Anne-Marie Caminade

• French National Centre for Scientific Research

(Text in French) Dendrimers, macromolecules with multiple properties Dendrimers, also known as “molecular trees”, are part of the large family of polymers. They are made up of branched repetitive units, grafted step by step from a central core. Dendrimers have a large number of surface functions, easily accessible and modifiable according to the pr...

Resistance to bortezomib (BTZ) represents a major bottleneck to continue using this proteasome inhibitor in the treatment of mantle cell lymphoma (MCL). In this study, we investigated the mechanisms by which TRIM24 (tripartite motif-containing 24), a ubiquitin ligase enriched in the ubiquitome of BTZ-resistant MCL cells, modulates proteasome-autoph...

Organoclays are promising materials for pollutant retention, medicinal applications, and catalysis, making them an intriguing research topic. In this study, beidellite/montmorillonite and phosphorus-based dendrimer organoclays were prepared, and their microstructure was examined using X-ray diffraction, thermal analysis, Fourier-transform infrared...

As the main pioneer in the field of dendrimers, a term that he coined in 1985 in reference to their tree-like structure, Prof. Donald A. Tomalia has inspired several generations of researchers worldwide [...]

Organoclays are promising materials for pollutant retention, medicinal applications, and catalysis, making them an intriguing research topic. In this study, beidellite/montmorillonite and phosphorus-based dendrimer organoclays were prepared, and their microstructure was examined using X-ray diffraction, thermal analysis, Fourier-transform infrared...

The interactions of dendrimers having a phosphorus atom at each branching point, of type poly(phosphorhydrazone) (PPH), with different types of materials based on silicon and aluminum are reviewed. These dendrimers can be used for the functionalization of solid surfaces at the nanoscale, either by covalent immobilization, or by electrostatic intera...

Random difunctionalization of dendrimer surfaces, frequently employed in biological applications, provides the advantage of dual functional groups through a synthetic pathway that is simpler compared to precise difunctionalization. However, is the random difunctionalization as efficient as the precise difunctionalization on the surface of dendrimer...

The field of supported catalysis has experienced increased attention with respect to the development of novel architectures for immobilizing catalytic species, aiming to maintain or enhance their activity while facil-itating...

Since the discovery of cisplatin in the 1960s, the search for metallo-drugs that are more efficient than platinum complexes with negligible side effects has attracted much interest. Among the other metals that have been examined for potential applications as anticancer agents is copper. The interest in copper was recently boosted by the discovery o...

This review describes the two-photon absorption properties of dendrimers, which are arborescent three-dimensional macromolecules differing from polymers by their perfectly defined structure. The two-photon absorption process is a third order non-linear optical property that is attractive because it can be used in a wide range of applications. In th...

Invited for the cover of this issue are the groups and colleagues of Anne‐Marie Caminade at the CNRS and University of Toulouse, Evamarie Hey‐Hawkins at Leipzig University, and Agustí Lledós from the Autonomous University of Barcelona. The image depicts birds crowned by a carborane competing for access to food, to illustrate the steric hindrance en...

Several ortho‐carboranes bearing a phenoxy or a phenylamino group in the B9 position were prepared employing various protection and deprotection strategies. Following established protocols, dendritic compounds were synthesized from a hexachlorocyclotriphosphazene or thiophosphoryl chloride core, and possible anchoring options for the B9‐substituted...

Two families of phosphorhydrazone dendrons having either an azide or an alkyne linked to the core and diverse types of pyridine derivatives as terminal functions have been synthesized and characterized. These dendrons were grafted via click reaction to graphene oxide (GO) functionalized with either alkyne or azide functions, respectively. The resul...

The presence of a large number of boron atoms in boron clusters make them attractive tools for the treatment of cancer using boron neutron capture therapy (BNCT). Since the quantity of boron atoms present in the target cell directly affects the effectiveness of BNCT, the idea of gathering a high number of boron atoms in a single entity has emerged...

This review presents the state of the art of interactions between two different families of nanoobjects: nanoparticles—mainly metal nanoparticles, and dendrimers—mainly phosphorhydrazone dendrimers (or dendrons). The review firstly presents the encapsulation/protection of existing nanoparticles (organic or metallic) by phosphorus-based dendrimers a...

