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31.
[structure: see text] An efficient total stepwise solid-phase synthesis of oligonucleotide-(3'-->N)-peptide conjugates is described that makes use of either a controlled pore glass support or macroporous polystyrene beads. Extending our previous homoserine linker approach, we prepared a range of conjugates containing one of four different cell or nuclear penetration peptides together with oligonucleotides containing 2'-deoxynucleoside or 2'-O-methylribonucleoside phosphodiesters, or gapmers containing 2'-deoxyphosphorothioates. The route also allows incorporation of a fluorescent label within the conjugate for cell uptake studies. 相似文献
32.
Coppens P Vorontsov II Graber T Kovalevsky AY Chen YS Wu G Gembicky M Novozhilova IV 《Journal of the American Chemical Society》2004,126(19):5980-5981
Using a stroboscopic technique, in which the molecule is repeatedly excited and the structural change is probed more than 5000 times per second immediately after excitation, we performed a 16 K time-resolved single-crystal study of the microsecond lifetime triplet state of the Cu(I)phenanthroline derivative[Cu(I)(dmp)(dppe)][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane). The geometry changes on excitation differ for the two symmetry-independent molecules, but are in the same direction as calculated for an isolated reference molecule, although the flattening distortion in the crystal is significantly smaller, implying that the reorganization energy is greatly affected by the confining medium. 相似文献
33.
Triazene‐substituted arylboronic esters were prepared readily from the corresponding aryl magnesium derivatives and shown to function as a new class of donor–acceptor‐substituted coupling reagents. The selective functionalization of these aromatic derivatives led to a wide variety of terphenyl derivatives in which the original bifunctional unit (often further substituted with another functional group) formed the central aromatic ring. The functionalized terphenyl derivatives were formed in two efficient cross‐coupling steps from the triazene‐substituted boronic esters: Suzuki cross‐coupling with an aryl halide was followed by BF3?OEt2‐induced palladium‐catalyzed coupling of the diazonium salt generated in situ from the triazene with an arylboronic acid. 相似文献
34.
An evaluation of analytical techniques for determination of lead, cadmium, chromium, and mercury in food-packaging materials 总被引:1,自引:0,他引:1
Perring L Alonso MI Andrey D Bourqui B Zbinden P 《Fresenius' Journal of Analytical Chemistry》2001,370(1):76-81
Closed microwave digestion and a high-pressure asher have been evaluated for wet-oxidation and extraction of lead, cadmium, chromium, and mercury from a range of typical packaging materials used for food products. For the high-pressure asher a combination of nitric and sulfuric acids was efficient for destruction of a range of packaging materials; for polystyrene, however, nitric acid alone was more efficient. For microwave digestion, a reagent containing nitric acid, sulfuric acid, and hydrogen peroxide was used for all materials except polystyrene. Use of the high-pressure asher resulted in the highest recoveries of spiked lead (median 92%), cadmium (median 92%), chromium (median 97%), and mercury (median 83%). All samples were spiked before digestion with 40 microg L(-1) Cd, Cr, and Pb and 8 microg L(-1) Hg in solution. The use of indium as internal standard improved the accuracy of results from both ICP-MS and ICP-AES. Average recovery of the four elements from spiked packaging materials was 92 +/- 14% by ICP-MS and 87 +/- 15% (except for mercury) by ICP-AES. For mercury analysis by CVAAS, use of tin(II) chloride as reducing agent resulted in considerably better accuracy than use of sodium borohydride reagent. 相似文献
35.
[reaction: see text] Rhodium-catalyzed oxygen transfer was used to generate benzyl 2-silyl-2-oxoacetates in good yields. The hydrogenation of these compounds led to chiral alpha-silyl-substituted alpha-hydroxyacetic acids. Resolution by means of HPLC using a chiral stationary phase afforded an enantiomerically pure representative of this class of compounds, which was successfully applied as a chiral ligand in an asymmetric aldol-type reaction. 相似文献
36.
