent yields under palladium- and solvent-free conditions. Based on the XPS results, the 4-ABPT ligand can adjust electron transfer between Ni and Cu in Fe3O4@SiO2@4-ABPT/Cu-Ni, promoting the formation and stabilization of Cu+ and Ni3+ species. Electronic interactions and the synergistic effect between these metals increased the selectivity and activity of Fe3O4@SiO2@4-ABPT/Cu-Ni catalyst in the Sonogashira and C-N cross-coupling reactions compared with its monometallic counterparts. Additionally, the magnetic properties of Fe3O4@SiO2@4-ABPT/Cu-Ni facilitated its separation from the reaction mixture, promoting its reuse for several times with no significant loss in its catalytic activity or performance.

Correction: A novel, efficient and magnetically recyclable Cu-Ni bimetallic nanocomposite as a highly active bifunctional catalyst for Pd-free Sonogashira and C-N cross-coupling reactions: a combined theoretical and experimental study.

[This corrects the article DOI: 10.1039/D3RA01965A.].

A novel, efficient and magnetically recyclable Cu-Ni bimetallic alloy nanoparticle as a highly active bifunctional catalyst for Pd-free Sonogashira and C-N cross-coupling reactions: a combined theoretical and experimental study.

In this study, a Fe3O4@SiO2@Cyt-Ni/Cu nanocomposite as a novel heterogeneous bimetallic catalyst was synthesized which exhibits efficient performance for the Sonogashira and C-N cross-coupling reactions. The characterization of the catalyst was studied by FT-IR, PXRD, VSM, EDX, TEM, FE-SEM and TGA analyses. The geometry optimization and relative energies of the designed bimetallic complexes were theoretically determined using density functional theory (DFT) calculation at the B3LYP/6-31G**/LANL2DZ level. The catalyst showed good activity in the coupling of various aryl halides with alkynes (Sonogashira reaction) as well as aryl halide with N-heterocycles and achieved coupling products with good to high yields for all of them in a short time. The high catalytic performance could be due to the synergistic effect between Ni and Cu, which causes the reaction to proceed more efficiently. This heterogeneous nanocatalyst could be easily recovered from the reaction mixture with an external magnet and reused for 7 consecutive runs with minimal loss of catalytic activity.

Comparison of Robot-Assisted and Manual Cannula Insertion in Simulated Big-Bubble Deep Anterior Lamellar Keratoplasty.

This study aimed to compare the efficacy of robot-assisted and manual cannula insertion in simulated big-bubble deep anterior lamellar keratoplasty (DALK). Novice surgeons with no prior experience in performing DALK were trained to perform the procedure using manual or robot-assisted techniques. The results showed that both methods could generate an airtight tunnel in the porcine cornea, and result in successful generation of a deep stromal demarcation plane representing sufficient depth reached for big-bubble generation in most cases. However, the combination of intraoperative OCT and robotic assistance received a significant increase in the depth of achieved detachment in non-perforated cases, comprising a mean of 89% as opposed to 85% of the cornea in manual trials. This research suggests that robot-assisted DALK may offer certain advantages over manual techniques, particularly when used in conjunction with intraoperative OCT.

Copper adorned magnetic nanoparticles as a heterogeneous catalyst for Sonogashira coupling reaction in aqueous media.

A nanomagnetic hydrophilic heterogeneous copper catalyst, termed γ-Fe2O3@PEG@PAMAM G0-Cu, has been successfully prepared and characterized using FT-IR, XRD, FE-SEM, TEM, EDX, mapping, TGA/DTG, VSM and ICP analyses. The catalyst displayed excellent activity for the palladium-free Sonogashira cross coupling reaction of various aryl iodides and bromides with phenylacetylene derivatives in pure water. The presence of polyethylene glycol coupled with hydrophilic character of the Cu-catalyst adorned on γ-Fe2O3 MNPs provides the ready dispersion of the catalyst particles in water, leading to higher catalytic performance as well as facile catalyst recovery via simple magnetic decantation. The recovered catalyst was reused for at least six successive runs with little reduction in its catalytic activity and any noticeable changes in its structure. The use of water as a green solvent, without requiring any additive or organic solvent, as well as the exploitation of abundant and low-cost copper catalyst instead of expensive Pd catalyst along with the catalyst recovery and scalability, make this method favorable from environmental and economic points of view for the Sonogashira coupling reaction.