Dendrimers, being highly branched monodispersed macromolecules, predominantly exhibit identical terminal functionalities within their structural framework. Nonetheless, there are instances where the presence of two distinct surface functionalities becomes advantageous for the fulfilment of specific properties. To achieve this objective, one approac...

This review presents the synthesis of dendrons (dendritic wedges) based on cyclotriphosphazene cores, in which one function is a fluorescent group, and the five remaining functions are used for growing the dendritic branches. The growing of the branches is carried out by a divergent method, using a two‐step process which implies hydroxybenzaldehyde...

The Staudinger reaction between a phosphine and an azide, applied to phosphorus azides, has been used for the synthesis of a large variety of dendritic structures, incorporating P=N−P=X moieties (X = mainly S, but also O and N−R). Conjugation of the P=N bond with the P=X bond greatly stabilizes the P=N bond. Highly branched structures such as dendr...

This Special Issue, “Personalized and Precision Medicine 2022” (https://www [...]

Hydrogels are hydrophilic, three-dimensional networks able to imprison large amounts of water and are largely used in pharmaceutical formulations. Hydrogels are frequently obtained from hydrophilic polymers, either natural, biohybrid, or synthetic. Owing to their peculiar structure, dendrimers can be considered prospective building blocks for hydro...

Combined chemo/gene therapy of cancer through different action mechanisms has been emerging to enhance the therapeutic efficacy towards cancer, and still remains a challenging task due to the lack of highly effective and biocompatible nanocarriers. In this work, we report a new nanosystem based on amphiphilic phosphorus dendron (1-C12G1) micelles t...

The structure of phosphorus-containing dendrimers has been studied by IR spectroscopy and optical polarization microscopy. The repeating units of dendrimer molecules are mesogens. This property arises from the conjugation of the aromatic ring and the hydrazone group. An analysis of the IR spectra showed that, with an increase in the generation numb...

Automated X-ray data recording and data reduction strategies are straightforward and powerful these days, as well as semi-automated routines to solve standard structures without, or at least with only little manual inter­vention and within a relatively short time. The structure determination of the amino-carborane closo-9-[4-(di­benzyl­amino)­phen­...

Dendrimers are highly branched macromolecules tailorable at will to fulfil precise requirements. They have generated a great many expectations and a huge number of publications and patents in relation to medicine, including in relation to personalized medicine, but have resulted in very poor clinical translation up to now. As clinical trials are th...

Dendrimers are highly branched macromolecules possessing, in most cases, identical terminal functions. However, it is sometimes desirable to have two types of surface functions in order to fulfil specific properties. The stochastic functionalization is frequently used for such purposes, but the presence of an uncontrolled number of each type of ter...

Conventional small molecular chemical drugs always have challenging limitations in cancer therapy due to their high systemic toxicity and low therapeutic efficacy. Nanotechnology has been applied in drug delivery, bringing new promising potential to realize effective cancer treatment. In this context, we develop here a new nanomicellar drug deliver...

Tumor cells with stem cell properties are considered to play major roles in promoting the development and malignant behavior of aggressive cancers. Therapeutic strategies that efficiently eradicate such tumor stem cells are of highest clinical need. Herein, we performed the validation of the polycationic phosphorus dendrimer-based approach for smal...

Dendritic molecules bearing metal complexes in their structure (metallodendrimers and metallodendrons) are considered prospective therapeutic entities. In particular, metallodendrons raise interest as antitumor agents for the treatment of poorly curable or drug-resistant tumors. Herein, we have synthesized amphiphilic triazine-phosphorus dendrons b...

Dendrimers are macromolecular hyperbranched nano-structures, which properties are mainly driven by the type of their terminal functions. This paper reports the synthesis of dendritic structures built from difunctional polyethylene glycols (PEGs) used as core. Three different PEG lengths have been used: PEG300 (ca 6 CH2CH2-O units), PEG1000 (ca 22 C...

