Gd complexes of diethylenetriaminepentaacetic acid conjugates of low-molecular-weight chitosan oligosaccharide as a new liver-specific MRI contrast agent

This study was to describe the synthesis of complexes of gadolinium diethylenetriaminepentaacetic acid conjugates of low-molecular-weight chitosan oligosaccharide Gd-DTPA-CSn (n = 6, 8, 11) as a new class of contrast agent as well as its magnetic property in a pilot magnetic resonance imaging. The efficacy of the contrast agent was assessed by measuring the longitudinal relaxivity (r₁), FLASH imaging in phantoms in vitro and signal intensity in vivo of the rat abdominal axial imaging. The r₁ of Gd-DTPA-CS₁₁ was up to 11.65 mM^− 1·s^− 1, which was 3 times higher than that of the analogous MRI contrast agent Gd-DTPA in commercial use. In vivo MR images of rat obtained with Gd-DTPA-CS₁₁ showed strong signal enhancement in liver and the vessels of the liver parenchyma during the extended period of time. The present study suggests that the new synthesized gadolinium complexes can be used as a new class of practical liver-specific MRI contrast agent because of its superior performance compared with Gd-DTPA.     

Cyclotriphosphazene,a scaffold for 19F MRI contrast agents

A cyclotriphosphazene substituted with six 3,5-bis(trifluoromethyl) benzyloxy units was designed as a novel ¹⁹F MRI contrast agent. The resulting molecule has 36 magnetically equivalent fluorine atoms and exhibited suitable MRI properties with high imaging sensitivity, confirming the proof-of-concept as a convenient scaffold for the production of new ¹⁹F MRI contrasts agents.     

Carboxylic Acids as Directing Groups for C−H Bond Functionalization

The selective transformation of C?H bonds is one of the most desirable approaches to creating complexity from simple building blocks. Several directing groups are efficient in controlling the regioselectivity of catalytic C?H bond functionalizations. Among them, carboxylic acids are particularly advantageous, since they are widely available in great structural diversity and at low cost. The carboxylate directing groups can be tracelessly cleaved or may serve as the anchor point for further functionalization through decarboxylative couplings. This Minireview summarizes the substantial progress made in the last few years in the development of reactions in which carboxylate groups direct C?H bond functionalizations with formation of C?C, C?O, C?N, or C?halogen bonds at specific positions. It is divided into sections on C?C, C?O, C?N, and C?halogen bond formation, each of which is subdivided by reactions and product classes. Particular emphasis is placed on methods that enable multiple derivatizations by combining carboxylate‐directed C?H functionalization with decarboxylative couplings.     

Concise Synthesis of (±)-Clopidogrel via Carboxylation of Benzylamine with CO2

A concise and efficient synthesis of (±)-clopidogrel, an antithrombotic agent, is achieved by inserting CO₂ at the benzylic position as the key reaction without using any toxic transition metals. The overall yield of the synthetic process is 38% and the salient features include operationally simple process chemistry and fewer steps.     

An Investigation into the Migration of Segments in Crosslinked Fluorinated Polyimide Adhesive

Crosslinked fluorinated polyimides (CFPI) were successfully synthesized to study and explore the effect of cross-linkage on the migration of fluorinated segments and on the adhesion strength. Characterization by dynamic thermomechanical analysis (DMA) and thermo gravimetric analysis (TGA) confirmed good thermal properties of CFPI. X-ray photoelectron spectroscopy (XPS) results showed that the ratio of fluorinated component (6FDA-ODA) concentration of the surface to the bulk decreased with the crosslink density. The water contact angle of CFPI was lower than that of non-crosslinked fluorinated polyimide, indicating that the migration of fluorinated groups to the surface was reduced by the presence of cross-linkage. Therefore, CFPI, with no fluorine segregation on the surface, exhibited excellent wetting of adherent surfaces and adhesion strength, which was proved by lap shear strength (LSS) measurements and scanning electron microscopy.     

Towards the Rational Design of Efficient Organic Structure‐Directing Agents for Zeolite Synthesis

Zeolites are crystalline microporous materials with application in diverse fields, especially in catalysis. The ability to prepare zeolites with targeted physicochemical properties for a specific catalytic application is a matter of great interest, because it allows the efficiency of the entire chemical process to be increased (higher product yields, lower undesired by‐products, less energy consumption, and cost savings, etc). Nevertheless, directing the zeolite crystallization towards the material with the desired framework topology, crystal size, or chemical composition is not an easy task, since several variables influence the nucleation and crystallization processes. The combination of accumulated knowledge, rationalization, and innovation has allowed the synthesis of unique zeolitic structures in the last few years. This is especially true in terms of the design of organic and inorganic structure‐directing agents (SDAs). In this Minireview we will present the rationale we have followed in our studies to synthesize new zeolite structures, while putting this in perspective with the advances made by other researchers of the zeolite community.     

New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications

The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H₂O)₄[15‐MC_Cu(II)Glyha‐5](Cl)₃ ( 1 (Gd)), Gd(H₂O)₄[15‐MC_Cu(II)Alaha‐5](Cl)₃ ( 2 (Gd)), Gd(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 3 (Gd)) and Gd(H₂O)₃[15‐MC_Cu(II)Tyrha‐5](Cl)₃ ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H₂O)_3,4[15‐MC_Cu(II)Rha‐5]³⁺ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r₁) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM^?1 s^?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications.     

Surface treatment of CaCO3 with a mixture of amino- and mercapto-functional silane coupling agents and tensile properties of the rubber composites

In order to reinforce the composite consisting of isoprene rubber (IR) and calcium carbonate (CaCO₃) particles, the surface treatment of CaCO₃ particles with a mixture of amino- and mercapto-functional silane coupling agents was investigated. The quantity of chemisorbed silanes in treated CaCO₃ measured using thermogravimetry was greater for amino- than for mercapto-silane and for the tri- than for the dialkoxy structure. Second, the molecular mobility of polycondensate of the mixtures with the trialkoxy structure measured using ¹H pulse nuclear magnetic resonance had the least molecular mobility, i.e., formed the highest density network. The greater values of stress at 500% strain, fracture stress, and elongation at break were determined for the treatment with amino- and mercapto-functional silanes having a trialkoxy structure from the stress-strain curves of composite. The mixture treatment with dialkoxy structure and with amino- or mercapto-functional silane only did not improve the mechanical properties sufficiently. Interactions between the amino group and the CaCO₃ surface, covalent bonding between the mercapto group and the IR, and high density network formation of trialkoxy silane were important for improving the mechanical properties of the composite.