Volume 91, Issue 4 - Special issue: IUPAC Distinguished Women in Chemistry and Chemical Engineering

Today, medicinal chemistry is still clearly dominated by organic chemistry, and commercially available boron-based drugs are rare. In contrast to hydrocarbons, boranes prefer the formation of polyhedral clusters via delocalized 3c2e bonds, such as polyhedral dicarba- closo -dodecaborane(12) ( closo -C 2 B 10 H 12 ). These clusters have remarkable biological stability, and the three isomers, 1,2- ( ortho ), 1,7- ( meta ), and 1,12-dicarba- closo -dodecaborane(12) ( para ), have attracted much interest due to their unique structural features. Furthermore, anionic nido clusters ([7,8-C 2 B 9 H 11 ] 2− ), derived from the neutral icosahedral closo cluster 1,2-dicarba- closo -dodecaborane(12) by deboronation followed by deprotonation are suitable ligands for transition metals and offer the possibility to form metallacarboranes, for example via coordination through the upper pentagonal face of the cluster. The isolobal analogy between the cyclopentadienyl(–1) ligand (Cp − ) and [C 2 B 9 H 11 ] 2− clusters (dicarbollide anion, Cb 2− ) is the motivation in using Cb 2− as ligand for coordination to a metal center to design compounds for various applications. This review focuses on potential applications of half- and mixed-sandwich-type transition metal complexes in medicine.

Different multicomponent 1,3-dipolar cycloadditions (1,3-DC) of cyclic α-amino acid derivatives with aldehydes and dipolarophiles have been described as efficient and simple methodologies for the synthesis of the pyrrolidine unit of pyrrolizidines and indolizidines. When free cyclic α-amino acids are used, a thermal promoted decarboxylative process generates in situ the corresponding non-stabilized azomethine ylides, which afforded the corresponding pyrrolizidines and indolizidines with a hydrogen in the bicyclic units. This methodology has been employed to the synthesis of complex systems including spiro derivatives when ketones are used as carbonyl component. In addition, working with cyclic α-amino acid derived esters, the three-component 1,3-DC takes place under milder reaction conditions giving the corresponding pyrrolizidines and indolizidines with an alkoxycarbonyl group in the bridge adjacent carbon to the nitrogen. This methodology can be carried out by a double consecutive or stepwise 1,3-DC to provide pyrrolizidines via the precursor prolinates. The conformation of the azomethine ylide controls the endo/exo diastereoselectivity of the 1,3-DC.

Acylphloroglucinols (ACPLs) are a broad class of compounds structurally derived from phloroglucinol and characterised by the presence of a CRO group. They are interesting for their biological activities and their potentialities as lead compounds in drug development. The current review considers a series of works which, altogether, sum up to a systematic computational study of ACPLs in vacuo and in three solvents – chloroform, acetonitrile and water. An initial set of studies, focusing on ACPLs as a class and utilising an adequately representative selection of molecules, identified patterns in the conformational preferences and molecular properties of ACPLs, which appear valid for the whole class or for specific subclasses such as monomeric ACPLs, dimeric ACPLs, ACPLs with substituents containing C=C double bonds, etc. The validity of the identified patterns was further verified through the study of additional and significantly different ACPL molecules, as well as other molecular structures containing ACPL units. Furthermore, the computational study of ACPLs proved interesting for the insights into the factors stabilising their conformers, first of all intramolecular hydrogen bonding, which plays dominant roles in determining conformational preferences and energetics. The current review outlines the objectives, approaches and main results of these studies. The obtained information may be relevant for further studies aimed at a better understanding of the molecular bases of the biological activities of ACPLs.

