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101.
S. V. Partsevskaya T. B. Zheltonozhskaya D. O. Klymchuk 《Molecular Crystals and Liquid Crystals》2018,671(1):128-139
AbstractA series of amphiphilic MOPEO-b-PCL copolymers (DBCs), based on biocompatible methoxypoly(ethylene oxide) with Mn=4.5?kDa and poly(ε-caprolactone) of a variable chain length, was synthesized by an anionic ring-opening block copolymerization. The structural investigations, performed by DSC and WAXS methods, revealed the microphase separation in DBC bulk structure and the existence of separate amorphous regions and microcrystalline domains of MOPEO and PCL blocks. Spectrophotometry and SLS were used to study the self-assembling of DBC macromolecules in selective dioxane/aqueous solution and to determine the main micellization parameters (CMC and -ΔG°). The DBC micelles morphology and their specific aggregation in mixed solvent were shown. 相似文献
102.
Mahsa Kiani Mojtaba Bagherzadeh Soraia Meghdadi Farzaneh Fadaei-Tirani Maryam Babaie Kurt Schenk-Joß 《应用有机金属化学》2020,34(11):e5911
The new Co(II) - carboxamide complex ( 1 ) and Co3O4 nanoparticles ( 2 ), by way of thermal decomposition of ( 1 ) have been efficiently synthesised in the environment-friendly. X-ray diffraction reveals a slightly distorted octahedral coordination of cobalt (four nitrogens and two oxygens) in ( 1 ) and regular octahedral or tetrahedral ones (oxygens only) in ( 2 ). The investigation of ( 1 ) and ( 2 ) in the Mizoroki-Heck and epoxidation of alkens reactions showed them both to be powerful, green and inexpensive catalysts. 相似文献
103.
Antoine Bardin Pierre-Yves Le Gac Hervé Bindi Bruno Fayolle 《Journal of polymer science. Part A, Polymer chemistry》2020,58(22):3170-3182
This publication highlights the structure–property relationships in several thermoplastic elastomers (TPEs): one poly(ether-block-amide) and two thermoplastic polyurethane elastomers with ester and ether soft blocks. Structural changes are induced by chemical degradation from virgin samples through hydrolysis and oxidation. Molar mass measurements show an exclusive chain scission mechanism for all TPEs, regardless of the chemical modification condition. Mechanical behavior was nevertheless obtained from uniaxial tensile testing and fracture testing while considering the essential work of fracture (EWF) concept. During the macromolecular scission process, elongation at break shows a plateau followed by a drop, while stress at break decreases steadily. Once again, the trend is identical for all TPEs in all conditions considered. The βwp parameter determined using the EWF concept exhibits an interesting sensitivity to scissions (i.e., molar mas decrease). Plotting elongation at break as a function of molar mass reveals a strong correlation between these two parameters. This master curve is particularly remarkable considering the range of TPEs and chemical breakdown pathways considered (hydrolysis and oxidation at several temperatures). Relevant structure–property relationships are proposed, highlighting that molar mass is a predominant parameter for determining the mechanical properties of thermoplastic elastomers. 相似文献
104.
Hyunchang Park Prof. Dr. Dongwhan Lee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(27):5916-5926
Novel functions emerge from novel structures. To develop efficient catalytic systems for challenging chemical transformations, chemists often seek inspirations from enzymatic catalysis. A large number of iron complexes supported by nitrogen-rich multidentate ligands have thus been developed to mimic oxo-transfer reactivity of dioxygen-activating metalloenzymes. Such efforts have significantly advanced our understanding of the reaction mechanisms by trapping key intermediates and elucidating their geometric and electronic properties. Critical to the success of this biomimetic approach is the design and synthesis of elaborate ligand systems to balance the thermodynamic stability, structural adaptability, and chemical reactivity. In this Concept article, representative design strategies for biomimetic atom-transfer chemistry are discussed from the perspectives of “ligand builders”. Emphasis is placed on how the primary coordination sphere is constructed, and how it can be elaborated further by rational design for desired functions. 相似文献
105.
Olga N. Vysochanskaya Dr. Victor A. Brotsman Dr. Alexey A. Goryunkov Dr. Christian G. Feiler Prof. Dr. Sergey I. Troyanov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(11):2338-2341
The carbon cage of buckminsterfullerene Ih-C60, which obeys the Isolated-Pentagon Rule (IPR), can be transformed to non-IPR cages in the course of high-temperature chlorination of C60 or C60Cl30 with SbCl5. The non-IPR chloro derivatives were isolated chromatographically (HPLC) and characterized crystallographically as 1809C60Cl16, 1810C60Cl24, and 1805C60Cl24, which contain, respectively two, four, and four pairs of fused pentagons in the carbon cage. High-temperature trifluoromethylation of the chlorination products with CF3I afforded a non-IPR CF3 derivative, 1807C60(CF3)12, which contains four pairs of fused pentagons in the carbon cage. Addition patterns of non-IPR chloro and CF3 derivatives were compared and discussed in terms of the formation of stabilizing local substructures on fullerene cages. A detailed scheme of the experimentally confirmed non-IPR C60 isomers obtained by Stone–Wales cage transformations is presented. 相似文献
106.