A new application of the polarized total internal reflection fluorescence (PTIRF) technique to study the orientation distribution of a fluorophore within a Langmuir monolayer in situ on an aqueous subphase is described. The technique utilizes the measurement of polarized fluorescence, excited by the evanescent field appearing upon total internal reflection. The excitation by the evanescent field is achieved by launching the beam into a prism that is brought into contact with the monolayer from above. We also show here that a combination of PTIRF of monolayers on water and those freshly deposited onto the prism by horizontal lift in the same experiment provide enough data to determine the dielectric constant of the actual local environment of the fluorophore in the monolayer to eliminate the ambiguity of the orientation determination, arising from uncertainty in the normal component of excitation field. The new technique was applied to several model systems: fatty acid monolayers containing amphiphilic dyes DiI or BODIPY and also a monolayer of a synthetic amphiphilic porphyrin-binding peptide AP0. This technique is more accurate than polarized epifluorescence (PEF) in determining the fluorophore orientation distribution due to the much higher normal component of the excitation, achievable in the evanescent field, and to the lack of surface vibrations caused by capillary waves. Comparison of the new PTIRF approach with PEF shows that the monolayer structure is not disturbed by weak van der Waals attachment to the hydrophobic substrate. 相似文献
37.
Sulfonated and sulfoacylated poly(styrene-divinylbenzene) copolymers as packing materials for cation chromatography 总被引:1,自引:0,他引:1
Pirogov AV Chernova MV Nemtseva DS Shpigun OA 《Analytical and bioanalytical chemistry》2003,376(5):745-752
Three different types of cation exchangers were produced from four basic poly(styrene-divinylbenzene) substrates with different properties. Porous PS-DVB resin beads were functionalized by sulfonation and sulfoacylation under various conditions to produce sulfonated resins with exchange capacities of 0.03-1.80 mM g(-1). The matrix with 50% of cross-linking is most suitable for updating by the proposed technique. Sulfuric and chlorosulfonic acids were used as the reagents for sulfonation. The sulfonating conditions, capacities, and the technique of the synthesis are given. The effects of parameters of the sulfonation reaction and the composition of the reactionary mixture on ion-exchange capacity of the sorbents were investigated. Selectivity and efficiency of the separation of some inorganic cations and derivatives of amines and hydrazines on the resins obtained are compared by ion chromatography with conductometric detection. As a result, the sulfoacylated resin was proved more efficient for the separation of these analytes. The resolution of the analytes strongly depends on the degree of functionalization. The best performance about 19,000 plates m(-1) was obtained using the sulfopropionylated beads with an ion-exchange capacity of 0.3 mM g(-1). The prepared sulfoacylated cation exchanger was compared with the commercially available Dionex CS-12 packing material. It was found that the separation of alkaline ions and 1,1-dimethylhydrazine (UDMH) were much better that those for the commercial material. 相似文献
38.
Nataliya A. Sanina Arina A. Starostina Andrey N. Utenyshev Pavel V. Dorovatovskii Nina S. Emelyanova Vladimir B. Krapivin Victor B. Luzhkov Viktoriya A. Mumyatova Anastasiya A. Balakina Alexei A. Terentiev Sergey M. Aldoshin 《Molecules (Basel, Switzerland)》2022,27(20)
In this work a new donor of nitric oxide (NO) with antibacterial properties, namely nitrosyl iron complex of [Fe(C6H5C-SNH2)2(NO)2][Fe(C6H5C-SNH2)(S2O3)(NO)2] composition (complex I), has been synthesized and studied. Complex I was produced by the reduction of the aqueous solution of [Fe2(S2O3)2(NO)2]2− dianion by the thiosulfate, with the further treatment of the mixture by the acidified alcohol solution of thiobenzamide. Based on the structural study of I (X-ray analysis, quantum chemical calculations by NBO and QTAIM methods in the frame of DFT), the data were obtained on the presence of the NO…NO interactions, which stabilize the DNIC dimer in the solid phase. The conformation properties, electronic structure and free energies of complex I hydration were studied using B3LYP functional and the set of 6–31 + G(d,p) basis functions. The effect of an aquatic surrounding was taken into account in the frame of a polarized continuous model (PCM). The NO-donating activity of complex I was studied by the amperometry method using an “amiNO-700” sensor electrode of the “inNO Nitric Oxide Measuring System”. The antibacterial activity of I was studied on gram-negative (Escherichia coli) and gram-positive (Micrococcus luteus) bacteria. Cytotoxicity was studied using Vero cells. Complex I was found to exhibit antibacterial activity comparable to that of antibiotics, and moderate toxicity to Vero cells. 相似文献
39.
