Chuiko Institute of Surface Chemistry, The National Academy of Sciences of Ukraine, 17 Generala Naumova Str., 17, Kyiv 03164, Ukraine.
Taurida National V.I. Vernadsky University, Akademika Vernadskogo av. 4, Simferopol 95007, Ukraine.
Nanoscale Res Lett. 2014 May 13;9(1):234. doi: 10.1186/1556-276X-9-234. eCollection 2014.
In this study, chemical transformations of benzyl ester of О-(phenyl-2-acetamido-2,3-dideoxy-1-thio-β-d-glucopyranoside-3-yl)-d-lactoyl-l-alanyl-d-isoglutamine (SPhMDPOBn) on the fumed silica surface were examined, and the surface complex structure was characterized by temperature-programmed desorption mass spectrometry (TPD-MS), infrared spectroscopy (FTIR) and electrospray ion trap mass spectrometry (ES IT MS). Stages of pyrolysis of SPhMDPOBn in pristine state and on the silica surface have been determined. Probably, hydrogen-bonded complex forms between silanol surface groups and the C = O group of the acetamide moiety NH-(CH3)-C = O…H-O-Si≡. The thermal transformations of such hydrogen-bonded complex result in pyrolysis of SPhMDPOBn immobilized on the silica surface under TPD-MS conditions. The shifts ∆ν of amide I band (measured from 1,626 to 1,639 cm(-l) for SPhMDPOBn in pristine state) of 33 and 35 cm(-l) which occurred when SPhMDPOBn was immobilized on the silica surface may be caused by a weakening of the intramolecular hydrogen bonding of the SPhMDPOBn because the interaction with the silica surface as hydrogen bond with silanol groups is weaker than that in associates.
本研究考察了苯甲酰基-O-(苯-2-乙酰氨基-2,3-二去氧-1-硫代-β-D-吡喃葡萄糖苷-3-基)-D-乳酰-L-丙氨酰-D-异谷氨酰胺（SPhMDPOBn）在无定形二氧化硅表面的化学转化，并通过程序升温脱附质谱（TPD-MS）、红外光谱（FTIR）和电喷雾离子阱质谱（ES IT MS）对表面配合物结构进行了表征。确定了 SPhMDPOBn 在原始状态和二氧化硅表面上的热解阶段。可能在硅醇表面基团和乙酰胺部分 NH-(CH3)-C = O…H-O-Si≡的 C = O 基团之间形成氢键配合物。在 TPD-MS 条件下，这种氢键配合物的热转化导致固定在二氧化硅表面上的 SPhMDPOBn 热解。当 SPhMDPOBn 固定在二氧化硅表面上时，酰胺 I 带（从 1,626 到 1,639 cm(-l) 测量）的位移 ∆ν 为 33 和 35 cm(-l)，这可能是由于 SPhMDPOBn 分子内氢键的减弱引起的，因为与二氧化硅表面的相互作用作为氢键与硅醇基团的相互作用比在缔合物中弱。
