Selective catalytic synthesis of new terpenic chlorides using NaDCC as an eco-friendly and highly stable FAC agent.

A simple, mild and efficient scope pathway for a selective catalytic chlorination of terpenic olefins is investigated in the presence of a highly efficient chlorination agent and a readily available Lewis acid catalyst. The sodium dichloroisocyanurate (NaDCC) used in the present work as an easy handling, sustainable and cost-effective chlorine donor due to its high free available chlorine (FAC), exhibits a high efficiency for selective catalytic chlorination. Herein, we report for the first-time the FeCl2/NaDCC combination system for the selective catalytic chlorination towards new functionalized terpenic olefins. In order to examine the general features of this catalytic reaction, the effects of pH, solvent, dilution, chlorination agent nature, stoichiometry and reaction kinetics are optimized using carvone as a model substrate. Among the studied parameters, catalyst stoichiometry was found to be determinant for highly controllable chlorination selectivity towards new allylic and vinylic chlorides. Indeed, the oxidation state, ligand and metal effects of the catalyst are examined using various Lewis acids, where the chlorinated ones (MClx), such as FeCl2, FeCl3 and SnCl2, exhibit a comprehensive approach for a controllable chlorination reaction. In addition, the homogeneous catalytic system shows good reusability with significant catalytic conversion depending on the FAC content in the reaction medium. The reaction proceeds under mild conditions with shorter reaction time and high selectivity towards new high added value allylic and vinylic chlorinated derivatives of naturally occurring terpenic olefins in good to excellent yields.

A DFT investigation of the catalytic oxidation of benzyl alcohol using graphene oxide.

CONTEXT: Metal-free heterogeneous materials have attracted great interest due to their potential to facilitate various organic transformations in line with circular economy and green chemistry principles. Among various 2D materials, graphene oxide (GO) is considered an attractive material for numerous applications in physics, chemistry, biology, material sciences, and catalysis. Furthermore, graphene-based catalysts exhibit good catalytic activity toward the selective oxidation of benzyl alcohol to benzaldehyde or benzoic acid under eco-friendly conditions. In this regard, a theoretical investigation was carried out to study both catalytic oxidation reaction pathways (i.e., benzyl alcohols to aldehyde and to benzoic acid) using GO as an eco-friendly and metal-free catalyst. METHODS: In this study, we report a theoretical investigation at the B3LYP/6-31G level to better understand the oxidation of benzyl alcohol using GO as a metal-free catalyst. The possible bond formation was investigated using the global and local reactivity indexes derived from Fukui functions. Furthermore, we performed a non-covalent interaction (NCI) analysis to unveil the stability and the interaction nature between both reagents and GO surface. The effect of the solvent on the oxidation efficiency was also performed and the results indicate that the solvent significantly affects the decrease of reactivity by increasing the activation barriers through oxidation reactions of benzyl alcohol. Additionally, the electron localization function (ELF) analysis was performed for all intermediates showing the ionic nature of the studied epoxide structure of GO and rules out any type of covalent interaction during the oxidation reaction of benzyl alcohol. All these obtained results are in good agreement with experimental observations and reveal that the epoxide functions on the graphene surface promote an excellent catalyst turnover.

Carboxymethyl cellulose nanocolloids anchored Pd(0) nanoparticles (CMC@Pd NPs): synthesis, characterization, and catalytic application in transfer hydrogenation.

Herein, we report on the preparation of novel colloidal system based on carboxymethyl cellulose (CMC) and Pd nanoparticles (CMC@Pd NPs) via an ecofriendly auto-reduction process under mild conditions. In the first step, the follow-up of reduction and preparation of CMC anchored palladium nanoparticles (Pd NPs) in aqueous solution was carried out using UV-Vis spectroscopy. Thereafter, the monodispersed colloids were fully characterized by advanced analytical, structural, and morphological techniques. Based on Scherrer equation, the as-synthesized CMC@Pd NPs crystallite size was about 10.88 nm. Accordingly, the detailed microscopic study revealed CMC nanocolloids anchored uniform distribution of Pd NPs and the presence of CMC nanofilm as protective monolayer. To the best of our knowledge, the observed nanoscale properties are reported for the first time for CMC-M system. The performance of the as-synthesized CMC@Pd nanocolloids was first investigated in the reduction of 4-nitrophenol, as a model substrate, to 4-aminophenol using NaBH4 as a hydrogen source. Moreover, the catalytic reduction of various nitroarenes bearing electron withdrawing or donating substituents was carried out and monitored by UV-Vis spectroscopy. The chemo- and regioselectivity of the catalytic reduction in presence of CMC@Pd NPs were also studied. Consequently, the prepared CMC@Pd nanocolloids exhibit remarkable activity, good heterogeneity, and higher reusability and stability for the catalytic reduction reaction under mild conditions.