Aleksandr S. Kazachenko Emine Tan Feride Akman Mouna Medimagh Noureddine Issaoui Omar Al-Dossary Leda G. Bousiakou Anna S. Kazachenko Dmitry Zimonin Andrey M. Skripnikov 《Molecules (Basel, Switzerland)》2022,27(22)
Imidazole derivatives have found wide application in organic and medicinal chemistry. In particular, benzimidazoles have proven biological activity as antiviral, antimicrobial, and antitumor agents. In this work, we experimentally and theoretically investigated N-Butyl-1H-benzimidazole. It has been shown that the presence of a butyl substituent in the N position does not significantly affect the conjugation and structural organization of benzimidazole. The optimized molecular parameters were performed by the DFT/B3LYP method with 6-311++G(d,p) basis set. This level of theory shows excellent concurrence with the experimental data. The non-covalent interactions that existed within our compound N-Butyl-1H-benzimidazole were also analyzed by the AIM, RDG, ELF, and LOL topological methods. The color shades of the ELF and LOL maps confirm the presence of bonding and non-bonding electrons in N-Butyl-1H-benzimidazole. From DFT calculations, various methods such as molecular electrostatic potential (MEP), Fukui functions, Mulliken atomic charges, and frontier molecular orbital (HOMO-LUMO) were characterized. Furthermore, UV-Vis absorption and natural bond orbital (NBO) analysis were calculated. It is shown that the experimental and theoretical spectra of N-Butyl-1H-benzimidazole have a peak at 248 nm; in addition, the experimental spectrum has a peak near 295 nm. The NBO method shows that the delocalization of the aσ-electron from σ (C1–C2) is distributed into antibonding σ* (C1–C6), σ* (C1–N26), and σ* (C6–H11), which leads to stabilization energies of 4.63, 0.86, and 2.42 KJ/mol, respectively. Spectroscopic investigations of N-Butyl-1H-benzimidazole were carried out experimentally and theoretically to find FTIR vibrational spectra. 相似文献
40.
Viktor A. Ilin Elena V. Pyzhik Anton B. Balakhonov Maksim A. Kiryushin Evgeniya V. Shcherbatova Andrey A. Kuznetsov Pavel A. Kostin Andrey V. Golovin Vladimir A. Korshun Vladimir A. Brylev Kseniya A. Sapozhnikova Alexey M. Kopylov Galina V. Pavlova Igor N. Pronin 《Molecules (Basel, Switzerland)》2023,28(1)
Central nervous system tumors related to gliomas are of neuroectodermal origin and cover about 30% of all primary brain tumors. Glioma is not susceptible to any therapy and surgical attack remains one of the main approaches to its treatment. Preoperative tumor imaging methods, such as positron emission tomography (PET), are currently used to distinguish malignant tissue to increase the accuracy of glioma removal. However, PET is lacking a specific visualization of cells possessing certain molecular markers. Here, we report an application of aptamers to enhancing specificity in imaging tumor cells bearing the epidermal growth factor receptor (EGFR). Glioblastoma is characterized by increased EGFR expression, as well as mutations of this receptor associated with active division, migration, and adhesion of tumor cells. Since 2021, EGFR has been included into the WHO classification of gliomas as a molecular genetic marker. To obtain conjugates of aptamers GR20 and GOL1-specific to EGFR, a 4-[18F]fluorobenzylazide radiotracer was used as a synthon. For the production of the synthon, a method of automatic synthesis on an Eckert & Ziegler research module was adapted and modified using spirocyclic iodonium ylide as a precursor. Conjugation of 4-[18F]fluorobenzylazide and alkyne-modified aptamers was carried out using Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) with/without the TBTA ligand. As a result, it was possible to obtain 18F-labelled conjugates with 97% radiochemical purity for [18F]FB-GR20 and 98% for [18F]FB-GOL1. The obtained conjugates can be used for further studies in PET analysis on model animals with grafted glioblastoma. 相似文献