The effect of the metal-support interaction (MSI) has been discussed for several types of catalytic systems comprising metal nanoparticles (Ni, Pd, Au, Fe) on oxide and carbon supports, showing promising catalytic properties in hydrogenation of unsaturated C–C bonds, hydrodechlorination (HDC) of chlorinated organic molecules and CO total oxidation. The MSI of a different strength, from the redistribution of the electron density of nanoparticles (NPs) to the chemical interactions, is determined by the composition of the support and the active site, the method of active metal deposition, calcination temperature, particle size etc. The types of MSI considered in this review include: (1) the interaction of the active metal (Me) NPs with alumina and modified zirconia to form several oxidation states of Me in the composition of surface or bulk chemical compounds with a support; (2) the influence of oxide (alumina, silica) or carbon (highly oriented pyrolytic graphite, Sibunit) supports on the formation of active sites in the catalysts with ultra-low Me loading prepared by deposition of pre-formed metal NPs produced by laser electrodispersion (LED) or as colloidal dispersion; (3) the anchoring of Me NPs on the surface of carbon supports (nanodiamonds and carbon nanotubes) directly with a support surface, e.g. through surface defects, or through surface functional groups; (4) ‘reverse’ MSI in the Me@C composites, consisting of metal NPs, covered with the defected graphene layers or immersed into carbon matrix. It is demonstrated on the example of LED systems, that oxidation of metal under MSI is less significant in carbon-supported systems than in oxide-supported ones, but charge effects can play a noticeable role for both types of supports. Different ways of MSI tuning provide the possibilities to achieve the optimal Me n+ /Me 0 ratio in the catalysts for HDC of mono- and polychlorinated organic molecules, including persistent organic pollutants. One of these ways is tuning the composition of functional groups on the surface of nanodiamonds and carbon nanotubes by additional treatments to achieve the desirable metal anchoring, the optimal metal NPs size and the improved catalytic properties. Unusual type of MSI is represented by the activation of thin graphene shell of Me@C composites by the presence of defects in the shell and a transition metal (Ni, Fe) in subsurface layer. This effect allows H 2 activation that is a significant step in many industrially important reactions. The selectivity and activity of such systems can be intentionally changed by varying the nature of metal and reaction temperature. Significant attention has been given in the review to the novel catalytic systems described in the previous works of the authors.

A mini-review is dedicated to the application of Pd(0)-catalyzed amination reactions for the synthesis of polymacrocyclic compounds of various architectures. Such molecules comprise diazacrown ether moieties or structural fragments of tri- and tetraazamacrocycles, polyamine or polyoxadiamine chains of different length and aromatic spacers. Polymacrocyclic compounds thus formed possess an increased number of coordination sites and are suitable for testing as potential receptors of metal cations. Some of these macrocyclic compounds were decorated with the exocyclic dansyl fluorophore group or were coupled with porphyrin units to form polymacrocyclic conjugates. Fluorescent spectra of these compounds were studied in the presence of various metal perchlorates and several macrocycles were found to act as chemosensors or molecular probes for such cations like Cu(II), Al(III), Cr(III).

Ferrocene and its derivatives constitute versatile and interesting scaffolds for the global chemical enterprise due to its multiple applications that range from biomedical to materials science. Ferrocenyl derivatives are the leading compounds in our research for the syntheses and characterization as well as their potential biological applications. Among them, our recent focus has been in ferrocenyl chalcones as a framework for further derivatization. The proposed modifications consist on the incorporation of heterocyclic moieties into the ferrocenyl chalcone core. This can be afforded either by introducing a heterocyclic aromatic moiety as a substituent or functionalizing the α-β unsaturated system. Another modification explored is the formation of ammonium or pyridinium salts to increase water solubility. Studied ferrocenyl chalcones exhibit remarkable stability, physical, and electrochemical properties. These factors have led the approaches for them to be precursors of biologically active compounds (cancer, bacteria, malaria, and neurobiological diseases). Moreover, other potential applications include molecular materials, redox-sensors, and polymers. Our goal in this mini review is to highlight the chemistry of ferrocene derivatives with particular prominence to those ferrocenyl chalcones studied in our laboratory and their applications. Moreover, we are providing a background on ferrocene, chalcones, and ferrocenyl chalcones, emphasizing the methodologies with preeminent yields.

This article provides a general overview of the results of research on the influence of the reaction media and various types of electromagnetic radiation on the polymerization of inorganic monomers, carried out during the last decade at UNESCO Chair in Green Chemistry for Sustainable Development of Dmitry Mendeleev University of Chemical Technology of Russia.

Since the second half of the 20 th century, bioceramics are used for bone repair and regeneration. Inspired by bones and teeth, and aimed at mimicking their structure and composition, several artificial bioceramics were developed for biomedical applications. And nowadays, in the 21 st century, with the increasing prominence of nanoscience and nanotechnology, certain bioceramics are being used to build smart drug delivery systems, among other applications. This minireview will mainly describe both tendencies through the research work carried out by the research team of María Vallet-Regí.

