1. Surface characterization and platelet compatibility evaluation of the binary mixed self-assembled monolayers
Meng-Yen Tsai, Yu-Ting Sun, Jui-Che Lin J Colloid Interface Sci. 2007 Apr 15;308(2):474-84. doi: 10.1016/j.jcis.2007.01.015. Epub 2007 Jan 12.
This report describes a technique that used mixed self-assembled monolayer (SAM) as a model surface to evaluate the effect of steric hindrance on the SAM packing quality and its platelet compatibility. Two series of binary mixed SAMs were formed by mixing the bulky terminated alkanethiol (HS(CH2)10PO3H2) with a smaller terminated one (HS(CH2)9CH3 and HS(CH2)11OH) respectively. Surface characterization results showed the hydrophilicity on these two series of mixed SAMs changed with the solution mole fraction of PO3H2 terminated thiol, chi(PO3H2,soln), and reached to a nearly constant value as chi(PO3H2,soln) was 0.6 for PO3H2+CH3 SAM and 0.4 for PO3H2+OH SAM. This finding should be due to the gradual saturation of surface PO3H2 functionality on these mixed SAMs. The XPS analysis indicated the addition of the CH3 and OH terminated thiol could reduce the steric hindrance effect of PO3H2 functionality on monolayer formation and, henceforth, improve the SAM packing quality. In vitro platelet adhesion assay revealed the platelet compatibility on the PO3H2+OH SAMs was better than that on the PO3H2+CH3 and the pure PO3H2 ones. Moreover, the PO3H2+OH SAM with a low chi(PO3H2,soln) value exhibited the least platelet activating property of these two mixed SAM systems. These findings suggested that material's surface wettability and surface charge density should act collectively in affecting its platelet compatibility.
2. 5-Phenyl-3-(2-phosphono-eth-yl)-1,2,3-triazol-1-ium chloride
Elpiniki Chachlaki, Duane Choquesillo-Lazarte, Konstantinos D Demadis IUCrdata. 2022 Feb 25;7(Pt 2):x220189. doi: 10.1107/S2414314622001894. eCollection 2022 Feb.
The new triazole-functionalized phospho-nic acid 5-phenyl-3-(2-phosphono-eth-yl)-1,2,3-triazol-1-ium chloride, C10H13N3O3P+·Cl- (PTEPHCl), was synthesized by the 'click' reaction of the alkyl azide diethyl-(2-azido-eth-yl)phospho-nate with phenyl-acetyl-ene to give the dieth-yl[2-(4-phenyl-1H-1,2,3-triazol-1-yl)eth-yl]phospho-nate ester, which was then hydrolyzed under acidic conditions (HCl) to give the 'free' phospho-nic acid. The use of HCl for the hydrolysis caused protonation of the triazole ring, rendering the compound cationic, charged-balanced by a Cl- anion. There are extensive hydrogen-bonding inter-actions in the structure of PTEPHCl, involving the phospho-nic acid (-PO3H2) group, the triazolium ring and the Cl- anion.
3. Design, synthesis, and photophysical characterization of water-soluble chlorins
K Eszter Borbas, Vanampally Chandrashaker, Chinnasamy Muthiah, Hooi Ling Kee, Dewey Holten, Jonathan S Lindsey J Org Chem. 2008 Apr 18;73(8):3145-58. doi: 10.1021/jo7026728. Epub 2008 Mar 15.
The use of chlorins as photosensitizers or fluorophores in a range of biological applications requires facile provisions for imparting high water solubility. Two free base chlorins have been prepared wherein each chlorin bears a geminal dimethyl group in the reduced ring and a water-solubilizing unit at the chlorin 10-position. In one design (FbC1-PO3H2), the water-solubilizing unit is a 1,5-diphosphonopent-3-yl ("swallowtail") unit, which has previously been used to good effect with porphyrins. In the other design (FbC2-PO3H2), the water-solubilizing unit is a 2,6-bis(phosphonomethoxy)phenyl unit. Two complementary routes were developed for preparing FbC2-PO3H2 that entail introduction of the protected phosphonate moieties either in the Eastern-half precursor to the chlorin or by derivatization of an intact chlorin. Water-solubilization is achieved in the last step of each synthesis upon removal of the phosphonate protecting groups. The chlorins FbC1-PO3H2 and FbC2-PO3H2 are highly water-soluble (>10 mM) as shown by 1H NMR spectroscopy (D2O) and UV-vis absorption spectroscopy. The photophysical properties of the water-soluble chlorins in phosphate-buffered saline solution (pH 7.4) at room temperature were investigated using static and time-resolved absorption and fluorescence spectroscopic techniques. Each chlorin exhibits dominant absorption bands in the blue and the red region (lambda = 398, 626 nm), a modest fluorescence yield (Phi f approximately 0.11), a long singlet excited-state lifetime (tau = 7.5 ns), and a high yield of intersystem crossing to give the triplet state (Phi isc = 0.9). The properties of the water-soluble chlorins in aqueous media are comparable to those of hydrophobic chlorins in toluene. The high aqueous solubility combined with the attractive photophysical properties make these compounds suitable for a wide range of biomedical applications.
