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491.
Johannes Winkler Benedikt Giessrigl Clemens Novak Ernst Urban Christian R. Noe 《Monatshefte für Chemie / Chemical Monthly》2010,9(3):809-815
Abstract
Development of therapeutically active oligonucleotides for sequence-specific gene knockdown relies on chemical modifications that confer high stability and target affinity and ideally enable cellular uptake. 2′-O-Lysylaminohexyluridine-containing antisense and siRNA oligonucleotides have been shown to be well suited for gene knockdown. They are highly resistant to enzymatic degradation while having good affinity for the targeted RNA strand and efficiently down-regulate their target in cell culture tumor models. The 2′-O-lysylaminohexyl modification was expanded to adenosine nucleosides. The corresponding phosphoramidite building block was prepared in a straightforward procedure comprising six steps starting from adenosine. After 2′-O-alkylation with N-(6-bromohexyl)phthalimide and removal of the N-protecting group, the protected lysine was specifically attached to the alkylamino group. Incorporation of 2′-O-lysylaminohexyladenosine nucleotides in a test sequence confirmed that the cationic chains lead only to minor duplex destabilization and do not disturb the duplex structure. Results further emphasize the advantageous properties of 2′-O-lysylaminohexyl modified oligonucleotides for therapeutic applications. 相似文献492.
Amanda P. Neves Kelly C.B. Maia Maria D. Vargas Lorenzo C. Visentin Annelise Casellato Miguel A. Novak Antônio S. Mangrich 《Polyhedron》2010
A novel versatile tridentate 3-(aminomethyl)naphthoquinone proligand, 3-[N-(2-pyridylmethyl)aminobenzyl]-2-hydroxy-1,4-naphthoquinone (HL), was obtained from the Mannich reaction of 2-hydroxy-1,4-naphthoquinone (Lawsone) with 2-aminomethylpyridine (amp) and benzaldehyde. The reactions of HL with CuCl2·2H2O yielded two novel dinuclear copper(II) complexes, [Cu(L)(H2O)(μ-Cl)Cu(L)Cl] (1b), [CuCl(L)(μ-Cl)Cu(amp)Cl] (2) and a polymeric compound, [Cu(L)Cl)]n (1a), whose relative yields were sensitive to temperature, reagents concentration and presence of base. The crystalline structures of 1b and 2 were determined by X-ray diffraction studies. The two copper atoms in complex 1b are connected by a single chloro bridge with a Cu?Cu separation of 4.1342(8) Å and Cu(1)–Cl(1)–Cu(2) angle of 109.31(4)°. In complex 2 the two copper atoms are held together by a chloro and a naphthalen-2-olate bridges [Cu(1)–Cl(2)–Cu(2) and Cu(1)–O(1)–Cu(2) angles being 83.31(3) and 109.70(9)°, respectively, and the Cu?Cu separation, 3.3476(9) Å]. As expected, variable-temperature magnetic susceptibility measurements of complex 1b showed weak antiferromagnetic intramolecular coupling between the copper(II) centers, with J = −5.7 cm−1, and evidenced for complex 2 strong antiferromagnetic coupling, with J ∼ −120 cm−1. Furthermore, the magnetic behaviour of compound 1a suggested an infinite 1D coordination polymeric structure in which the copper(II) centers are connected by Cl–Cu–Cl bridges. Solution data (UV–Vis spectroscopy and cyclic voltammetry) indicated structural changes of 2 and 1a in CH3CN, and evidenced conversion of polymer 1a into dimer 1b. 相似文献
493.
Electrochemical oxidation of (?)‐epigallocatechin gallate (EGCG), the main monomer flavanol found in green tea, has been investigated over a wide pH range at a glassy‐carbon electrode using square‐wave voltammetry (SWV). Square‐wave voltammograms of (?)‐epigallocatechin (EGC) and gallic acid have been studied as well. The I–E profile of EGCG, i.e. the oxidation potentials and the current responses of the first and the second peak, is pH dependent. The oxidation of EGCG is a quasireversible process over the studied pH range, which was also confirmed by the non‐linear relationship between the peak currents and squre root of frequency. The best SWV responses for EGCG were obtained at pH 2.0, frequency of 100 Hz, step of 2 mV and amplitude of 50 mV. Under these conditions, linear responses for EGCG were obtained for concentrations from 1×10?7 M to 1×10?6 M, and calculated LOD and LOQ for the first oxidation peak were 6.59×10?8 M and 2.19×10?7 M, respectively. The proposed electroanalytical procedure was applied for the determination of EGCG content in green tea. Developed SWV methodology represents a potential analytical tool in determination of catechins in tea samples. 相似文献
494.