Dendritic structured palladium complexes: magnetically retrievable, highly efficient heterogeneous nanocatalyst for Suzuki and Heck cross-coupling reactions.

The recyclable nanomagnetic Pd-complex PAMAM G0-Pd@γ-Fe2O3 is reported for catalytic C-C cross-coupling reactions of challenging substrates. Mainly, a great variety of aryl chlorides can be used as substrates for Suzuki-Miyaura and Mizoroki-Heck reactions under mild reaction conditions (60-90 °C) and low catalyst loading (<1 mol% Pd) in aqueous media. The presence of numerous polar groups in the polymer matrix increases the solubility of the catalyst in water, thus facilitating its operation in aqueous environments. The immobilization of the catalyst on the surface of a magnetic platform allows its effective recovery and reuse without significant loss of catalytic activity for at least six cycles with total leaching of <1% palladium metal, meeting the requirements for acceptable metal residues in the pharmaceutical industry.

A Tool for High-Resolution Volumetric Optical Coherence Tomography by Compounding Radial-and Linear Acquired B-Scans Using Registration.

Optical coherence tomography (OCT) is a medical imaging modality that is commonly used to diagnose retinal diseases. In recent years, linear and radial scanning patterns have been proposed to acquire three-dimensional OCT data. These patterns show differences in A-scan acquisition density across the generated volumes, and thus differ in their suitability for the diagnosis of retinal diseases. While radial OCT volumes exhibit a higher A-scan sampling rate around the scan center, linear scans contain more information in the peripheral scan areas. In this paper, we propose a method to combine a linearly and radially acquired OCT volume to generate a single compound volume, which merges the advantages of both scanning patterns to increase the information that can be gained from the three-dimensional OCT data. We initially generate 3D point clouds of the linearly and radially acquired OCT volumes and use an Iterative Closest Point (ICP) variant to register both volumes. After registration, the compound volume is created by selectively exploiting linear and radial scanning data, depending on the A-scan density of the individual scans. Fusing regions from both volumes with respect to their local A-scan sampling density, we achieve improved overall anatomical OCT information in a high-resolution compound volume. We demonstrate our method on linear and radial OCT volumes for the visualization and analysis of macular holes and the surrounding anatomical structures.

Fe3O4@Sap/Cu(ii): an efficient magnetically recoverable green nanocatalyst for the preparation of acridine and quinazoline derivatives in aqueous media at room temperature.

Saponin, as a green and available phytochemical, was immobilized on the surface of magnetite nanoparticles then doped with Cu ions (Fe3O4@Sap/Cu(ii)) and used as an efficient nanocatalyst for the synthesis of quinazoline and acridine derivatives, due to their high application and importance in various fields of science. Different spectroscopic and microscopic techniques were used for the catalyst characterization such as FT-IR, XRD, FE-SEM, EDX, TEM, TGA, VSM, BET, DLS, CV, and XPS analyses. All characterization data were correlated with each other so that the structure of the catalyst was accurately characterized. The reactions were performed in the presence of a low amount of Fe3O4@Sap/Cu(ii) (0.42 mol%) as a green catalyst in water over a short period of time. The results show well the effective role of saponin in solving the problem of mass transfer in aqueous medium, which is the challenge of many organic reactions in aqueous medium and in the presence of heterogeneous medium. High catalytic activity was found for the catalyst and high to excellent efficiency was obtained for all quinazoline (68-94% yield) and acridine (66-97% yield) derivatives in short reaction times (less than 1 hour) under mild reaction conditions in the absence of any hazardous or expensive materials. There is not any noticeable by-product found whether for acridine or quinazoline derivatives, which reflects the high selectivity. Two reasonable mechanisms were proposed for the reactions based on observations from control experiments as well as literature reports. The catalyst could be easily recovered magnetically for at least six consecutive runs with insignificant reactivity loss.

A Co-Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C-N cross-coupling reactions in water.

