Mechanochemical Applications of Reactive Extrusion from Organic Synthesis to Catalytic and Active Materials

In the past, the use of mechanochemical methods in organic synthesis was reported as somewhat of a curiosity. However, perceptions have changed over the last two decades, and this technology is now being appreciated as a greener and more efficient synthetic method. The qualified “offer” of ball mills that make use of different set-ups, materials, and dimensions has allowed this technology to mature. Nevertheless, the intrinsic batch nature of mechanochemical methods hinders industrial scale-ups. New studies have found, in reactive extrusion, a powerful technique with which to activate chemical reactions with mechanical forces in a continuous flow. This new environmentally friendly mechanochemical synthetic method may be able to miniaturize production plants with outstanding process intensifications by removing organic solvents and working in a flow mode. Compared to conventional processes, reactive extrusions display high simplicity, safety, and cleanliness, which can be exploited in a variety of applications. This paper presents perspective examples in the better-known areas of reactive extrusions, including oxidation reactions, polymer processing, and biomass conversion. This work should stimulate further developments, as it highlights the versatility of reactive extrusion and the huge potential of solid-phase flow chemistry.

The Role of Rosmarinic Acid on the Bioproduction of Gold Nanoparticles as Part of a Photothermal Approach for Breast Cancer Treatment

Breast cancer is a high-burden malignancy for society, whose impact boosts a continuous search for novel diagnostic and therapeutic tools. Among the recent therapeutic approaches, photothermal therapy (PTT), which causes tumor cell death by hyperthermia after being irradiated with a light source, represents a high-potential strategy. Furthermore, the effectiveness of PTT can be improved by combining near infrared (NIR) irradiation with gold nanoparticles (AuNPs) as photothermal enhancers. Herein, an alternative synthetic method using rosmarinic acid (RA) for synthesizing AuNPs is reported. The RA concentration was varied and its impact on the AuNPs physicochemical and optical features was assessed. Results showed that RA concentration plays an active role on AuNPs features, allowing the optimization of mean size and maximum absorbance peak. Moreover, the synthetic method explored here allowed us to obtain negatively charged AuNPs with sizes favoring the local particle accumulation at tumor site and maximum absorbance peaks within the NIR region. In addition, AuNPs were safe both in vitro and in vivo. In conclusion, the synthesized AuNPs present favorable properties to be applied as part of a PTT system combining AuNPs with a NIR laser for the treatment of breast cancer.

A facile and scale-up synthetic method for covalent organic nanosheets: ultrasonic polycondensation and photocatalytic degradation of organic pollutants

Covalent organic framework nanosheets (COF NSs or CONs), as compared to their bulk counterparts two-dimensional (2D) covalent organic frameworks (COFs), exhibit superior performance in many aspects due to their fully...

Synthesis of Fluorenes and Their Related Compounds from Biaryls and Meldrum’s Acid Derivatives

A new synthetic method for preparing fluorenes from amino group-containing biaryls and Meldrum’s acid derivatives was developed. The reaction proceeded without a catalyst and loss of functional groups. The corresponding...

The Influence of Different Carbonate Ligands on the Hydrolytic Stability and Reduction of Platinum(IV) Prodrugs

Pt(IV) complexes bearing axial carbonate linkages have drawn much attention recently. A synthetic method behind it allows to attach the hydroxyl group of bioactive ligands to the available hydroxyl group...

Nb doped TiO2 nanoparticles derived from titanate with improved lithium storage performance

In the present work, a facile synthetic method has been used to prepared Nb doped TiO2 nanoparticles with titanate as precursor. The synthesized electrodes materials were characterized by X-ray diffraction,...

Noël Coypel’s educational journey to Rome at the end of 1672 and the beginning of 1673

The aim of this article is to present the circumstances of Noël Coypel’s appointment as rector of the French Academy in Rome and to trace the route of his didactic journey from Paris to Rome with the Prix de Rome scholars entrusted to him. The paper is an attempt to answer the following questions: why a more difficult route through the Alps was chosen (and not, for example, a river and sea route), in what way was the journey educational, and what role did the documents given to Coypel play in securing the expedition. The article is based on an analysis of administrative records during the reign of Louis XIV, lists of superintendents and directors of the French Academy in Rome, accounts of royal buildings, and minutes of the Royal Academy of Painting and Sculpture in Paris. The paper uses the analytical method, the comparative method, the synthetic method, source criticism, argumentum ex silentio inference, and the geographical method when discussing the itinerary. Although the trip was purposeful and related to Coypel’s new position, he designed it in such a way as to not so much get to the destination quickly, but to show his students as much as possible. Coypel introduced the royal scholars to masterpieces of painting and sculpture at centers along a route through Dijon, Lyon, Chambéry, the Mont Cenis Pass, Turin, Milan, Bologna and Florence. The crossing of the Alps, though dangerous, was most often chosen because of the artistic reputation of the cities there. The trip was educational at the expense of comfort or safety. Coypel, as a guide and teacher (paidagōgós – παιδαγωγός) led his charges by overseeing their learning during and through the journey. Wandering to the Eternal City was part of a painter’s education (paideía – παιδεία) in the seventeenth century and was part of Coypel’s didactic work allowing young people to be inspired by direct exposure to masterpieces. The journey had an eminently didactic and artistic character, but also an initiatory one, as it gradually initiated and prepared the students for the experience of Rome, the center of artistic life at that time.

