526221-05-6Relevant academic research and scientific papers
Added Alkane Allows Thermal Thinning of Supramolecular Columns by Forming Superlattice?-An X-ray and Neutron Study
Yen, Ming-Huei,Chaiprapa, Jitrin,Zeng, Xiangbing,Liu, Yongsong,Cseh, Liliana,Mehl, Georg H.,Ungar, Goran
, p. 5757 - 5760 (2016)
We report a columnar superlattice formed by blends of dendron-like Li 3,4,5-Tris(n-Alkoxy)benzoates with n-Alkanes. Without the alkane, the wedge-shaped molecules form liquid crystal columns with 3 dendrons in a supramolecular disk. The same structure exi
Spiroborate-based dimeric assembly of oligo(ethylene glycol) end-capped with phenolic gallates
Yang, Jian-Ping,Wu, Xiao-Yu,Wang, Wan-Jun,Huang, Zuo-Gang,Jiang, Biao
, p. 2742 - 2745 (2016)
The synthesis of oligo(ethylene glycol) with biphenolic gallates as termini and their assembly to dimeric structures upon spiroborate formation are described. Complexation of these dimeric structures with alkali metal ions showed selectivity to lithium and potassium by tuning the length of the ethyleneoxy units. The methoxycarbonyl group on the dimeric compound could be manipulated in harsh conditions without destruction of the dimeric structure.
An Accelerated Modular-Orthogonal Ni-Catalyzed Methodology to Symmetric and Nonsymmetric Constitutional Isomeric AB2to AB9Dendrons Exhibiting Unprecedented Self-Organizing Principles
Daud, Hina,Hoffman, David J.,Huang, Ning,Jezorek, Ryan L.,Malineni, Jagadeesh,McClure, Emily R.,Partridge, Benjamin E.,Percec, Virgil,Peterca, Mihai,Sahoo, Dipankar,Song, Se Lin,Sung, Paul D.,Wang, Shitao,Wang, Xuefeng,Zhang, Na
supporting information, p. 17724 - 17743 (2021/11/04)
Five libraries of natural and synthetic phenolic acids containing five AB3, ten constitutional isomeric AB2, one AB4, and one AB5 were previously synthesized and reported by our laboratory in 5 to 11 steps. They were employed to construct seven libraries of self-assembling dendrons, by divergent generational, deconstruction, and combined approaches, enabling the discovery of a diversity of supramolecular assemblies including Frank-Kasper phases, soft quasicrystals, and complex helical organizations, some undergoing deracemization in the crystal state. However, higher substitution patterns within a single dendron were not accessible. Here we report three libraries consisting of 30 symmetric and nonsymmetric constitutional isomeric phenolic acids with unprecedented sequenced patterns, including two AB2, three AB3, eight AB4, five AB5, six AB6, three AB7, two AB8, and one AB9 synthesized by accelerated modular-orthogonal Ni-catalyzed borylation and cross-coupling. A single etherification step with 4-(n-dodecyloxy)benzyl chloride transformed all these phenolic acids, of interest also for other applications, into self-assembling dendrons. Despite this synthetic simplicity, they led to a diversity of unprecedented self-organizing principles: lamellar structures of interest for biological membrane mimics, helical columnar assemblies from rigid-solid angle dendrons forming Tobacco Mosaic Virus-like assemblies, columnar organizations from adaptable-solid angle dendrons forming disordered micellar-like nonhelical columns, columns from supramolecular spheres, five body-centered cubic phases displaying supramolecular orientational memory, rarely encountered in previous libraries forming predominantly Frank-Kasper phases, and two Frank-Kasper phases. Lessons from these self-organizing principles, discovered within a single generation of self-assembling dendrons, may help elaborate design principles for complex helical and nonhelical organizations of synthetic and biological matter.