This article reviews the surface forces measurement as a novel tool for materials science. The history of the measurement is briefly described in the Introduction. The general overview covers specific features of the surface forces measurement as a tool for studying the solid-liquid interface, confined liquids and soft matter. This measurement is a powerful way for understanding interaction forces, and for characterizing (sometime unknown) phenomena at solid-liquid interfaces and soft complex matters. The surface force apparatus (SFA) we developed for opaque samples can study not only opaque samples in various media, but also electrochemical processes under various electrochemical conditions. Electrochemical SFA enables us to determine the distribution of counterions between strongly bound ones in the Stern layer and those diffused in the Gouy-Chapman layer. The shear measurement is another active area of the SFA research. We introduced a resonance method, i.e. the resonance shear measurement (RSM), that is used to study the effective viscosity and lubricity of confined liquids in their thickness from μm to contact. Advantages of these measurements are discussed by describing examples of each measurement. These studies demonstrate how the forces measurement is used for characterizing solid-liquid interfaces, confined liquids and reveal unknown phenomena. The readers will be introduced to the broad applications of the forces measurement in the materials science field.

This contribution describes the experiences with three careers: leading and building an academic research institute, heading a research area in a multinational pharma company and founding and leading a biotech company, which saw its first drug successfully enter the market in its 11 th year of existence. The three positions had very different challenges, the common denominator for success was good and innovative science. However, research in a commercial environment, in addition to scientific excellence, also means to demonstrate the likely commercial success of the particular research. The most challenging, but at the same time the most interesting mission was the foundation of a new company, securing the financial means and developing the drugs, which had been discovered, in the clinics.

The main purpose of academic studies is to be beneficial to humanity. Women in science are active contributors to academic research. Talented young women should be encouraged to pursue careers in academic science, in spite of long hours and low pay, because their contributions are valuable. This paper has been designed to explain the position of women in an academic organization and some situations faced by female academics as well as some of my academic experience.

I discovered novel copper and silver carbonyl catalysts while at the National Institute of Advanced Industrial Science and Technology. The energy saving synthesis of tert -carboxylic acids was developed using the carbonylation reaction of olefins or alcohols using these novel copper or silver carbonyl catalysts under atmospheric pressure and at room temperature. After retiring from the institute, I was involved in efforts to improve women’s status in natural science, technology, engineering, and mathematics. I worked for the gender equality committee of the Chemical Society of Japan and the Japan Inter-Society Liaison Association Committee for Promoting Equal Participation of Men and Women in Science and Engineering, which sent recommendations to the government on how to realize a society with gender equality. The government accepted our recommendations, and the numerical target for female researchers was written into the 3 rd Science and Technology Basic Plan in 2006. Based on the plan, the Ministry of Education, Culture, Sports, Science and Technology started programs to aid universities in increasing the percentage of female researchers from 2006.

Women have achieved great advances standing up for themselves in the last 100 years. Many important women were essential for the development of science but only a few (5% from total awarded individuals) have won Nobel prizes for their work. In this brief contribution, we would like to show that gender equality is in process and highlight the gaps that still have to be addressed. We also give an overview of the Brazilian scenario on this matter. In many countries, such as Brazil, women are already half of the researchers in Chemistry, but their representation become scarcer as their career advances, in coordination and direction positions.

This paper presents an overview of my career from my first contact with chemistry in 1948, when I was in the second year of secondary school and realized, for the first time, the importance of this science. This discovery led me to focus my university studies toward a bachelor’s degree in Chemistry. It was then that I had my first experience with the discipline of Crystallography, taught by Elisiário Távora, a young mineralogist who received his doctorate from MIT. Recognizing the importance of X-ray Crystallography for the elucidation of the molecular and crystal structure of all substances and for the understanding of their chemical and physical properties, I decided to dedicate myself to improving my knowledge of this subject with several visits to excellent international research groups working under the supervision of well-known crystallographers. Along with my scientific activities in Crystallography, another of my interests was to contribute to efforts to increase the number of crystallographers in Brazil and Latin-America, orienting several Master and PhD students. The support given by foreign visiting scientists and by those that became permanent members of our Institute and of other Brazilian research groups have been very important throughout my career.