Different types of water‐soluble phosphorous dendrimers have been synthesized and display many different biological properties. It has been shown in particular that phosphorous dendrimers of first generation functionalized with azabisphosphonate terminal functions are able to stimulate the human immune system ex vivo. These dendrimers are internali...

Hydrogels are biocompatible matrices for local delivery of nucleic acids; however, functional dopants are required to provide efficient delivery into cells. In particular, dendrimers, known as robust nucleic acid carriers, can be used as dopants. Herein, we report the first example of impregnating neutral hydrogels with siRNA–dendrimer complexes. T...

The aim of this review is to present precisely defined amphiphilic dendrons (dendritic wedges), generally based on known dendrimers (aryl ether, amidoamine, amide, quaternary carbon, alkyl ether, ester, main group element), their self‐association properties, and their uses, in particular for encapsulation and delivery of bioactive entities. In most...

This review presents precisely defined amphiphilic dendrons, their self‐association properties, and their different uses. Dendrons, also named dendritic wedges, are composed of a core having two different types of functions, of which one type is used for growing or grafting branched arms, generally multiplied by 2 at each layer by using 1→2 branchi...

AB5 compounds issued from the reactivity of hexachlorocyclotriphosphazene are relatively easy to obtain using two ways: either first the reaction of one chloride with one reagent, followed by the reaction of the five remaining Cl with another reagent, or first the reaction of five chlorides with one reagent, followed by the reaction of the single r...

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers...

Dendrimers are hyperbranched macromolecules, having a large number of terminal functions, easily accessible and modifiable to afford the desired properties. Metal complexes of dendrimers are frequently used as catalysts in diverse reactions, but they can be used also as innovative biological tools. This review focusses on the recent advances (last...

We designed and synthesized several families of novel amphiphilic fluorescent phosphorus dendron-based micelles showing relevant antiproliferative activities for use in the field of theranostic nanomedicine. Based on straightforward synthesis pathways, 12 amphiphilic phosphorus dendrons bearing 10 protonated cyclic amino groups (generation one), or...

Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are known, this review focusses on the use of trivalent phosphorus derivatives (essentially phosphines and phosphoramidites) for the synthesis of dendrimers. The first part presents den...

Design of new families of dendritic soft nanoparticles constituted of phosphorus, viologen and carbosilane fragments and their properties as nanomaterials and applications in biology.

Phosphorus dendrimers are highly branched macromolecules, built with one phosphorus atom at each branching point. These dendrimers can be functionalized at will on the terminal functions. Grafting as terminal functions ligands suitable for the complexation of copper has been carried out several times, in particular with the aim of using the corresp...

A new class of phosphorus dendritic compounds (PDCs) having a cyclotriphosphazene (P3N3) core and decorated with six β-cyclodextrin (βCD) units, named P3N3-[O-C6H4-O-(CH2)n-βCD]6, where n = 3 or 4 was designed, and the synthesis was performed using copper (I) catalyzed alkyne-azide cycloaddition (CuAAC). To obtain the complete substitution of the P...

A small water-soluble phosphorus-containing dendrimer was engineered for the complexation of gold(I) and for its reduction under mild conditions. Gold nanoparticles were obtained as colloidal suspensions simply and only when the powdered form of this dendrimer was dissolved in water, as shown by transmission electron microscopy (TEM) and energy dis...

This review concerns the use of dendrimers, especially of phosphorhydrazone dendrimers, against cancers. After the introduction, the review is organized in three main topics, depending on the role played by the phosphorus dendrimers against cancers: (i) as drugs by themselves; (ii) as carriers of drugs; and (iii) as indirect inducer of cancerous ce...

Dendrimers are nanosized, arborescent macromolecules synthesized in a stepwise fashion with attractive degrees of functionality and structure definition. This is one of the reasons why they are widely used for biomedical applications. Previously, we have shown that a poly(phosphorhydrazone) (PPH) dendrimer capped with anionic azabisphosphonate grou...

This chapter will focus on the methods of synthesis of phosphorus-containing dendritic architectures, mainly of phosphorhydrazone type, but also on other types of phosphorus dendrimers. The different types of cores, branches and surface functionalities of phosphorhydrazone dendrimers will be displayed. An overview of the field will be given, concer...