A novel magnetically recyclable bimetallic catalyst was prepared by anchoring imidazolium moiety and PEG chains on Fe3O4 NPs and named as Fe3O4@PEG/Cu-Co. It was found to be a powerful catalyst for the Sonogashira, Suzuki, and C-N cross-coupling reactions in water as a green solvent without the need for any external base. Fe3O4@PEG/Cu-Co was well characterized with FT-IR, FE-SEM, TEM, VSM, EDX, ICP, UV-visible, CV, and XPS analyses. Optimum ranges of parameters such as time, temperature, and amount of catalyst were investigated by Design-Expert 10.0.7 software for C-C Suzuki, Sonogashira, and C-N cross-coupling reactions to find the optimum conditions. The catalyst was compatible with a variety of aryl halides and N-arenes and gave favorable coupling products with good to high yields for all of them. Hot filtration and Hg poisoning tests involving the nanocatalyst revealed the stability, low metal leaching, and heterogeneous nature of the catalyst. Reaction mechanisms were proposed by study of the UV-visible spectra in situ as well as hydroquinone tests during the progress of reactions. In situ XPS analysis was also used to study the reaction mechanism. To prove the synergistic performance of Co and Cu in the catalyst, its various homologues were synthesized and applied to a model reaction separately, and then their catalytic activities were investigated. Finally, the catalyst could be recovered from the reaction mixture simply, and reused for several cycles with a minimum loss in catalytic activity and performance.

Functionalized magnetic PAMAM dendrimer as an efficient nanocatalyst for a new synthetic strategy of xanthene pigments.

A green protocol has been developed for preparation of the wide variety of colored xanthene derivatives using a new efficient magnetic solid acid catalyst bearing polyamidoamine dendrimer moiety as a nanoscopic compound. Dendrimers, highly symmetric molecules around a core and 3D spherical morphology, show interesting traits based on their functionalized groups on the branched surface. They can be designed to provide water soluble structures or pseudo-active sites of biomolecules. The catalyst was assembled via a polyamidoamine dendrimer immobilized on the surface of γ-Fe2O3 followed by the sulfonylation of the amine groups by chlorosulfonic acid resulting in γ-Fe2O3@PAMAM-SO3H. Herein, PAMAM dendrimer with repeating amine/amide branches as catchable sites of sulfonic acid groups was introduced as transformer of homogeneous to heterogeneous acidic catalysts. The physicochemical properties of synthesized catalyst were studied using by FT-IR, FE-SEM, XRD, VSM, EDS, TGA/DTG, and TEM. Finally, the catalytic activity of γ-Fe2O3@PAMAM-SO3H was evaluated for the preparation of xanthene derivatives via a one-pot, three components reaction of aromatic aldehydes with i) ß-naphthol, ii) cyclic 1,3-dicarbonyl, iii) ß-naphthol and cyclic 1,3-dicarbonyl compounds, iv) 2-hydroxy-1,4-naphthoquinone, leading to the eco-riendly preparation of the target compounds in good to excellent yields. The catalyst could be easily recycled for at least five consecutive runs without significant loss in its catalytic activity.

Selective oxidation of alcohols and sulfides via O2 using a Co(ii) salen complex catalyst immobilized on KCC-1: synthesis and kinetic study.

The aim of this study was to immobilize a Co(ii) salen complex on KCC-1 as a catalyst that can be recovered (Co(ii) salen complex@KCC-1). Field-emission transmission electron microscopy, FT-IR spectroscopy, thermogravimetric analysis, elemental analysis, atomic absorption spectroscopy, and XRD were used to confirm the structure and chemical nature of Co(ii) salen complex@KCC-1. The oxidation efficiency was obtained for an extensive range of sulfides and alcohols using this sustainable catalyst, alongside O2 as an oxygen source and isobutyraldehyde (IBA) as an oxygen acceptor, with superior selectivity and conversion for the relevant oxidation products (sulfoxides and ketones or aldehydes) under moderate conditions. The µ-oxo and peroxo groups on the ligands of the Co complex appeared to be responsible for the superior activity of the catalyst. Essential factors behind the oxidation of alcohol and sulfoxides were investigated, including the catalyst, solvent, and temperature. In this paper, molecular oxygen (O2) was used as a green oxidant. Furthermore, kinetic studies were conducted, revealing a first-order reaction for the oxidation of both benzyl alcohol and sulfide. The reaction progressed at mild temperature, and the catalyst could be easily recovered and reused for numerous consecutive runs under the reaction conditions, without any substantial reduction in the functionality of the catalytic system.

The CuFe2O4@SiO2@ZrO2/SO4 2-/Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water.