Out with Acetonitrile: Water-assisted Accelerated-Aging Synthesis of CuI-Pyrazine Hybrid Materials

CuI and pyrazine form three hybrid materials, [(CuI)2(pyrazine)] (Yellow), [(CuI)2(pyrazine)2] (Orange), and [(CuI)(pyrazine)] (Red). In this work, Red was prepared using a green synthetic method, water-assisted accelerated-aging synthesis, for the first time. The syntheses were performed under ambient conditions with only water and no organic solvents. Depending on the reaction conditions, the other two hybrid materials can be formed as well: Orange was formed immediately after dry grinding CuI and pyrazine, while Yellow can be formed from Red and excess amount of CuI at mildly elevated temperatures. The impacts of temperature and types and amounts of liquid added to the aging mixture on the accelerated-aging synthesis were studied, and mechanisms of the synthesis and interconversions between the three CuI-pyrazine hybrid materials were proposed.

The Search for New Antibacterial Agents among 1,2,3-Triazole Functionalized Ciprofloxacin and Norfloxacin Hybrids: Synthesis, Docking Studies, and Biological Activity Evaluation

Among all modern antibiotics, fluoroquinolones are well known for their broad spectrums of activity and efficiency toward microorganisms and viruses. However, antibiotic resistance is still a problem, which has encouraged medicinal chemists to modify the initial structures in order to combat resistant strains. Our current work is aimed at synthesizing novel hybrid derivatives of ciprofloxacin and norfloxacin and applying docking studies and biological activity evaluations in order to find active promising molecules. We succeeded in the development of a synthetic method towards 1,2,3-triazole-substituted ciprofloxacin and norfloxacin derivatives. The structure and purity of the obtained compounds were confirmed by 1H NMR, 13C NMR, 19F NMR, LC/MS, UV-, IR- spectroscopy. Docking studies, together with in vitro research against Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, Bacillus subtilis ATCC 6633, Pseudomonas aeruginosa ATCC 27853, Candida albicans NCTC 885-653 revealed compounds in which activity exceeded the initial molecules.

METHOD FOR THE PREPARATION OF 2,4,6-TRIHYDROXYTOLUENE FROM 2,4,6-TRINITROTOLUENE

Статья посвящена усовершенствованию способа получения 2,4,6-тригидрокситолуола, востребованного химического реагента в синтезе азокрасителей и пигментов, а также химико-фармацевтических препаратов и различных полимеров. Основным сырьем для его получения является 2,4,6-тринитротолуол, который подвергают каталитическому гидрированию с последующим гидролизом образовавшегося 2,4,6-триаминотолуола. В данной работе предложены условия многоциклового использования палладиевого катализатора гидрирования 2,4,6-тринитротолуола, позволяющие сохранять активность катализатора и повысить выход 2,4,6-триаминотолуола выше 98 %. Аминопроизводное выделяется в виде дисульфата действием концентрированной серной кислоты. Кроме того, изучено влияние соотношения вода/дисульфат 2,4,6-триаминотолуола на выход 2,4,6-тригидрокситолуола; найдены условия, в которых выход на стадии гидролиза увеличен до 83-84 %. Проведен сравнительный анализ различных способов выделения 2,4,6-тригидрокситолуола из реакционной массы. The paper is concerned with upgrading the synthetic method for 2,4,6-trihydroxytoluene, an in-demand chemical reactant in the synthesis of azo-dyes and pigments, as well as chemical pharmaceuticals and various polymers. The basic feedstock for the synthesis thereof is 2,4,6-trinitrotoluene, which is subjected to catalytic hydrogenation followed by hydrolysis of the resulting 2,4,6-triaminotoluene. Here we suggest conditions for the multicycle use of Pd catalyst employed for the hydrogenation of 2,4,6-trinitrotoluene, which allow the catalyst activity to be retained and the yield of 2,4,6-triaminotoluene to be enhanced above 98%. The amino derivative is liberated as the disulfate by concentrated sulfuric acid. Moreover, we examined how the ratio of water / 2,4,6-triaminotoluene disulfate influences the yield of 2,4,6-trihydroxytoluene. Conditions were found in which the yield from hydrolysis is 83-84 %. Different methods for the isolation of 2,4,6-trihydroxytoluene from the reaction mixture were comparatively analyzed.