One-Component Multifunctional Sequence-Defined Ionizable Amphiphilic Janus Dendrimer Delivery Systems for mRNA
Zhang, Dapeng,Atochina-Vasserman, Elena N.,Maurya, Devendra S.,Huang, Ning,Xiao, Qi,Ona, Nathan,Liu, Matthew,Shahnawaz, Hamna,Ni, Houping,Kim, Kyunghee,Billingsley, Margaret M.,Pochan, Darrin J.,Mitchell, Michael J.,Weissman, Drew,Percec, Virgil
supporting information, p. 12315 - 12327 (2021/08/20)
Efficient viral or nonviral delivery of nucleic acids is the key step of genetic nanomedicine. Both viral and synthetic vectors have been successfully employed for genetic delivery with recent examples being DNA, adenoviral, and mRNA-based Covid-19 vaccines. Viral vectors can be target specific and very efficient but can also mediate severe immune response, cell toxicity, and mutations. Four-component lipid nanoparticles (LNPs) containing ionizable lipids, phospholipids, cholesterol for mechanical properties, and PEG-conjugated lipid for stability represent the current leading nonviral vectors for mRNA. However, the segregation of the neutral ionizable lipid as droplets in the core of the LNP, the "PEG dilemma", and the stability at only very low temperatures limit their efficiency. Here, we report the development of a one-component multifunctional ionizable amphiphilic Janus dendrimer (IAJD) delivery system for mRNA that exhibits high activity at a low concentration of ionizable amines organized in a sequence-defined arrangement. Six libraries containing 54 sequence-defined IAJDs were synthesized by an accelerated modular-orthogonal methodology and coassembled with mRNA into dendrimersome nanoparticles (DNPs) by a simple injection method rather than by the complex microfluidic technology often used for LNPs. Forty four (81%) showed activity in vitro and 31 (57%) in vivo. Some, exhibiting organ specificity, are stable at 5 °C and demonstrated higher transfection efficiency than positive control experiments in vitro and in vivo. Aside from practical applications, this proof of concept will help elucidate the mechanisms of packaging and release of mRNA from DNPs as a function of ionizable amine concentration, their sequence, and constitutional isomerism of IAJDs.
Extraordinary Acceleration of Cogwheel Helical Self-Organization of Dendronized Perylene Bisimides by the Dendron Sequence Encoding Their Tertiary Structure
Wang, Li,Wang, Li,Partridge, Benjamin E.,Huang, Ning,Olsen, James T.,Sahoo, Dipankar,Zeng, Xiangbing,Ungar, Goran,Ungar, Goran,Graf, Robert,Spiess, Hans W.,Percec, Virgil
, p. 9525 - 9536 (2020/06/27)
The cogwheel model of hierarchical self-organization provides a route to highly ordered crystalline helical columnar hexagonal arrays of perylene bisimides (PBIs) conjugated to (3,4,5)-dimethyloctyl (racemic dm8*, r) minidendrons. Cogwheel PBIs assemble with identical structural order irrespective of molecular chirality to generate helical columns jacketed with an alkyl coat with length equal to half the helical pitch, exhibiting helical deracemization in the crystal state. These assemblies were accessible only via annealing or cooling and reheating at 1 °C/min. Recently it was discovered that hybrid rr8 sequence-defined dendrons with r and linear n-octyl (8) chains enabled the formation of the cogwheel phase at 10 °C/min upon heating but not cooling. Here we report four libraries of hybrid PBIs with sequence-defined dendrons containing r and n-alkyl (CnH2n+1) chains with n = 6, 7, 9, and 10. Structural analysis of these libraries by fiber X-ray diffraction and differential scanning calorimetry reveals that the 9r9 sequence enables an extraordinary acceleration of cogwheel assembly at rates of up to 50 °C/min on heating and cooling, providing, to the best of our knowledge, the fastest crystallizing supramolecular or covalent macromolecule known. Solid-state NMR studies help to elucidate this unexpected and unprecedented extraordinary acceleration of hierarchical self-organization, which arises from a combination of crystal packing of the ideal tertiary structure and alkyl chain dynamics. This general model raises questions about the use of achiral motifs to achieve high structural order in chiral systems and the need for disorder to create order in complex biological and bioinspired synthetic systems.
