31772-06-2Relevant articles and documents
Electrostatic Control of Macrocyclization Reactions within Nanospaces
Wang, Kaiya,Cai, Xiaoyang,Yao, Wei,Tang, Du,Kataria, Rhea,Ashbaugh, Henry S.,Byers, Larry D,Gibb, Bruce C.
supporting information, p. 6740 - 6747 (2019/05/06)
The intrinsic structural complexity of proteins makes it hard to identify the contributions of each noncovalent interaction behind the remarkable rate accelerations of enzymes. Coulombic forces are evidently primary, but despite developments in artificial nanoreactor design, a picture of the extent to which these can contribute has not been forthcoming. Here we report on two supramolecular capsules that possess structurally identical inner-spaces that differ in the electrostatic potential (EP) field that envelops them: one positive and one negative. This architecture means that only changes in the EP field influence the chemical properties of encapsulated species. We quantify these influences via acidity and rates of cyclization measurements for encapsulated guests, and we confirm the primary role of Coulombic forces with a simple mathematical model approximating the capsules as Born spheres within a continuum dielectric. These results reveal the reaction rate accelerations possible under Coulombic control and highlight important design criteria for nanoreactors.
PH-responsive dendritic core-multishell nanocarriers
Fleige, Emanuel,Achazi, Katharina,Schaletzki, Karolina,Triemer, Therese,Haag, Rainer
, p. 99 - 108 (2014/06/09)
In this paper we describe novel pH-responsive core-multishell (CMS) nanocarrier (pH-CMS), obtained by introducing an aromatic imine linker between the shell and the core. At a pH of 5 and lower the used imine linker was rapidly cleaved as demonstrated by NMR studies. The CMS nanocarriers were loaded with the dye Nile red (NR) and the anticancer drug doxorubicin (DOX), respectively. The transport capacities were determined using UV/Vis spectroscopy, and the sizes of the loaded and unloaded CMS nanocarriers were investigated using dynamic light scattering (DLS). We could show that CMS nanocarriers efficiently transported NR in supramolecular aggregates, while DOX was transported in a unimolecular fashion. After cellular uptake the DOX-loaded pH-responsive nanocarriers showed higher toxicities than the stable CMS nanocarriers. This is due to a more efficient DOX release caused by the cleavage of the pH-labile imine bond at lower pH within the intracellular compartments.
Dynamic assessment of bilayer thickness by varying phospholipid and hydraphile synthetic channel chain lengths
Weber, Michelle E.,Schlesinger, Paul H.,Gokel, George W.
, p. 636 - 642 (2007/10/03)
A library of "hydraphile" synthetic ion channel analogues that differ in overall length from ~28-58 A has been prepared. A new and convenient ion-selective electrode (ISE) method was used to assay Na+ release. Liposomes were formed from three d
Convenient and convergent syntheses of long-chain α,ω-dibromides and diphosphines of the formula X(CH2)nX (n = 18-32)
Mohr, Wolfgang,Horn, Clemens R.,Stahl, Juergen,Gladysz
, p. 1279 - 1285 (2007/10/03)
The known tetrahydropyranyl ethers Br(CH2)yOTHP (y = 6, 9, 11), which are easily prepared from commercial bromoalcohols, are sequentially treated with Mg, Li2CuCl4, and X(CH2)2X (z/X = 6/Br, 7/Br, 8/Br, 10/Br, 10/I) to give the diethers THPO(CH2)nOTHP in 68-40% yields (n = 2 y + z = 18, 19, 20, 22, 24, 28, 32). Subsequent reactions with Ph3P and 2,4,4,6-tetrabromocyclohexa-2,5-dienone give the title compounds Br(CH2)nBr in 91-75% yields. Reactions with commercial K+PPh2 give the diphosphines Ph2P(CH2)nPPh2 in 95-74% yields.
Iron-tetraphenylporphine complex having phosphocholine group
-
, (2008/06/13)
Disclosed is an iron-5,10,15,20-tetra(α, α, α, α-o-substituted phenyl)porphine complex having one or four substituents with a phosphocholine group at the terminal end thereof. The substituents are positioned ortho of the phenyl group or groups.
Photocyclization of ω-Anilinoalkylphthalimides: A Photochemical Macrocyclic Synthesis
Machida, Minoru,Takechi, Haruko,Kanaoka, Yuichi
, p. 1579 - 1587 (2007/10/02)
Upon irradiation, a homologous series of N-phthalimides 5, having a nonconjugated bichromopholic system, undergoes regioselective remote photocyclization to give medium- to large-sized (up to twenty-two-membered) diazacyclols 6.Key