Search results for: palladium nanocluster absorbates

Authors: Majid Farsadrouh Rashti, Amir Shafiee Kisomi, Parisa Jahani

Abstract:

The direct ethanol fuel cells (DEFCs) are contemplated as a promising energy source because, In addition to being used in portable electronic devices, it is also used for electric vehicles. The synthesis of bimetallic nanostructures due to their novel optical, catalytic and electronic characteristic which is precisely in contrast to their monometallic counterparts is attracting extensive attention. Galvanic replacement (sometimes is named to as cementation or immersion plating) is an uncomplicated and effective technique for making nanostructures (such as core-shell) of different metals, semiconductors, and their application in DEFCs. The replacement of galvanic does not need any external power supply compared to electrodeposition. In addition, it is different from electroless deposition because there is no need for a reducing agent to replace galvanizing. In this paper, a fast method for the palladium (Pd) wire nanostructures synthesis with the great surface area through galvanic replacement reaction utilizing copper nanowires (CuNWS) as a template by the assistance of ultrasound under room temperature condition is proposed. To evaluate the morphology and composition of Pd@ Copper nanowires/MultiWalled Carbon nanotubes-Chitosan, emission scanning electron microscopy, energy dispersive X-ray spectroscopy were applied. In order to measure the phase structure of the electrocatalysts were performed via room temperature X-ray powder diffraction (XRD) applying an X-ray diffractometer. Various electrochemical techniques including chronoamperometry and cyclic voltammetry were utilized for the electrocatalytic activity of ethanol electrooxidation and durability in basic solution. Pd@ Copper nanowires/MultiWalled Carbon nanotubes-Chitosan catalyst demonstrated substantially enhanced performance and long-term stability for ethanol electrooxidation in the basic solution in comparison to commercial Pd/C that demonstrated the potential in utilizing Pd@ Copper nanowires/MultiWalled Carbon nanotubes-Chitosan as efficient catalysts towards ethanol oxidation. Noticeably, the Pd@ Copper nanowires/MultiWalled Carbon nanotubes-Chitosan presented excellent catalytic activities with a peak current density of 320.73 mAcm² which was 9.5 times more than in comparison to Pd/C (34.2133 mAcm²). Additionally, activation energy thermodynamic and kinetic evaluations revealed that the Pd@ Copper nanowires/MultiWalled Carbon nanotubes-Chitosan catalyst has lower compared to Pd/C which leads to a lower energy barrier and an excellent charge transfer rate towards ethanol oxidation.

Keywords: core-shell structure, electrocatalyst, ethanol oxidation, galvanic replacement reaction

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Authors: Karim Hrratha, Khaled Essalahb, Christophe Morellc, Henry Chermettec, Salima Boughdiria

Abstract:

Among the carbon-carbon bond formation types, allylation of active methylene compounds with cyclic Baylis-Hillman (BH) alcohols is a reliable and widely used method. This reaction is a very attractive tool in organic synthesis of biological and biodiesel compounds. Thus, in view of an insistent and peremptory request for an efficient and straightly method for synthesizing the desired product, a thorough analysis of various aspects of the reaction processes is an important task. The product afforded by the reaction of active methylene with BH alcohols depends largely on the experimental conditions, notably on the catalyst properties. All experiments reported that catalysis is needed for this reaction type because of the poor ability of alcohol hydroxyl group to be as a suitable leaving group. Within the catalysts, several transition- metal based have been used such as palladium in the presence of acid or base and have been considered as reliable methods. Furthemore, acid catalysts such as BF3.OEt2, BiX3 (X= Cl, Br, I, (OTf)3), InCl3, Yb(OTf)3, FeCl3, p-TsOH and H-montmorillonite have been employed to activate the C-C bond formation through the alkylation of active methylene compounds. Interestingly a report of a smoothly process for the ability of 4-imethyaminopyridine(DMAP) to catalyze the allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol appeared recently. However, the reaction mechanism remains ambiguous, since the C- allylation process leads to an unexpected product (noted P1), corresponding to a direct allylation instead of conjugate allylation, which involves the most electrophilic center according to the electron withdrawing group CO effect. The main objective of the present theoretical study is to better understand the role of the DMAP catalytic activity as well as the process leading to the end- product (P1) for the catalytic reaction of a cyclic BH alcohol with active methylene compounds. For that purpose, we have carried out computations of a set of active methylene compounds varying by R1 and R2 toward the same alcohol, and we have attempted to rationalize the mechanisms thanks to the acid–base approach, and conceptual DFT tools such as chemical potential, hardness, Fukui functions, electrophilicity index and dual descriptor, as these approaches have shown a good prediction of reactions products.The present work is then organized as follows: In a first part some computational details will be given, introducing the reactivity indexes used in the present work, then Section 3 is dedicated to the discussion of the prediction of the selectivity and regioselectivity. The paper ends with some concluding remarks. In this work, we have shown, through DFT method at the B3LYP/6-311++G(d,p) level of theory that: The allylation of active methylene compounds with cyclic BH alcohol is governed by orbital control character. Hence the end- product denoted P1 is generated by direct allylation.

