RESUMO
Four types of calcined MCM-41 silica nanoparticles, loaded with dyes and capped with different gating ensembles are prepared and characterized. N1 and N2 nanoparticles are loaded with rhodamine 6G and capped with bulky poly(ethylene glycol) derivatives bearing ester groups (1 and 2). N3-N4 nanoparticles are loaded with sulforhodamine B and capped with self-immolative derivatives bearing ester moieties. In the absence of esterase enzyme negligible cargo release from N1, N3 and N4 nanoparticles is observed whereas a remarkable release for N2 is obtained most likely due to the formation of an irregular coating on the outer surface of the nanoparticles. In contrast, a marked delivery is found in N1, N3, and N4 in the presence of esterase enzyme. The delivery rate is related to the hydrophilic/hydrophobic character of the coating shell. The use of hydrophilic poly(ethylene glycol) derivatives as gating ensembles on N1 and N2 enables an easy access of esterase to the ester moieties with subsequent fast cargo release. On the other hand, the presence of a hydrophobic monolayer on N3 and N4 partially hinders esterase enzyme access to the ester groups and the rate of cargo release was decreased.
RESUMO
A new hybrid material based on sulforhodamineâ B dye-loaded silica mesoporous nanoparticles capped with a self-immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly.
RESUMO
The development of quantitative strategies for targeted biomarker analysis represents an urgent task especially in the field of clinical diagnosis. In this regard, the measurement of glycohaemoglobin (HbA(1c)) in blood has become the most specific way of monitoring long-term glycaemia in diabetic patients. Thus, there is an urgent need for methods that provide accurate and precise HbA(1c) results. A new method for the determination of HbA(1c) in blood samples based on the complementary use of multidimensional liquid chromatography (LC) and elemental (inductively coupled plasma mass spectrometry, ICP-MS) and molecular (electrospray-mass spectrometry, ESI-MS) MS techniques has been developed and validated. Different multidimensional separation possibilities by combining affinity and cation exchange chromatography have been explored for the adequate isolation of HbA(1c), which purity is addressed by ESI-MS. The workflow includes a final quantitative determination of HbA(1c) by elemental (Fe) isotope dilution analysis (IDA) with ICP-MS. For this purpose, the post-column addition of the isotopically labeled iron ((57)Fe) has been used to quantify the eluting Fe-species from the column. The IDA methodology has been validated by analyzing a certified reference material and several samples from patients whose HbA(1c) levels were determined by a standard reference method.