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21.
Five new CuII complexes of general formula [Cu2(Rdtc)tpmc](ClO4)3, (1)–(5), where tpmc and Rdtc
– refer to N,N,N,N-tetrakis(2-pyridylmethyl)-1,4,8,11-teraazacyclotetradecane and piperidine- (Pipdtc), 4-morpholine- (Morphdtc), 4-thiomorpholine- (Timdtc), piperazine- (Pzdtc) or N-methylpiperazine- (N-Mepzdtc) dithiocarbamates, respectively, have been prepared. Elemental analyses, conductometric and magnetic measurements, u.v./vis, i.r., e.p.r. and mass spectroscopy have been employed to characterize them. The complexes adopt an exo coordination of CuII ions and tpmc. The dithiocarbamate ion joins both the sulphur and the copper atoms acting as a bridging ligand The presence of different heteroatoms in the piperidine ring influences the (C=N) and (C=S) vibrations which decrease in the order of the complexes: Pipdtc>N-Mepipdtc>Pzdtc>Morphdtc>Timdtc ligands. Attention has been paid to the detailed mechanism of the mass spectral fragmentation of the complexes. The g
eff factors of the complexes have been also estimated by e.p.r. spectra. Finally, the complexes obtained demonstrate microbiologycal activity against some bacteria. 相似文献
22.
Oikonomakos NG 《Current protein & peptide science》2002,3(6):561-586
The regulation of the hepatic glucose output through glycogenolysis is an important target for type 2 diabetes therapy. Glycogenolysis is catalyzed in liver, muscle and brain by tissue specific isoforms of glycogen phosphorylase (GP). Because of its central role in glycogen metabolism, GP has been exploited as a model for structure-assisted design of potent inhibitors, which may be relevant to the control of blood glucose concentrations in type 2 diabetes. Several regulatory binding sites have been identified in GP, such as the catalytic, the allosteric, and the inhibitor binding sites. Protein crystallography has contributed significant structural information on the specificity and interactions that distinguish the binding sites, and also revealed a new unexpected binding site (new allosteric site). In this review, the kinetic, crystallographic binding, and physiological studies of a number of compounds, inhibitors of GP, are described, and the essential inhibitory and binding properties of specific compounds are analyzed in an effort to provide rationalizations for the affinities of these compounds and to exploit the molecular interactions that might give rise to a better inhibitor. These studies have given new insights into fundamental structural aspects of the enzyme enhancing our understanding of how the enzyme recognizes and specifically binds ligands, that could be of potential therapeutic value in the treatment of type 2 diabetes. 相似文献
23.
The molar conductivities (Λ) of solutions of n-tetrabutylammonium tetraphenylborate (NBu4BPh4) in 3-pentanone have been measured in the temperature range from 283.15 to 329.15 K. The conductance data have been analyzed
using the Lee-Wheaton conductivity equation with the distance parameter (a) set at Bjerrum’s pairing distance, and the limiting molar conductivities (Λo) and the association equilibrium constants (K
A) have been derived. The limiting ion conductivities (λ_±o) have been evaluated according to the method of Krumgalz. The λ+
o values have been compared with λ+
o values calculated from the empirical equation of Gill. The thermodynamic functions, Gibbs energy (Δ G
A
o), enthalpy (Δ H
A
o) and entropy (Δ S
A
o) for the process of ion-pair formation as well as the activation energy of the ionic movement (ΔH
∗) have been evaluated. The obtained results are discussed in terms of ion-ion and ion-solvent interactions. 相似文献
24.
Karam Asad Dr. Anastasios Stergiou Dr. Andreas Kourtellaris Prof. Nikos Tagmatarchis Prof. Nikos Chronakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13879-13886
The multiaddition chemistry of azafullerene C59N has been scarcely explored, and the isolation of pure bisadducts is in its infancy. Encouraged by the recent regioselective synthesis of the inherently chiral equatorialface bisadduct of C59N, we focused on the isolation of the first trans-4 bisadduct in a simple two-step approach. The first regioselective synthesis of the trans-4 bisadduct of C59N by using cyclo-[2]-dodecylmalonate as a tether is now reported. The newly synthesized bisadduct has C1 symmetry, as evidenced by 13C NMR, while X-ray crystallography validated the trans-4′ addition pattern. Furthermore, the inherently chiral trans-4′ C59N bisadduct was enantiomerically resolved, and the mirror-image relation of the two enantiomers was probed by circular dichroism spectroscopy. Finally, UV-Vis and redox assays suggested that the addition pattern has a reflection in the light-harvesting and redox properties of the bisadduct. 相似文献
25.
De Wang Nikos Hadjichristidis 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(19):6361-6365
The first synthesis of well‐defined poly[(phenylmethylene‐co‐methylpropenylene)‐b‐methylene, [(C1‐co‐C3)‐b‐C1], terpolymers was achieved by one‐pot borane‐initiated random copolymerization of ω‐methylallyl (C3 units, chain is growing by three carbon atoms at a time) and benzyltriphenylarsonium (C1 units, chain is growing by one carbon atom at a time) ylides, followed by polymerization of sulfoxonium methylide (C1 units). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4‐fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium. The obtained terpolymers are well‐defined, possess a predictable molecular weight and low polydispersity (Mn,NMR=1.83–9.68×103 g mol?1, ?=1.09–1.22). An unexpected light emission phenomenon was discovered in these non‐conjugated terpolymers, as confirmed by fluorescence and NMR spectroscopy. This phenomenon can be explained by the isomerization of the double bonds of allylic monomeric units along the chain of the terpolymers (isomerization‐induced light emission). 相似文献
26.