Gene delivery, one important cancer therapy mode, still remains to be challenging due to the shortage of highly efficient and safe non-viral vectors. Here, we revisit the development of cationic phosphorus dendrimers by synthesizing them with different generations (G1-3) and surface ligands (1-(2-aminoethyl) pyrrolidine, 1-(3-aminopropyl) piperidin...

First‐in‐class CuII and AuIII metaled phosphorus dendrons were synthesized and showed significant antiproliferative activity against several aggressive breast cancer cell lines. The data suggest that the cytotoxicity increases with reducing length of the alkyl chains, whereas the replacement of CuII with AuIII considerably increases the antiprolife...

Attaining absolute control over a catalytic process and, therewith, exploiting its full potential pleases scientists in their ambitious and ongoing endeavor to perform catalysis like Nature does. In this regard, redox‐switchable catalysis certainly holds great potential, constantly gaining importance in modern catalysis research. Herein, we report...

The synthesis of a G0 polyamidoamide (PAMAM) dendrimer end‐capped with four β‐cyclodextrin (β‐CD) units, named as Tetra‐CD was performed by using copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC). This new platform presents a considerable high water‐solubility in comparison to native β‐CD. Tumbling process involving half of the CD cavities in...

The discovery of ferrocene is often associated with the rapid growth of organometallic chemistry. Dendrimers are highly branched macromolecules that can be functionalized at will at all levels of their structure. The functionalization of dendrimers with ferrocene derivatives can be carried out easily as terminal functions on the surface, but also a...

The versatile functionalization of thiazoles and benzothiazoles at different locations in their backbone offers the possibility to design many substituted heterocyclic derivatives bearing active groups for applications in coordination chemistry, catalysis, and medicinal chemistry. The grafting of various phosphorus groups (phosphines, phosphine oxi...

Different types of two-photon absorbing (TPA) fluorophores have been synthesized and specifically functionalized to be incorporated in the structure of phosphorus dendrimers (highly branched macromolecules). The TPA fluorophores were included in the periphery as terminal functions, in the core, or in the branches of the dendrimer structures, respec...

Dendrimers are nanosized, arborescent polymers of which size and structure are perfectly controlled. This is one reason why they are widely used for biomedical purposes. Previously, we showed that a phosphorus-based dendrimer capped with anionic azabisphosphonate groups (so-called ABP dendrimer) has immuno-modulatory and anti-inflammatory propertie...

Several metal‐based phosphorus dendrimers were prepared. The first series developed by us was the Cu(II) series. In this series, the most potent is the third generation‐Cu(II) showing original mechanism of action with activation of the pro‐apoptotic Bax protein. To our knowledge, it is the first example of nanoparticles displaying Bax protein activ...

Fluorescent derivatives of phosphorhydrazone dendrimers are reviewed. Diverse types of fluorophores have been used, such as pyrene, naphthol, anthracene, dansyl, diketone, phthalocyanine, maleimide, julolidine, rhodamine, fluorescein, or fluorene derivatives. The fluorescent groups can be located either as terminal groups on the surface, at the cor...

The possibility to incorporate diverse chemical species inside clays, especially swelling clay minerals, is known since more than two millennia, but the first examples of man-made polymers interacting with clays only dates back to about 30 years. Dendrimers and hyper-branched polymers differ from classical polymers by their intrinsically 3-dimentio...

Dendrimers are highly branched macromolecules, which have properties in many different fields, in particular for catalysis. This review presents an exhaustive view about complexes of phosphorus-containing dendrimers (having a phosphorus atom at each branching point), used as homogeneous catalysts in a range of reactions. First, catalysed reactions...

Phosphorus dendrimers (dendrimers having one phosphorus atom at each branching point) possess versatile properties, depending on the type of their terminal functions. This perspective article focusses on the synthesis and study of properties of phosphorus dendrimers functionalised on their surface by nitrogen ligands and their complexes. It is orga...

Noncovalent interactions often provide the spine of biomolecular and material structures, and can therefore play a key role in biological and catalytic processes. Selectivity in chemical reactions, particularly in catalytic processes, is often an orchestral action of various noncovalent interactions occurring in intermediates and transition states....

