1,721,072 research outputs found
Synthesis of a rigidified bicyclic AAZTA-like ligand and relaxometric characterization of its GdIII complex
The synthesis of a novel constrained polydentate ligand CpAAZTA derived from the heptadentate polyaminocarboxylic ligand AAZTA (6-amino-6-methylperhydro-1,4-diazepine-N, N’,N’’,N’’-tetraacetic acid) in which the ethylene bridge of the 1,4-diazepine ring is replaced by a cyclopentyl bridge is reported. In order to compare the effect of the different size and rigidity induced on the chelate by a 5-membered ring vs. a previously-reported cyclohexane-derivative, the relaxivity of the corresponding bis-hydrated GdIII complex was also investigated as a function of the magnetic field, temperature and pH
Beyond gadolinium: The potential of manganese nanosystems in MRI and multimodal imaging agents
Manganese-based nanoparticles (Mn-NPs) hold great promise as MRI contrast agents and components of theranostic nanoplatforms, serving as a promising alternative to the more established gadolinium(III)-based nanosystems. This potential stems from their unique physicochemical properties and improved safety profile.
This review introduces the fundamental principles of relaxation to highlight the key physicochemical characteristics of Mn-based nanosystems that influence their effectiveness. We primarily examine two oxidation states of manganese, Mn(II) and Mn(III), to demonstrate the efficacy of Mn-NPs as relaxation probes, with a brief
discussion of one Mn(IV) system. Subsequently, we review recent studies on Mn-NP-based MRI contrast agents, focusing on the correlation between nanoparticle structure and the oxidation state of the paramagnetic centre.
For Mn(II), the most common strategy involves utilizing stable Mn-chelates anchored to or encapsulated within the nanoparticles. In contrast, for the higher oxidation state, Mn(III), Mn(III)-porphyrin and phthalocyanine NPs are the primary non-Mn oxide nanosystems of choice. Regarding nanoplatform composition, Mn(II)-based
platforms utilizing lipids (micelles or liposomes), polysaccharides (nanogels), dendrimers, metal-organic frameworks, inorganic NPs, and silicas are among the most frequently investigated. While numerous in vitro and in vivo animal MRI studies of Mn nanoplatforms have been reported, none have yet received clinical approval. We describe innovative surface modification and functionalization procedures designed to improve NP characteristics (e.g., size, stability, dispersibility, relaxivity, targeting, and toxicity) and impart multifunctionality for multimodal imaging. These strategies may provide valuable guidance for the development of Mn-NPs toward future clinical applications, particularly in cancer theranostics.
Statement of significance: This review provides a critical analysis of the current landscape of Mn-based nano particles, which are increasingly being explored as MRI contrast agents and for multimodal imaging. This growing interest is largely driven by concerns over the potential toxicity and environmental impact of traditional
Gd-based systems. The review introduces the key structural and dynamic parameters that determine the effectiveness of these nanosystems, highlighting their direct relationship with molecular design. It also examines the crucial stability and kinetic inertness requirements that influence their development. By critically discussing
selected recent examples across a diverse range of nanosystems, including micelles, liposomes, silica-based platforms, and MOFs, this review identifies existing challenges and provides key insights to guide their future clinical translation
Selective functionalization of 6-amino-6-methyl-1,4-perhydrodiazepine for the synthesis of a library of polydentate chelators
Polydentate chelators are an important part of an imaging probe, which consists of an agent that usually produces signals for imaging purposes connected to a targeting moiety. The goal of this study was to set up a generic protocol to prepare a library of polydentate ligands having a 6-amino-6-methyl-1,4-perhydrodiazepine (AMPED) core and able to chelate metal ions of interest for various diagnostic imaging techniques, including Magnetic Resonance Imaging (MRI), Positron Emission Tomography (PET) and Single-Photon Emission Computed Tomography (SPECT). These ions, among which we can include Mn(ii), Cu(ii), Al(iii) or Ga(iii), require penta- or hexa-dentate chelators for this purpose, and the AMPED scaffold has considerable potential to support various pendant arms for coordination of such ions. AMPED already has three amino nitrogen donors; thus, only two or three additional arms should be introduced to obtain penta- or hexa-dentate systems. This condition implies that symmetrical or asymmetrical structures have to be developed, depending on the functionalization of cyclic and exocyclic amines. Starting from easily available materials, we have designed a convenient protocol for the preparation of multiple AMPED-based ligands endowed with different characteristics, several of which were synthesized as examples. This journal i
Synthesis of 6-Substituted 6-Nitroperhydro-1,4-diazepines via Novel Tandem Retro-Henry and Mannich/Michael Reactions
Going Beyond Counting First Authors in Author Co-citation Analysis
The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Relaxivity Modulation of Gd-HPDO3A-like Complexes by Introducing Polar and Protic Peripheral Groups
In the last three decades, high-relaxivity Magnetic Resonance Imaging (MRI) contrast
agents (CAs) have been intensively sought, aiming at a reduction in the clinically injected dose while maintaining the safety of the CA and obtaining the same pathological information. Thus, four new Gd(III) complexes based on modified 10-(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (HP-DO3A) macrocyclic structure were designed and synthesized by introducing further polar and protic functional groups (amides, phosphonates, and diols) adjacent to the metalcoordinated hydroxyl group. A detailed 1H NMR relaxometric analysis allowed us to investigate the effect of these functional groups on the relaxivity, which showed a 20–60% increase (at 0.5 T, 298 K, and pH 7.4) with respect to that of clinically approved CAs. The contribution of the water molecules H-bonded to these peripheral functional groups on the relaxivity was evaluated in terms of the second sphere effect or prototropic exchange of labile protons
On the gas storage properties of 3D porous carbons derived from hyper-crosslinked polymers
The preparation of porous carbons by post-synthesis treatment of hypercrosslinked polymers is described, with a careful physico-chemical characterization, to obtain new materials for gas storage and separation. Different procedures, based on chemical and thermal activations, are considered; they include thermal treatment at 380 degrees C, and chemical activation with KOH followed by thermal treatment at 750 or 800 degrees C; the resulting materials are carefully characterized in their structural and textural properties. The thermal treatment at temperature below decomposition (380 degrees C) maintains the polymer structure, removing the side-products of the polymerization entrapped in the pores and improving the textural properties. On the other hand, the carbonization leads to a different material, enhancing both surface area and total pore volumethe textural properties of the final porous carbons are affected by the activation procedure and by the starting polymer. Different chemical activation methods and temperatures lead to different carbons with BET surface area ranging between 2318 and 2975 m(2)/g and pore volume up to 1.30 cc/g. The wise choice of the carbonization treatment allows the final textural properties to be finely tuned by increasing either the narrow pore fraction or the micro- and mesoporous volume. High pressure gas adsorption measurements of methane, hydrogen, and carbon dioxide of the most promising material are investigated, and the storage capacity for methane is measured and discussed
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