753031-26-4

Upstream product

• 53876-68-9 C₁₆H₁₂N₄O₄ 
• 619-65-8 4-cyanobenzoic Acid 
• 14080-23-0 2-cyanopyrimidine 

Relevant academic research and scientific papers

Synthesis, characterization and self-assembly of new cholesteryl-substitued sym-tetrazine: Fluorescence, gelation and mesogenic properties

Fluorescent liquid crystalline organogels have been considered as proper candidates for low-energy consumption electronic displays particularly for portable flexible electronics. Herein, we synthesized novel fluorescent symmetric 3,6-bis(4-(cholesterylester)phenyl)-1,2,4,5-tetrazine (sym-Tetrazine; DCh-Tz) liquid crystalline low molecular weight organogelator (LMWO). The molecular structure of the prepared sym-Tetrazine was characterized by different spectroscopic methods, including 1H/13C NMR and FT-IR spectra. The new oganogelator, sym-tetrazine, was synthesized via an addition reaction of hydrazine monohydrate with 4-cyanobenzoic acid to give the corresponding dihydrotetrazine. The product of the addition reaction was subjected to an oxidation reaction to give 3,6-bis(4-carboxyphenyl)-tetrazine to interact with cholesterol affording the desired DCh-Tz. It was proved to possess fairly high gelation capability to generate nanofibers in various alcohols, such as 1,6-dihydroxyhexane, n-octanol and n-butanol. The mesogenic phases of the prepared cholesterylester s-tetrazine were studied by POM and DSC. The photophysical properties of the new fluorescent and thermoreversible low molecular weight organogelator from cholesterylester s-tetrazine were discussed. Both of UV-Vis absorption and fluorescence spectra showed a solvatochromic and solvatofluorochromic activities, respectively. The supramolecular self-assembly of the synthesized cholesterylester s-tetrazine occurred via van der Waals and π-stack interaction forces to result in the gelation of various organic solvents. A dried xerogel of the cholesterylester s-tetrazine was studied by scanning electron microscopy (SEM) to show fiber-like nano-scaled scaffolds. Both of cytotoxicity and antimicrobial properties were explored to prove the use the current DCh-Tz for other potential applications, such as bioimaging and drug delivery systems.

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals

The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability, and porosity, all relevant to photocatalysis. We use solvent-assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution and the reaction time control the distribution of this linker in the sibling crystals for a uniform mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.

Tetrazine-Based Metal-Organic Frameworks as Scaffolds for Post-Synthetic Modification by the Click Reaction

Metal-organic frameworks are one of the most active research fields today. Despite the progress in recent years, synthesis of highly porous structures bearing functional groups for specific applications remains a challenge. Here, we describe synthesis of Zr(IV) and Hf(IV)-based tetrazine containing metal-organic frameworks, ZrTz-68 and HfTz-68 with pore size of 2.1 nm, specific surface area up to 4217 m2 g–1, and a UiO-68 topology. The synthesis can be done on a multi-gram scale from inexpensive linker 4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid (H2TzDB). Moreover, because of the π-conjugated tetrazine groups these MOFs can be easily post-synthetically modified by a “click” reaction maintaining the crystallinity of the framework. Due to the diversity of “clickable” substituents, this strategy represents highly versatile tool for a wide range of applications.

Towards a potential 4,4′-(1,2,4,5-tetrazine-3,6-diyl) dibenzoic spacer to construct metal-organic frameworks

The ligand 4,4′-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid has been designed and explored with the aim of using it as a linker to construct three-dimensional metal-organic frameworks (MOFs). We have been successful in the formation of a potassium 3D-MOF using this novel linker. This compound has a three-dimensional structure, wherein the layers formed by potassium ions and carboxylate groups are separated by this organic ligand. Luminescence and cytotoxicity studies have been performed. We used molecular simulations to predict the porous properties of an isoreticular compared to IRMOF-16 based on this linker due to the similarity of the newly designed ligand with p-terphenyl-4,4′′-dicarboxylate present in IRMOF-16.

Clicking 1,2,4,5-tetrazine and cyclooctynes with tunable reaction rates

Substituted tetrazines have been found to undergo facile inverse electron demand Diels-Alder reactions with "tunable" reaction rates.

Preparation of carbohydrate arrays by using Diels-Alder reactions with inverse electron demand

Carbohydrate microarrays are an emerging tool for the high-throughput screening of carbohydrate-protein interactions that represent the basis of many biologically and medicinally relevant processes. The crucial step in the preparation of carbohydrate arrays is the attachment of carbohydrate probes to the surface. We examined the Diels-Alder reaction with inverse-electron-demand (DARinv) as an irreversible, chemoselective ligation reaction for that purpose. After having shown the efficiency of the DARinv in solution, we prepared a series of carbohydrate-dienophile conjugates that were printed onto tetrazine-modified glass slides. Binding experiments with fluorescently labeled lectins proved successful and homogeneous immobilization was achieved by the DARinv. For immobilization of nonfunctionalized reducing oligosaccharides we developed a bifunctional chemoselective linker that enabled the attachment of a dienophile tag to the oligosaccharides through oxime ligation. The conjugates obtained were successfully immobilized on glass slides. The presented strategies for the immobilization of both synthetic carbohydrate derivatives and unprotected reducing oligosaccharides facilitate the preparation of high-quality carbohydrate microarrays by means of the chemoselective DARinv. This concept can be readily adapted for the preparation of other biomolecule arrays. Copyright