Sequence-defined dendrons dictate supramolecular cogwheel assembly of dendronized perylene bisimides
Partridge, Benjamin E.,Wang, Li,Sahoo, Dipankar,Olsen, James T.,Leowanawat, Pawaret,Roche, Cecilé,Ferreira, Henrique,Reilly, Kevin J.,Zeng, Xiangbing,Ungar, Goran,Heiney, Paul A.,Graf, Robert,Spiess, Hans W.,Percec, Virgil
supporting information, p. 15761 - 15766 (2019/10/11)
A dendronized perylene bisimide (PBI) that self-organizes into hexagonal arrays of supramolecular double helices with identical single crystal-like order that disregards chirality was recently reported. A cogwheel model of selfassembly that explains this process was proposed. Accessing the highly ordered cogwheel phase required very slow heating and cooling or extended periods of annealing. Analogous PBIs with linear alkyl chains did not exhibit the cogwheel assembly. Here a library of sequence-defined dendrons containing all possible compositions of linear and racemic alkyl chains was employed to construct self-assembling PBIs. Thermal and structural analysis of their assemblies by differential scanning calorimetry (DSC) and fiber X-ray diffraction (XRD) revealed that the incorporation of n-alkyl chains accelerates the formation of the high order cogwheel phase, rendering the previously invisible phase accessible under standard heating and cooling rates. Small changes to the primary structure, as constitutional isomerism, result in significant changes to macroscopic properties such as melting of the periodic array. This study demonstrated how changes to the sequencedefined primary structure, including the relocation of methyl groups between two constitutional isomers, dictate tertiary and quaternary structure in hierarchical assemblies. This led to the discovery of a sequence that self-organizes the cogwheel assembly much faster than even the corresponding homochiral compounds and demonstrated that defined-sequence, which has long been recognized as determinant for the complex structure of biomacromolecules including proteins and nucleic acids plays the same role also in supramolecular synthetic systems.
Drug compound for treating hepatopathy and application thereof
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Paragraph 0230-0232, (2019/10/15)
The invention discloses a drug compound for treating hepatopathy and application thereof. The drug compound specifically serves as a compound shown in general formula (I) or an optical isomer or a pharmaceutically-acceptable salt of the compound. The compound or the optical isomer or the pharmaceutically-acceptable salt of the compound has a good curative effect and low toxicity on hepatopathy, especially fatty liver. Experiments show that the compound has an obvious protective effect on zebrafish nonalcoholic fatty liver, so that the drug compound has a good application prospect in medicinesfor treatment or prevention of hepatopathy, especially fatty liver or liver fibrosis or liver cirrhosis.
A Regio- and Diastereoselective Anodic Aryl–Aryl Coupling in the Biomimetic Total Synthesis of (?)-Thebaine
Lipp, Alexander,Ferenc, Dorota,Gütz, Christoph,Geffe, Mario,Vierengel, Nina,Schollmeyer, Dieter,Sch?fer, Hans J.,Waldvogel, Siegfried R.,Opatz, Till
supporting information, p. 11055 - 11059 (2018/08/21)
The biosynthesis of thebaine is based on the regioselective, intramolecular, oxidative coupling of (R)-reticuline. For decades, chemists have sought to mimic this coupling by using stoichiometric oxidants. However, all approaches to date have suffered from low yields or the formation of undesired regioisomers. Electrochemistry would represent a sustainable alternative in this respect but all attempts to accomplish an electrochemical synthesis of thebaine have failed so far. Herein, a regio- and diastereoselective anodic coupling of 3′,4′,5′-trioxygenated laudanosine derivatives is presented, which finally enables electrochemical access to (?)-thebaine.
A [...] crown compound and its preparation method and application
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Paragraph 0043-0046, (2018/12/13)
The invention provides a boron-assistant crown ether compound and its preparation method and use. The boron-assistant crown ether compound has a structure shown in a general structural formula 1 and in the formula, groups are defined in the specification. Boron is introduced into crown ether, the boron-assistant crown ether with electric neutrality and an alkali metal complex can improve extraction distribution and separation coefficients, the boron-oxygen bond-closed boron-assistant crown ether compound as an extraction agent can be subjected to proton ring opening and realizes selective alkali metal ion complexing opening and closing, and the boron-assistant crown ether compound solves the problem of alkali metal ion extraction and separation based on the traditional crown ether and has a wide application prospect in alkali metal ion extraction and separation and especially in lithium ion separation.
Synthesis and solid-state polymerization of a macrocyclic compound with two butadiyne units
Kikuchi, Kohei,Tatewaki, Yoko,Okada, Shuji
supporting information, p. 387 - 394 (2017/06/14)
A macrocyclic compound 1 with two butadiyne and four dodecyloxy-substituted benzamide moieties was successfully synthesized, and its ring structure was confirmed by the MALDI-TOF mass spectra and the 1HNMR spectra. Compound 1 showed two modifications depending on solvent for the solidification. Characteristic excitonic absorption bands of polydiacetylene were observed at around 500 nm for one of the modifications after UV irradiation. Quantitative conversion of butadiyne moieties to the corresponding polydiacetylene structure was confirmed by the Raman spectra.
