The effect of hydrophilic ionic liquids (ILs) on the activity of chloroperoxidase (CPO) was checked through kinetic and stereochemical studies. The possibility to employ this enzyme in synthesis has been demonstrated investigating the chemo- and stereoselectivity of oxidation of phenyl methylsulfide in several citrate buffer-IL mixtures. 相似文献
Triacetyl α-cyclodextrin, triacetyl β-cyclodextrin and triacetyl γ-cyclodextrin were tested as possible hydrophobic carriers
to prolong the release of hydrophilic teicoplanin (TCP). Physical–chemical characterization of individual components, drug-carrier
physical mixtures at 0.5, 0.67 and 0.75 mass fraction of carrier, and the respective interaction products by kneading or evaporative
crystallization under microwave irradiation was carried out using differential scanning calorimetry (DSC) and thermogravimetric
analysis (TGA). In vitro drug release in pH 7.4 phosphate buffer at 37 °C was determined by intrinsic dissolution rate (IDR)
measurements on non disintegrating compressed discs. Solid-state interactions of TCP with triacetyl α-cyclodextrin by evaporative
crystallization and kneading and with triacetyl β-cyclodextrin by evaporative crystallization (probably resulting in carrier
amorphization) were demonstrated. The role of carrier hydrophobicity, carrier mass fraction and preparation method of solid
drug-carrier combinations on solid-state drug-carrier interactions and slowing down of TCP release was assessed. Modulation
of drug release can be achieved using TCP-triacetyl γ-cyclodextrin combinations at 0.5 mass fraction of carrier. 相似文献
We report a novel, fast, and automatic SPME-based method capable of extracting a small molecule-drug conjugate (SMDC) from biological matrices. Our method relies on the extraction of the drug conjugate followed by direct elution into an electrospray mass spectrometer (ESI-MS) source for qualitative and quantitative analysis. We designed a tool for extracting the targeting head of a recently synthesized SMDC, which includes acetazolamide (AAZ) as high-affinity ligand specific to carbonic anhydrase IX. Specificity of the extraction was achieved through systematic optimization. The design of the extraction tool is based on noncovalent and reversible interaction between AAZ and CAII that is immobilized on the SPME extraction phase. Using this approach, we showed a 330% rise in extracted AAZ signal intensity compared to a control, which was performed in the absence of CAII. A linear dynamic range from 1.2 to 25 μg/ml was found. The limits of detection (LOD) of extracted AAZ from phosphate-buffered saline (PBS) and human plasma were 0.4 and 1.2 μg/ml, respectively. This with a relative standard deviation of less than 14% (n = 40) covers the therapeutic range.
A new electrochemical sensor, based on NdFeO3 nanoparticles as electrocatalytic material, was proposed here for the detection of dopamine (DA). NdFeO3 nanoparticles were first synthesized by a simple thermal treatment method and subsequent annealing at high temperature (700 °C). The prepared electrocatalytic material has been characterized in detail by SEM-EDX, XRD, and Raman techniques. Characterization results display its sheet-like morphology, constituted by a porous network of very small orthorhombic NdFeO3 nanoparticles. NdFeO3 electrocatalytic material was then used to modify the working electrode of screen-printed carbon electrodes (SPCEs). Electrochemical tests demonstrated that NdFeO3– modified screen-printed carbon electrode (NdFeO3/SPCE) exhibited a remarkable enhancement of the dopamine electrooxidation, compared to the bare SPCE one. The analytical performance of the developed sensor has been evaluated for the detection of this analyte by means of the square-wave voltammetry (SWV) technique. The modified electrode showed two linear concentration ranges, from 0.5 to 100 μM and 150 to 400 μM, respectively, a limit of detection (LOD) of 0.27 μM (at S/N = 3), and good reproducibility, stability, and selectivity. Additionally, we also report an attempt made to propose the modified sensor for the simultaneous detection of dopamine and uric acid (UA). The procedure was also applied for the determination of dopamine in spiked real samples. So, this paper reports for the first time the use of a modified NdFeO3 screen-printed electrode for developing an electrochemical sensor for the quantification of important biomolecules.
AbstractIn this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865–1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones. 相似文献
4-Acyl-1H-1,2,3-triazoles are formed from diethylaluminum azide and α′-(N,N-dibenzylamino)-α,β-unsaturated ketones by [3+2] cycloaddition of azide, followed by 1,5 hydride transfer to the β carbon of the triazoline side chain and fragmentation of the tertiary amino group promoted by coordination of the latter to the Lewis acid. The structure of a triazole product is confirmed by X-ray crystallography. 相似文献
The synthesis and characterization of a tetranuclear Pt complex, cis-trans-cis-trans tetra[μ-2,6-diethynyl-4-nitroaniline-bis(tri(p-tolyl)phosphine) platinum(II)], namely [L2Pt-DENA]4 with L = tri-p-tolylphosphine, is reported. The complex was obtained by the dehydrohalogenative condensation of 2,6-diethynyl-4-nitroaniline (DENA) with cis-[dichlorobis(tri(p-tolyl)phosphine)platinum(II)]. The single crystal structure determination of [L2Pt-DENA]4 indicated the formation of a neutral molecular cycle with four alternating platinum units in cis and trans configurations, all bridged with DENA spacers with the presence of solvent (toluene) crystallization molecules. A twisted tetranuclear cyclic feature was identified. The formation of intermolecular stacks of the tetranuclear complex in solution was assessed by means of nuclear Overhauser enhancement spectroscopy (NOESY) and rotating frame Overhauser effect spectroscopy (ROESY) characterizations. 相似文献
[graphs: see text] QM GIAO calculations of 13C and 1H chemical shift values of the ArCH2Ar group have been performed, using the hybrid DFT functional MPW1PW91 and the 6-31G(d,p) basis set, on some representative calixarenes and on a series of simplified calixarene models allowing derivation of chemical shift surfaces versus phi and chi dihedral angles. A good reproduction of experimental data was obtained. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated. 相似文献