Covalently Bonded Organic Structures via On‐Surface Synthesis

2021 ◽  
pp. 135-169
Author(s):  
Can Wang ◽  
Haiming Zhang ◽  
Lifeng Chi
Keyword(s):  
Author(s):  
Richard J. Spontak ◽  
Steven D. Smith ◽  
Arman Ashraf

Block copolymers are composed of sequences of dissimilar chemical moieties covalently bonded together. If the block lengths of each component are sufficiently long and the blocks are thermodynamically incompatible, these materials are capable of undergoing microphase separation, a weak first-order phase transition which results in the formation of an ordered microstructural network. Most efforts designed to elucidate the phase and configurational behavior in these copolymers have focused on the simple AB and ABA designs. Few studies have thus far targeted the perfectly-alternating multiblock (AB)n architecture. In this work, two series of neat (AB)n copolymers have been synthesized from styrene and isoprene monomers at a composition of 50 wt% polystyrene (PS). In Set I, the total molecular weight is held constant while the number of AB block pairs (n) is increased from one to four (which results in shorter blocks). Set II consists of materials in which the block lengths are held constant and n is varied again from one to four (which results in longer chains). Transmission electron microscopy (TEM) has been employed here to investigate the morphologies and phase behavior of these materials and their blends.


Author(s):  
S.D. Smith ◽  
R.J. Spontak ◽  
D.H. Melik ◽  
S.M. Buehler ◽  
K.M. Kerr ◽  
...  

When blended together, homopolymers A and B will normally macrophase-separate into relatively large (≫1 μm) A-rich and B-rich phases, between which exists poor interfacial adhesion, due to a low entropy of mixing. The size scale of phase separation in such a blend can be reduced, and the extent of interfacial A-B contact and entanglement enhanced, via addition of an emulsifying agent such as an AB diblock copolymer. Diblock copolymers consist of a long sequence of A monomers covalently bonded to a long sequence of B monomers. These materials are surface-active and decrease interfacial tension between immiscible phases much in the same way as do small-molecule surfactants. Previous studies have clearly demonstrated the utility of block copolymers in compatibilizing homopolymer blends and enhancing blend properties such as fracture toughness. It is now recognized that optimization of emulsified ternary blends relies upon design considerations such as sufficient block penetration into a macrophase (to avoid block slip) and prevention of a copolymer multilayer at the A-B interface (to avoid intralayer failure).


2020 ◽  
Author(s):  
Haoyang Yu ◽  
Alyxandra Thiessen ◽  
Md Asjad Hossain ◽  
Marc Julian Kloberg ◽  
Bernhard Rieger ◽  
...  

<div><div><div><p>Covalently bonded organic monolayers play important roles in defining the solution processability, ambient stability, and electronic properties of two-dimensional (2D) materials such as Ge nanosheets (GeNSs); they also hold promise of providing avenues for the fabrication of future generation electronic and optical devices. Functionalization of GeNS normally involves surface moieties linked through covalent Ge−C bonds. In the present contribution we extend the scope of surface linkages to include Si−Ge bonding and present the first demonstration of heteronuclear dehydrocoupling of organosilanes to hydride-terminated GeNSs obtained from the deintercalation and exfoliation of CaGe2. We further exploit this new surface reactivity and demonstrated the preparation of directly bonded silicon quantum dot-Ge nanosheet hybrids.</p></div></div></div>


1989 ◽  
Vol 54 (11) ◽  
pp. 3011-3024 ◽  
Author(s):  
Vlastimil Fidler ◽  
Stefan Vajda ◽  
Zuzana Limpouchová ◽  
Jiří Dvořák ◽  
Karel Procházka ◽  
...  

The methodology of polarization time-resolved fluorometry and interpretation of its results are outlined at a general level, and the measurement on and use of facilities of the Edinburgh Instruments Model 299T apparatus are discussed in detail. The dynamics of conformational changes in chains of poly(methacrylic acid) containing covalently bonded dansyl labels are studied in aqueous solutions at various pH. It is shown that at pH > 6, the shorter effective rational correlation time τr < 2 ns corresponds to the rotation of the free dansyl label about bonds by which it is attached to the polymeric chain; at pH < 4 the longer effective rational correlation time τr = 20-26 ns corresponds to the rotation of the compact spherical formation constituted by a part of the collapsed polymeric chain in which the label is fixed and whose relative molecular mass is approx. 15 000-20 000.


2006 ◽  
Vol 71 (5) ◽  
pp. 756-768 ◽  
Author(s):  
Karel Jelínek ◽  
Filip Uhlík ◽  
Zuzana Limpouchová ◽  
Pavel Matějíček ◽  
Karel Procházka

The multimolecular micelles formed by polystyrene-block-poly(methacrylic acid) (PS-PMA) copolymer and by hydrophobically modified PS-PMA copolymer with naphthalene and anthracene (PS-N-PMA-A) were studied by self-consistent field (SCF) calculations in aqueous media. The labeling with covalently bonded naphthalene between PS and PMA blocks and with anthracene at the free end of PMA blocks, which is suitable for experimental nonradiative excitation energy transfer (NRET) studies of PS-N-PMA-A micelles, modifies the structure of micellar shell. The study was aimed at understanding structure and behavior of micelles at different pH and ionic strength. The results show that the presence of hydrophobic tags has only a small influence on the overall structure of micelles but it strongly affects the distribution of PMA free ends. The hydrophobic labels (anthracenes) try to return into the shell and their certain fraction is localized close to the core/shell interface, which causes a fairly high NRET efficiency. The calculated and experimentally measured NRET efficiency were compared; their trends are reasonable at the semiquantitative level.


2005 ◽  
Vol 109 (44) ◽  
pp. 20854-20857 ◽  
Author(s):  
Wenfang Sun ◽  
Qiu Dai ◽  
James G. Worden ◽  
Qun Huo

2021 ◽  
pp. 118186
Author(s):  
Aurora C. Hernández-González ◽  
Lucía Téllez-Jurado ◽  
Luis M. Rodríguez-Lorenzo

Foods ◽  
2021 ◽  
Vol 10 (7) ◽  
pp. 1618
Author(s):  
Xin-Hui Pang ◽  
Yang Yang ◽  
Xin Bian ◽  
Bing Wang ◽  
Li-Kun Ren ◽  
...  

In order to make HPI have a wide application prospect in the food industry, we used EGCG to modify HPI. In this study, we prepared different concentrations (1, 2, 3, 4, and 5 mM) of (−)-epigallocatechin gallate (EGCG) covalently linked to HPI and use methods such as particle size analysis, circular dichroism (CD), and three-dimensional fluorescence spectroscopy to study the changes in the structure and functional properties of HPI after being covalently combined with EGCG. The particle size data indicated that the covalent HPI-EGCG complex was larger than native HPI, and the particle size was mainly distributed at about 200 μm. CD and three-dimensional fluorescence spectroscopy analyses showed that the conformation of the protein was changed by conjugation with EGCG. The β-sheet content decreased from 82.79% to 66.67% after EGCG bound to the protein, and the hydrophobic groups inside the protein were exposed, which increased the hydrophobicity of the protein and changed its conformation. After HPI and 1 mM of EGCG were covalently bonded, the solubility and emulsifying properties of the covalent complex were improved compared with native HPI. These results indicated that HPI-EGCG conjugates can be added in some foods.


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