Nikos Karanikolopoulos Ioannis Choinopoulos Marinos Pitsikalis 《Journal of polymer science. Part A, Polymer chemistry》2020,58(11):1582-1600
A series of well-defined poly{dl -lactide-b-[oligo(ethylene glycol) methyl ether (meth)acrylate)]} (PDLLA-b-POEG[M]A) functional amphiphilic diblock copolymers was synthesized by employing a multistep procedure involving: (a) ring-opening polymerization of dl -lactide using n-decanol and stannous octoate as the initiating system, (b) esterification reaction of the PDLLA hydroxyl end groups with 2-bromoisobutyryl bromide, (c) atom transfer radical polymerization of OEG(M)A with the newly created bromoisobutyryl initiating site, and (d) incorporation of biotin or folic acid at the POEGA chain ends using click chemistry. The products were characterized by NMR spectroscopy and SEC analysis. The aggregation behavior of the synthesized block copolymers was investigated by dynamic light scattering at 25°C in aqueous solutions. The hydrophobic model compounds Nile red and pyrene were efficiently incorporated into the copolymer aggregates in aqueous solutions. High partition coefficient values were determined by fluorescence spectroscopy. 相似文献
27.
Diblock copolymers of polystyrene‐b‐poly(1,3‐cyclohexadiene) exhibiting unique three‐phase microdomain morphologies
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Konstantinos Misichronis Jihua Chen Jong K. Kahk Adam Imel Mark Dadmun Kunlun Hong Nikos Hadjichristidis Jimmy W. Mays Apostolos Avgeropoulos 《Journal of Polymer Science.Polymer Physics》2016,54(16):1564-1572
The synthesis and molecular characterization of a series of conformationally asymmetric polystyrene‐block‐poly(1,3‐cyclohexadiene) (PS‐b‐PCHD) diblock copolymers (PCHD: ~90% 1,4 and ~10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ ?PS ≤ 0.91) was studied by transmission electron microscopy and small‐angle X‐ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD‐1,4)–shell(PCHD‐1,2) cylinders in PS matrix and three‐phase (PS, PCHD‐1,4, PCHD‐1,2) four‐layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strong dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS‐b‐PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1564–1572 相似文献
28.
Manuela F. Frasco Vicky Vamvakaki Nikos Chaniotakis 《Journal of nanoparticle research》2010,12(4):1449-1458
In this study, we report on a novel hybrid structure for the direct sensing of metal ions based on the use of CdSe quantum
dots functionalized with tetrapyridyl-substituted porphyrin, a cation-selective carrier. It is shown that the porphyrin ion
carrier coordinates to Cd atoms of the CdSe quantum dots through the Lewis basic pyridyl groups. The porphyrin-quantum dot
ligation allows for the direct communication between the porphyrin and the underlying CdSe quantum structure. The quantum
yield of CdSe is maintained despite the robust capping generated when the unmetallated porphyrins coordinate onto the quantum
dots. Upon coordination with zinc ions, this porphyrin capping is shown to strongly contribute to the increase in the fluorescence
efficiency of CdSe, via an activating interaction with the quantum dots surface. The results provide the grounds for the development
of highly sensitive and selective nano-optode sensing systems. 相似文献
29.
Dr. Matteo P. Placidi Prof. Dr. Mauro Botta Dr. Ferenc K. Kálmán Dr. Gisela E. Hagberg Dr. Zsolt Baranyai Andreas Krenzer Alexandria K. Rogerson Prof. Dr. Imre Tóth Prof. Dr. Nikos K. Logothetis Priv.‐Doz. Dr. Goran Angelovski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11644-11660
A series of low molecular weight lanthanide complexes were developed that have high 1H longitudinal relaxivities (r1) and the potential to be used as dual frequency 1H and 19F MR probes. Their behavior was investigated in more detail through relaxometry, pH‐potentiometry, luminescence, and multinuclear NMR spectroscopy. Fitting of the 1H NMRD and 17O NMR profiles demonstrated a very short water residence lifetime (<10 ns) and an appreciable second sphere effect. At lower field strengths (20 MHz), two of the complexes displayed a peak in r1 (21.7 and 16.3 mM ?1 s?1) caused by an agglomeration, that can be disrupted through the addition of phosphate anions. NMR spectroscopy revealed that at least two species are present in solution interconverting through an intramolecular binding process. Two complexes provided a suitable signal in 19F NMR spectroscopy and through the selection of optimized imaging parameters, phantom images were obtained in a MRI scanner at concentrations as low as 1 mM . The developed probes could be visualized through both 1H and 19F MRI, showing their capability to function as dual frequency MRI contrast agents. 相似文献
30.
A novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given. 相似文献