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991.
A. S. Mendkovich M. A. Syroeshkin L. V. Mikhalchenko A. I. Rusakov V. P. Gultyai 《Russian Chemical Bulletin》2008,57(7):1492-1495
The protonation of the electrochemically generated (0.1 M solution of tetrabutylammonium perchlorate in DMF) 1,3-dinitrobenzene (1) dianions with phenol, ethanol, tert-butanol, and 1-butyl-3-methylimidazolium cation was studied by cyclic voltammetry and chronoamperometry at the carbositall
working electrode. The rate constants for the protonation (k) of the dianion of compound 1 by phenol, 1-butyl-3-methylimidazolium cation, ethanol, and tert-butanol were estimated by the comparison of the data of cyclic voltammetry and chronoamperometry with the digital simulation
results, being 100, 50, 1.5, and 0.01 L mol−1 s−1, respectively. The similarly obtained k value for the protonation of the dianion of 1,4-dinitrobenzene (2) with phenol is 13 L mol−1 s−1. According to the quantum chemical calculation results, the protonation of the dianions of compounds 1 and 2 with phenol and 1-butyl-3-methylimidazolium cation can be classified as orbital-controlled reactions.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1463–1466, July, 2008. 相似文献
992.
Filippi A Speranza M Paladini A De Carolis R Guidoni AG Laganà A Satta M 《Journal of mass spectrometry : JMS》2006,41(1):98-102
Diastereomeric clusters of general formula [MAB(2)](+) and [MA(2)B](+) (M = Li(I), Na(I), Ag(I), Ni(II)-H, or Cu(II)-H; A = (R)-(-)- and (S)-(+)-(1-aminopropyl)phosphonic acid; B = (1R)-(-)- and (1S)-(+)-(1-aminohexyl)phosphonic acid) have been readily generated in the electrospray ionization (ESI) source of a triple-quadrupole mass spectrometer and their collision-induced dissociation (CID) investigated. CID of diastereomeric complexes, e.g. [MA(S)(B(S))(2)](+) and [MA(R)(B(S))(2)](+), leads to fragmentation patterns characterized by R(homo) = [MA(S)B(S)](+)/[M(B(S))(2)](+) and R(hetero) = [MA(R)B(S)](+)/[M(B(S))(2)](+) abundance ratios, which depend upon the relative stability of the diastereomeric [MA(S)B(S)](+) and [MA(R)B(S)](+) complexes in the gas phase. The chiral resolution factor R(chiral) = R(homo)/R(hetero) is found to depend not only on the nature of the M ion but also on that of the fragmenting species, whether [MAB(2)](+) or [MA(2)B](+). The origin of this behavior is discussed. 相似文献
993.
Fructosamine-3-kinase (FN3K) mediates the regeneration of lysine from fructosamines formed on proteins as a result of the
‘early’ Maillard reaction. As fructosamines and advanced glycation endproducts derived therefrom are supposed to play an adverse
role in the development of diabetic complications, FN3K is discussed as a protein-repairing enzyme. In this study, a method
for the determination of FN3K activity in erythrocyte lysate is described which overcomes the complexity of currently known
assays. The assay is based on the FN3K-dependent conversion of the synthetic UV-active fructosamine N
α-hippuryl-N
ε-(1-deoxy-D-fructosyl)lysine (BzGFruK) to N
α-hippuryl-N
ε-(phosphofructosyl)lysine (BzGpFruK). The FN3K activity was quantified by measuring the formation of BzGpFruK using RP-HPLC
with UV detection. Identification of the metabolite BzGpFruK was achieved by means of UV and mass spectroscopy. The results
are related to the content of haemoglobin for standardisation. First activity measurements with a chosen number of normoglycaemic
subjects confirmed the convenient applicability of the method and showed distinctly different individual activities, as already
discovered recently. The new established assay needs only the equipment of a routine laboratory with HPLC instrumentation.
This should facilitate further studies about a possible relationship between the FN3K activity and the development of diabetic
complications. 相似文献
994.
Young Jun Koh Byung-Hyun Park Ji-Hyun Park Jinah Han In-Kyu Lee Jin Woo Park Gou Young Koh 《Experimental & molecular medicine》2009,41(12):880-895
We sought to determine the effects of activation of peroxisome proliferator-activated receptor-γ (PPAR-γ) on multilocularization of adipocytes in adult white adipose tissue (WAT). Male C57BL/6 normal, db/db, and ob/ob mice were treated with agonists of PPAR-γ, PPAR-α, or β3-adrenoceptor for 3 weeks. To distinguish multilocular adipocytes from unilocular adipocytes, whole-mounted adipose tissues were co-immunostained for perilipin and collagen IV. PPAR-γ activation with rosiglitazone or pioglitazone induced a profound change of unilocular adipocytes into smaller, multilocular adipocytes in adult WAT in a time-dependent, dose-dependent, and reversible manner. PPAR-α activation with fenofibrate did not affect the number of locules or remodeling. db/db and ob/ob obese mice exhibited less multilocularization in response to PPAR-γ activation compared to normal mice. Nevertheless, all adipocytes activated by PPAR-γ contained a single nucleus regardless of locule number. Multilocular adipocytes induced by PPAR-γ activation contained substantially increased mitochondrial content and enhanced expression of uncoupling protein-1, PPAR-γ coactivator-1-α , and perilipin. Taken together, PPAR-γ activation induces profound multilocularization and enhanced mitochondrial biogenesis in the adipocytes of adult WAT. These changes may affect the overall function of WAT. 相似文献
995.