Synergistic effect of GO/SrFe12O19 as magnetic hybrid nanocatalyst for regioselective ring-opening of epoxides with amines under eco-friendly conditions.

Herein, a highly efficient magnetically separable hybrid GO/SrFe12O19 nanocomposite was synthesized via dispersing M-type strontium hexaferrite (SrFe12O19) on graphene oxide (GO) sheets. First, SrFe12O19 nanoparticles (NPs) and GO sheets were prepared via chemical coprecipitation and chemical oxidation of graphite powder, respectively. Chemically reduced GO (rGO) and rGO/SrFe12O19 were also prepared for comparison purposes. Thereafter, the prepared nanostructured materials were explored by XRD, FTIR, FESEM-EDX, BET, and Zetasizer analyses. All the characterizations confirm the nanoscale and the high stability structures of the prepared materials. The prepared hybrid magnetic nanocomposite GO/SrFe12O19 exhibited a high surface area value resulting in a high catalytic activity and selectivity for the epoxide ring-opening with amines in neat water. The use of hybrid GO/SrFe12O19 compared with pure SrFe12O19 and GO sheets is of great interest for using environmentally benign heterogeneous nanocatalysts, for the synthesis of ß-amino alcohols, with excellent recyclability under eco-friendly conditions. Moreover, a mechanistic study was performed through density functional theory (DFT) calculations and Parr functions to explain the observed reactivity and selectivity of SrFe-GO catalyst in the epoxide ring-opening reactions.

[Narcolepsy]. / La narcolepsie.

Narcolepsy is a chronic neurologic disease whose main features are excessive daytime sleepiness and cataplexy. It is a rare disorder which is most frequently sporadic. The age of onset shows tow peaks. Both genetic and environmental factors play in its pathophysiolgy. Association with a specific HLA antigen and implication of the hypocretin system are very important findings. Narcolepsy's diagnosis is based on clinical findings but polysomnographic monitoring and multiple sleep latency test are usually necessary. Treatment of narcolepsy has been substantially modified with the advent of Modafinil which is effective as amphetamine with less undesirable effects. New etiologic treatments, such as hypocretin agonists, are currently being developed.

[A rare primary pulmonary tumor: pleomorphic carcinoma]. / Une tumeur primitive rare du poumon: le carcinome pléomorphe.

INTRODUCTION: Pleomorphic carcinoma is a rare malignancy in the family of non-small cell lung cancers. CASE: This 65-year-old woman, a nonsmoker, was hospitalized for hemoptysis and weight loss. Computed tomography showed a peripheral tumor of the right upper lobe, and the radiography showed signs of malignancy. Pathologic examination of the transparietal biopsy confirmed the tumor diagnosis, classifying it as stage III A. The patient underwent 2 cycles of induction chemotherapy that combined gemcitabine and cisplatin. Disease progression continued, however, and distant metastases were observed. The patient died 4 months after diagnosis. DISCUSSION: Pleomorphic carcinoma is identified by purely histologic criteria: the concomitant presence of malignant epithelial and homologous sarcomatoid spindle-cell components. Like the other non-small cell lung cancers, treatment is primarily surgical, and the invasive character of this tumor makes it very difficult. Pleomorphic carcinoma has a poorer prognosis than conventional non-small cell lung cancers despite surgery, irradiation and chemotherapy, because relapse occurs early.

[Toward optimization of small cell lung cancer management]. / Vers une optimisation de la prise en charge des carcinomes à petites cellules du poumon.

Small cell carcinoma represents 20 to 25 % of all lung cancers. It is characterized by his quickly dissemination. Chemotherapy is the comer stone of small cell lung cancer therapy. However, therapeutic approach are depending on patient's performans states and the disease's extension. The role of radiotherapy is established in the treatment of limited disease. However irradiation's modalities are still discussed. Surgery, usually, contraindicated is, actually, possible in early stages (T1T2N0). Recent advances in molecular biology have created new molecular targeted therapies for SCC but the benefits are not still evaluated. In this article, we review briefly classic strategies that have been evaluated in the management of patients with small cell carcinoma. This review will, also, focus in the main novel cytotoxic drugs and radiotherapy's modalities and for their clinical implication.

[Localised bronchi amyloidosis: a case report]. / Amylose bronchique localisée: une observation.

Localised pulmonary amyloïdosis is exceptional. Tracheobronchial symptoms are the most frequent. We report a case of a 68 year-old man complaining of cough and breathlessness. Bronchoscopy showed a submucosal infiltration with stenosis of left upper and lower bronchi. Multiples biopsy were performed and concluded to amyloïdosis of AL type. Our objective is to describe the anatomopathologic aspects of localised pulmonary amyloïdosis and to discuss its pathogeny.