Bodil Lousen Dr. Stephan K. Pedersen Pernille Bols Kasper H. Hansen Michelle R. Pedersen Prof. Ole Hammerich Dr. Sergey Bondarchuk Prof. Boris Minaev Dr. Glib V. Baryshnikov Prof. Hans Ågren Prof. Michael Pittelkow 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4935-4940
This work describes a synthetic approach where a non-planar aromatic heterocyclic [7]helicene is compressed to yield a hetero[8]circulene containing an inner antiaromatic cyclooctatetraene (COT) core. This [8]circulene consists of four benzene rings and four heterocyclic rings, and it is the first heterocyclic [8]circulene containing three different heteroatoms. The synthetic pathway proceeds via a the flattened dehydro-hetero[7]helicene, which is partially a helicene and partially a circulene: it is non-planar and helically chiral as helicenes, and contains a COT motif like [8]circulenes. The antiaromaticity of the COT core is confirmed by nucleus independent chemical shift (NICS) calculations. The planarization from a helically π-conjugated [7]helicene to a fully planar heterocyclic [8]circulene significantly alters the spectroscopic properties of the molecules. Post-functionalization of the [7]helicenes and the [8]circulenes by oxygenation of the thiophene rings to the corresponding thiophene-sulfones allows an almost complete fluorescence emission coverage of the visible region of the optical spectrum (400–700 nm). 相似文献
107.
Atsuki Nagata Shinsuke Hiraoka Dr. Shuichi Suzuki Prof. Dr. Masatoshi Kozaki Prof. Dr. Daisuke Shiomi Prof. Dr. Kazunobu Sato Prof. Dr. Takeji Takui Dr. Rika Tanaka Prof. Dr. Keiji Okada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3166-3172
A triplet ground-state diradical molecule, bis(nitronyl nitroxide)-substituted diphenyldihydrophenazine ( 1 ..), that can be converted into a one-electron oxidized species, 1 … + , in the quartet ground state has been developed. Surprisingly, these species, 1 .. and 1 … + , can be used under ambient conditions because they are reasonably stable under aerobic conditions, even in solution. The temperature-dependent magnetic susceptibilities reveal that 1 .. and 1 … + are in the triplet state, with a weak exchange interaction (J1/kB = +3.1 K) and quartet ground state with a strong exchange interaction (J2/kB = +160 K), respectively. The interconversion between the neutral and one-electron oxidized species can be realized through electrochemical reactions. Significantly different absorption bands in the near-IR region newly appeared in the electronic spectra acquired during electrochemical oxidation/reduction. 相似文献
108.
Dr. Yuman Sayed-Ahmad-Baraza Dr. Christopher P. Ewels 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6686-6693
Density functional studies of the edges of single-layer 1H-MoS2 are presented. This phase presents a rich variability of edges that can influence the morphology and properties of MoS2 nano-objects, play an important role in industrial chemical processes, and find future applications in energy storage, electronics and spintronics. The so-called Mo-100 %S edges vertical S-dimers were confirmed to be stable, however the authors also identified a family of metastable edges combining Mo atoms linked by two-electron donor symmetrical disulfide ligands and four-electron donor unsymmetrical disulfide ligands. These may be entropically favored, potentially stabilizing them at high temperatures as a “liquid edge” phase. For Mo-50 %S edges, S-bridge structures with 3× periodicity along the edge are the most stable, compatible with a Peierls’ distortion arising from the d-bands of the edge Mo atoms. An additional explanation for this periodicity is proposed through the formation of 3-center bonds. 相似文献
109.
Daniela Cappello Dr. Ryan R. Maar Prof. Dr. Viktor N. Staroverov Prof. Dr. Joe B. Gilroy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5522-5529
The creation of dimeric boron difluoride complexes of chelating N-donor ligands is a proven strategy for the enhancement of the optoelectronic properties of fluorescent dyes. We report dimers based on the boron difluoride hydrazone (BODIHY) framework, which offer unique and sometimes unexpected substituent-dependent absorption, emission, and electrochemical properties. BODIHY dimers have low-energy absorption bands (λmax=421 to 479 nm, ϵ=17 200 to 39 900 m −1 cm−1) that are red-shifted relative to monomeric analogues. THF solutions of these dimers exhibit aggregation-induced emission upon addition of water, with emission enhancement factors ranging from 5 to 18. Thin films of BODIHY dimers are weakly emissive as a result of the inner-filter effect, attributed to intermolecular π-type interactions. BODIHY dimers are redox-active and display two one-electron oxidation and two one-electron reduction waves that strongly depend on the N-aryl substituents. These properties are rationalized using density-functional theory calculations and X-ray crystallography experiments. 相似文献
110.
Dr. Hirokazu Tsukamoto Saki Nakamura Akito Tomida Prof. Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12528-12532
Haouamines A, B, and their derivatives were synthesized via Suzuki–Miyaura coupling and three key cyclization reactions as follows: the newly developed palladium(0)-catalyzed arylative cyclization of phenylalanine-derived alkyne–aldehydes with 2-bromoarylboronic acid (an “anti-Wacker”-type cyclization); BF3 ⋅ OEt2-promoted Friedel–Crafts-type cyclization of symmetrical electron-rich aromatic rings adjacent to a tertiary allylic alcohol leading to the indeno-tetrahydropyridine skeleton; and (cyanomethyl)trimethylphosphonium iodide-mediated macrocyclization of amino alcohols to afford aza-paracyclophane precursors. The palladium-catalyzed reduction of mono- and di-triflate intermediates in the later stages enabled the alteration of both the position and number of hydroxyl groups on the C-ring. The instability of haouamine B was dramatically improved by salt formation with formic acid. An unambiguous evaluation of the cytotoxicity of the prepared haouamine derivative formates with and without hydroxyl groups at different positions on the C-ring indicated that the catechol structure in haouamine B produced weak cytotoxicity. 相似文献