Cross-beta amyloid is implicated in over 20 human diseases. Experiments suggest that specific sequence elements within amyloidogenic proteins play a major role in seeding amyloid formation. Identifying these seeding sequences is important for rationalizing the molecular mechanisms of amyloid formation and for elaborating therapeutic strategies that target amyloid. Theoretical techniques play an important role in facilitating the identification and structural characterization of putative seeding sequences; most amyloid species are not amenable to high resolution experimental structure techniques. In this study we have combined a coarse-grained physicochemical protein model with a highly efficient Monte Carlo sampling technique to identify amyloidogenic sequences in four proteins for which respective experimental peptide fragmentation data exist. Peptide sequences were defined as amyloidogenic if the ensemble structure predicted for three interacting peptides described a stable and regular three-stranded beta-sheet. For such peptides, free energies were calculated to provide a measure of amyloid propensity. The overall agreement between the experimental and predicted data is good, and we correctly identify several self-recognition motifs proposed to define the cross-beta amyloid fibril architectures of two of the proteins. Our results compare very favorably with those obtained using atomistic molecular dynamics methods, though our simulations are 30-40 times faster. 相似文献
996.
Confocal laser scanning microscopy (CLSM) was used to study single‐ and two‐component protein uptake for α‐lactalbumin (ALA) and β‐lactoglobulin (BLG), as models for whey proteins, to SP Sepharose FF at pH 3.7 during batch experiments in a finite bath. By coupling a fluorescent dye with the protein molecule, the penetration into individual adsorbent particles at different times during batch uptake was visualised. In a single‐component system, BLG penetrated fast into the adsorbent beads and gradually filled them in a shell‐wise fashion, while adsorption of ALA was mostly confined to the outer shells of the adsorbent. For the two‐component studies, the results showed that ALA was able to displace BLG despite its lower affinity to the adsorbent under the employed conditions. CLSM results were then compared both qualitatively and quantitatively to their counterparts obtained in traditional experiments by indirect measurements of the protein concentration in the fluid phase. A novel quantitative approach was undertaken by modifying the simple kinetic rate model traditionally used to determine the kinetic rate constant, k1, for batch uptake experiments, in order to describe batch uptake kinetics based on CLSM data. Although BLG results were in good agreement, there was a discrepancy in ALA results. 相似文献
997.
A convenient method for attaching fluorescein (via its epoxy derivate) to natural starch and its temperature/pH‐sensitive qualities of fluorescence were investigated. 3‐epoxypropoxy fluorescein (EPF) was first synthesized through the reaction between fluorescein and epichlorohydrin, and starch‐bearing fluorescein (ST‐EPF) was prepared via ring‐opening reaction with EPF in dimethyl sulfoxide (DMSO) solution, in the presence of NaH as a catalyst. Both of them were characterized by the methods of 1H NMR, MS, IR, XRD, UV–Vis, and luminescence spectra, respectively. The chemiluminescent and photophysical behaviors of the dye fluorescein derivative and the polymer‐containing fluorescein were studied. The results indicated that ST‐EPF could still provide temperature and pH sensitivity similar to that of fluorescein and could achieve better long‐term stability and fast equilibrium response. ST‐EPF had an excellent linear response between relative fluorescence intensity and temperature in the range of 0–60°C and a nonlinear relationship between relative fluorescence intensity and pH in the wide range of 0.0–12.0, and so it has promise as an optical transducer for temperature and pH value determinations. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
998.
Fabien Pascale Klaus Doll Francesco Silvio Gentile Roberto Dovesi 《Journal of computational chemistry》2023,44(2):65-75
The ferromagnetic and antiferromagnetic wave functions of the KMnF3 perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented. 相似文献
999.
Dr. Dao-Sheng Liu Zhaoyu Zhang Dr. Yufei Zhang Dr. Minghui Ye Song Huang Shunzhang You Zijian Du Jiangfeng He Dr. Zhipeng Wen Dr. Yongchao Tang Prof. Xiaoqing Liu Prof. Cheng Chao Li 《Angewandte Chemie (International ed. in English)》2023,62(5):e202215385
The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al2(SO4)3 is proposed as decent electrolyte additive to manipulate OH−-mediated cross-communication between Zn anode and NaV3O8 ⋅ 1.5H2O (NVO) cathode. The hydrolysis of Al3+ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH− accumulation by Al3+ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH− toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH−-mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates. 相似文献
1000.
Prof. Xiaona Li Yang Xu Prof. Changtai Zhao Duojie Wu Dr. Limin Wang Matthew Zheng Xu Han Dr. Simeng Zhang Junyi Yue Prof. Biwei Xiao Dr. Wei Xiao Dr. Ligen Wang Prof. Tao Mei Prof. Meng Gu Prof. Jianwen Liang Prof. Xueliang Sun 《Angewandte Chemie (International ed. in English)》2023,62(48):e202306433
As exciting candidates for next-generation energy storage, all-solid-state lithium batteries (ASSLBs) are highly dependent on advanced solid-state electrolytes (SSEs). Here, using cost-effective LaCl3 and CeCl3 lattice (UCl3-type structure) as the host and further combined with a multiple-cation mixed strategy, we report a series of UCl3-type SSEs with high room-temperature ionic conductivities over 10−3 S cm−1 and good compatibility with high-voltage oxide cathodes. The intrinsic large-size hexagonal one-dimensional channels and highly disordered amorphous phase induced by multi-metal cation species are believed to trigger fast multiple ionic conductions of Li+, Na+, K+, Cu+, and Ag+. The UCl3-type SSEs enable a stable prototype ASSLB capable of over 3000 cycles and high reversibility at −30 °C. Further exploration of the brand-new multiple-cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density. 相似文献