Keywords: DFT calculation, gas phase pKa, theoretical mechanism, orbital control, charge control, Fukui function, transition state

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Authors: Ruth Goldschmidt, Vyacheslav Kalchenko, Lilah Agemy, Rachel Elmoalem, Avigdor Scherz

Abstract:

Vascular Targeted Photodynamic therapy (VTP) is a new modality for selective cancer treatment that leads to the complete tumor ablation. A photosensitizer, a bacteriochlorophyll derivative in our case, is first administered to the patient and followed by the illumination of the tumor area, by a near-IR laser for its photoactivation. The photoactivated drug releases reactive oxygen species (ROS) in the circulation, which reacts with blood cells and the endothelium leading to the occlusion of the blood vasculature. If the blood vessels are only partially closed, the tumor may recover, and cancer cells could survive. On the other hand, excessive treatment may lead to toxicity of healthy tissues nearby. Simultaneous VTP monitoring and image processing independent of the photoexcitation laser has not yet been reported, to our knowledge. Here we present a method for blood flow monitoring, using a real-time laser speckle imaging (RTLSI) in the tumor during VTP. We have synthesized over the years a library of bacteriochlorophyll derivatives, among them WST11 and STL-6014. Both are water soluble derivatives that are retained in the blood vasculature through their partial binding to HSA. WST11 has been approved in Mexico for VTP treatment of prostate cancer at a certain drug dose, and time/intensity of illumination. Application to other bacteriochlorophyll derivatives or other cancers may require different treatment parameters (such as light/drug administration). VTP parameters for STL-6014 are still under study. This new derivative mainly differs from WST11 by its lack of the central Palladium, and its conjugation to an Arg-Gly-Asp (RGD) sequence. RGD is a tumor-specific ligand that is used for targeting the necrotic tumor domains through its affinity to αVβ3 integrin receptors. This enables the study of cell-targeted VTP. We developed a special RTLSI module, based on Labview software environment for data processing. The new module enables to acquire raw laser speckle images and calculate the values of the laser temporal statistics of time-integrated speckles in real time, without additional off-line processing. Using RTLSI, we could monitor the tumor’s blood flow following VTP in a CT26 colon carcinoma ear model. VTP with WST11 induced an immediate slow down of the blood flow within the tumor and a complete final flow arrest, after some sporadic reperfusions. If the irradiation continued further, the blood flow stopped also in the blood vessels of the surrounding healthy tissue. This emphasizes the significance of light dose control. Using our RTLSI system, we could prevent any additional healthy tissue damage by controlling the illumination time and restrict blood flow arrest within the tumor only. In addition, we found that VTP with STL-6014 was the most effective when the photoactivation was conducted 4h post-injection, in terms of tumor ablation success in-vivo and blood vessel flow arrest. In conclusion, RTSLI application should allow to optimize VTP efficacy vs. toxicity in both the preclinical and clinical arenas.

Keywords: blood vessel occlusion, cancer treatment, photodynamic therapy, real time imaging

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