Tomas Polcar Tomas Vitu Ladislav Cvrcek Rudolf Novak Jiri Vyskocil Albano Cavaleiro 《Solid State Sciences》2009,11(10):1757-1761
The development of a mechanically stable, functionally graded Ti-doped a-C:H interface layer in combination with a functional a-C:H coating requires a reduction of the brittle phases which induce generally problems in the transitions from Ti to TiC/a-C:H. The core objective of this study was to develop an optimum interlayer between the substrate and the functional top layer for biomedical applications, namely for tooth implants. Since the interlayer may be exposed to the sliding process, in the case of local failure of the top layer it has to fulfil the same criteria: biocompatibility, high wear resistance and low friction.The functional Ti-C:H layers with thickness in the range 2.5–3.5 μm were deposited by a magnetron sputtering/PECVD hybrid process by sputtering a Ti-target in a C2H2 + Ar atmosphere in dc discharge regime. The sets of coating samples were prepared by varying the C and H concentrations controlled by the C2H2 flow during the deposition process. The tribological properties were evaluated on a pin-on-disc tribometer at room temperature (RT) and at 100 °C using 440C balls with a diameter of 6 mm. The tests at 100 °C were performed to investigate the effect of the sterilization temperature on the tribological properties and the coating lifetime as well. The tribological performance was examined with respect to the friction coefficient, the wear rates of the coating and the counter-parts and the analysis of the wear debris. The Ti/C ratio decreased almost linearly from 4.5 to 0.1 with increasing C2H2 flow; the hydrogen content showed a minimum of 5 at.% at C2H2 flow of 30 sccm, while for lower flows it was about 10 at.%. The coatings could be divided into three groups based on the C2H2 flow: (i) 10–15 sccm, exhibiting severe abrasive damage during the sliding tests, (ii) 20–45 sccm, showing the highest hardness and friction values, and (iii) 52–60 sccm, with moderate hardness and minimal values of the friction coefficient and the wear rate. 相似文献
495.
M. A. G. Soler L. G. Paterno J. P. Sinnecker J. G. Wen E. H. C. P. Sinnecker R. F. Neumann M. Bahiana M. A. Novak P. C. Morais 《Journal of nanoparticle research》2012,14(3):653
The internal morphology and magnetic properties of layer-by-layer assembled nanofilms of polyaniline (PANI) and maghemite
(γ-Fe2O3—7.5-nm diameter) were probed with cross-sectional transmission electron microscopy (TEM) and magnetization measurements (magnetic
hysteresis loops, magnetization using zero-field cooled/field-cooled protocols, and ac magnetic susceptibility). Additionally,
simulations of the as-produced samples were performed to assess both the nanofilm’s morphology and the corresponding magnetic
signatures using the cell dynamic system (CDS) approach and Monte Carlo (MC) through the standard Metropolis algorithm, respectively.
Fine control of the film thickness and average maghemite particle–particle within this magnetic structure was accomplished
by varying the number of bilayers (PANI/γ-Fe2O3) deposited onto silicon substrates or through changing the concentration of the maghemite particles suspended within the
colloidal dispersion sample used for film fabrication. PANI/γ-Fe2O3 nanofilms comprising 5, 10, 25 and 50 deposited bilayers displayed, respectively, blocking temperatures (T
B) of 30, 35, 39 and 40 K and effective energy barriers (ΔE/k
B) of 1.0 × 103, 2.3 × 103, 2.8 × 103 and 2.9 × 103 K. Simulation of magnetic nanofilms using the CDS model provided the internal morphology to carry on MC simulation of the
magnetic properties of the system taking into account the particle–particle dipolar interaction. The simulated (using CDS)
surface–surface particle distance of 0.5, 2.5 and 4.5 nm was obtained for nanofilms with thicknesses of 36.0, 33.9 and 27.1 nm,
respectively. The simulated (using MC) T
B values were 33.0, 30.2 and 29.5 K for nanofilms with thicknesses of 36.0, 33.9 and 27.1 nm, respectively. We found the experimental
(TEM and magnetic measurements) and the simulated data (CDS and MC) in very good agreement, falling within the same range
and displaying the same systematic trend. Our findings open up new perspectives for fabrication of magnetic nanofilms with
pre-established (simulated) morphology and magnetic properties. 相似文献
496.
Igor Novak 《Heteroatom Chemistry》1994,5(2):145-148
Molecular and electronic structures and properties of NH2Br, NHBr2, and NBr3 have been studied using ab initio calculations at the Hartree–Fock (HF) and MP2 levels with the aim of complementing very scarce experimental information available for the title molecules. The properties and molecular structures of bromamines are discussed in relationship to other haloamines (fluor- and chloramines). 相似文献