The synthesis and the photophysical properties of a new class of fully organic monodisperse nanoparticles for combined two‐photon imaging and photodynamic therapy are described. The design of such nanoparticles is based on the covalent immobilization of a dedicated quadrupolar dye that combines excellent two‐photon absorbing (2PA) properties, fluor...

The diversity of structures of inorganic dendrimers has been presented in Chapter 5, and the properties of inorganic dendrimers are emphasized in this chapter. However, only two families of inorganic dendrimers have attracted significant attention for their properties: the carbosilane dendrimers and the phosphorhydrazone dendrimers. Different types...

Dendrimers are a special class of hyperbranched polymers, constituted of branched constitutional repeating units. Contrary to common polymers, dendrimers are not synthesized by polymerization reactions, but by the step‐by‐step approach around a central core unit. Most dendrimers are organic compounds with nitrogen or quaternary carbon or benzene ri...

This study investigates the non‐covalent coating of cobalt magnetic nanoparticles (MNPs) involving a graphene surface with pyrene‐tagged dendritic poly(vinylidene fluoride) (PVDF). Dendrimers bearing a pyrene moiety were selected to play the role of spacers between the graphene surface of the MNPs and the PVDF chains, the pyrene unit being expected...

The role of phosphorhydrazide derivatives, in particular of type RP(X)(NMeNH2)2 for the synthesis of macrocycles and of type Cl2P(X)NMeNH2 (X = O, S in both cases) for the synthesis of dendrimers, will be shown in this review. In both cases, condensation reactions with different types of aldehydes (often aromatic) afford phosphorhydrazone derivativ...

The study of chelating ligands is undoubtedly one of the most significant fields of research in chemistry. The present work is directed to the synthesis of new functionalized derivatives of tripodal C-scorpionate compounds. Tris-2,2,2-(1-pyrazolyl)ethanol, HOCH2C(pz)3 (1), one of the most important derivatives of hydrotris(pyrazolyl)methane, was us...

Dectin-2 is a C-type lectin involved in the recognition of several pathogens such as Aspergillus fumigatus, Candida albicans, Schistosoma mansonii, and Mycobacterium tuberculosis that triggers Th17 immune responses. Identifying pathogen ligands and understanding the molecular basis of their recognition is one of the current challenges. Purified M....

We present here the development of multifunctional doxorubicin (DOX)-conjugated poly(amidoamine) (PAMAM) dendrimers as a unique platform for pH-responsive drug release and targeted chemotherapy of cancer cells. In this work, we covalently conjugated DOX onto the periphery of partially acetylated and folic acid (FA)-modified generation 5 (G5) PAMAM...

The adsorption capacities of nano-sized organoclays composed of a stevensite-rich clay (R), phosphorus dendrimers (GC1 and GC2) and Na ⁺ -saturated clay were evaluated for their capacity to adsorb chromate and methylene blue (MB) in the range of 298–318 K. The adsorption kinetics and the isotherms were analysed based on kinetic equations and isothe...

In this work, we report the assemblage of hydrogels from phosphorus dendrimers in the presence of biocompatible additives and the study of their interactions with nucleic acids. As precursors for hydrogels, phosphorus dendrimers of generations 1–3 based on the cyclotriphosphazene core and bearing ammonium or pyridinium acetohydrazones (Girard reage...

Tuberculosis (TB) is a contagious infection that usually attacks not only the lungs, but also brain and spine. More than twenty drugs have been developed for the treatment of TB, but most of them were developed some years ago. They are used in different combinations. Isoniazid and Rifampicin are examples of the five first line TB drugs, whereas, fo...

The presence of an azido group directly linked to phosphorus functionalized monomeric species allows the synthesis of neutral or polycationic original phosphorus dendrimers of reduced symmetry bearing branches of different...

At the intersection between treatment and diagnosis, nanoparticles technologies are strongly impacting the development of both therapeutic and diagnostic agents. Consequently, the development of novel modalities for concomitant noninvasive therapy and diagnostics known as theranostics as a single platform has gained significant interests. These mul...