Herein, the synthesis and application of copper-incorporated sulfated zirconium oxide supported on CuFe2O4 NPs (CuFe2O4@SiO2@ZrO2/SO4 2-/Cu NPs) as a novel Lewis/Brønsted acid nanocatalyst were studied for the Sonogashira C-C cross-coupling reaction. The fabricated CuFe2O4@SiO2@ZrO2/SO4 2-/Cu catalyst exhibited efficient activity for a large variety of aryl iodides/bromides and, most importantly, aryl chlorides in water and in the presence of NaOH as a base in short reaction times. The catalyst was fully characterized by FTIR, TG-DTG, VSM, XRD, EDX, FE-SEM and TEM analyses. A synergetic effect could be considered to have arisen from the various Lewis acid and Brønsted acid sites present in the catalyst. The efficient incorporation of copper into zirconia provided a robust highly stable hybrid, which prevented any metal leaching, whether from the magnetite moiety and/or Cu sites in the reaction mixture. Moreover, the catalyst was successfully recovered from the mixture by a simple external magnet and reused for at least 9 consecutive runs. Zero metal leaching, stability, consistency with a variety of substrates, fast performance, cost-effectiveness, environmental friendliness, and preparation with accessible and cheap materials are some of the advantages and highlights of the current protocol.

Fast 5DOF needle tracking in iOCT.

PURPOSE: Intraoperative optical coherence tomography (iOCT) is an increasingly available imaging technique for ophthalmic microsurgery that provides high-resolution cross-sectional information of the surgical scene. We propose to build on its desirable qualities and present a method for tracking the orientation and location of a surgical needle. Thereby, we enable the direct analysis of instrument-tissue interaction directly in OCT space without complex multimodal calibration that would be required with traditional instrument tracking methods. METHOD: The intersection of the needle with the iOCT scan is detected by a peculiar multistep ellipse fitting that takes advantage of the directionality of the modality. The geometric modeling allows us to use the ellipse parameters and provide them into a latency-aware estimator to infer the 5DOF pose during needle movement. RESULTS: Experiments on phantom data and ex vivo porcine eyes indicate that the algorithm retains angular precision especially during lateral needle movement and provides a more robust and consistent estimation than baseline methods. CONCLUSION: Using solely cross-sectional iOCT information, we are able to successfully and robustly estimate a 5DOF pose of the instrument in less than 5.4 ms on a CPU.

Synthesis of dual-action parthenolide prodrugs as potent anticancer agents.

Cancer stem cells are responsible for the failure of a large number of cancer treatments and the re-emergence of cancer in patients. Parthenolide is a potent anticancer sesquiterpene lactone that is also able to kill cancer stem cells. The main problem with this compound is its poor solubility in water. To solve this problem, medicinal chemists have tried to prepare amino-derivatives of parthenolide, however, most amino-derivatives have less potency than that of parthenolide. In this paper, we proposed a new approach to synthesize parthenolide derivatives with better solubility and higher potency. We prepared novel parthenolide derivatives through the aza-Michael addition of nitrogen-containing anticancer drug molecules (cytarabine and melphalan) to the α-methylene-γ-lactone group of parthenolide. Different types of catalysts were used to catalyze the aza-Michael addition. Among all the used catalysts, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was found to have the highest catalytic activity. In addition, we examined the effects of parthenolide-anticancer drug hybrids on the growth and proliferation of three cancer cell lines (MCF-7, LNcaP, Hep G2) and CHO. The parthenolide prodrugs showed potent cytotoxic property with IC50 values ranging from 0.2 to 5.2µM, higher than those of parthenolide and anticancer drugs (cytarabine and melphalan).

Magnetic nanoparticle supported hyperbranched polyglycerol catalysts for synthesis of 4H-benzo[b]pyran.

ABSTRACT: A magnetic nanoparticle supported hyperbranched polyglycerol catalyst was prepared readily from inexpensive starting materials in aqueous medium that catalyzed the synthesis of 4H-benzo[b]pyran under solvent-free conditions at room temperature. X-ray diffraction, transmission electron microscopy, thermal gravimetric analysis, vibrating sample magnetometry, and selected-area electron diffraction were employed to characterize the properties of the synthesized catalyst. Its high catalytic activity and ease of recovery from the reaction mixture using an external magnet, and the possibility of reusing several times without significant loss of performance are additional eco-friendly attributes of this catalytic system. GRAPHICAL ABSTRACT: .