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31.
Vera Deneva 《Molecular physics》2019,117(13):1613-1620
ABSTRACTThe tautomeric optical sensors based on 4-(phenyldiazenyl)naphthalen-1-ol exist in their pure enol tautomeric form as free ligands, while the addition of metal ion fully shifts the equilibrium towards the keto tautomer allowing a red shift in the measured absorbance. This effect is achieved when a side ionophore group is connected to a tautomeric backbone by a spacer in a way that stabilizes the enol form via hydrogen boding. When the ionophore captures the metal ion the keto form is stabilized due to C─O tautomeric group participation in the complex. In the current study, we model theoretically the effect of symmetric tweezer like ionophores (RCOXCOR, where X, being CH or N, is the linker to the tautomeric backbone) on the tautomeric state and complexation ability of 4-(phenyldiazenyl)naphthalen-1-ol containing ligands. It was found that enol form stabilisation is achieved when R?=?NMe2, independing on the linker. Both ligands are unsuitable for capturing alkali metal ions. The calculations predict that the complexation with alkali earth metal ions could lead to a full shift of the tautomeric equilibrium towards keto tautomer. 相似文献
32.
Dr. Stepas Toliautas Dr. Jelena Dodonova Audrius Žvirblis Ignas Čiplys Artūras Polita Dr. Andrius Devižis Prof. Sigitas Tumkevičius Prof. Juozas Šulskus Dr. Aurimas Vyšniauskas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10342-10349
Molecular rotors are a class of fluorophores that enable convenient imaging of viscosity inside microscopic samples such as lipid vesicles or live cells. Currently, rotor compounds containing a boron-dipyrromethene (BODIPY) group are among the most promising viscosity probes. In this work, it is reported that by adding heavy-electron-withdrawing −NO2 groups, the viscosity-sensitive range of a BODIPY probe is drastically expanded from 5–1500 cP to 0.5–50 000 cP. The improved range makes it, to our knowledge, the first hydrophobic molecular rotor applicable not only at moderate viscosities but also for viscosity measurements in highly viscous samples. Furthermore, the photophysical mechanism of the BODIPY molecular rotors under study has been determined by performing quantum chemical calculations and transient absorption experiments. This mechanism demonstrates how BODIPY molecular rotors work in general, why the −NO2 group causes such an improvement, and why BODIPY molecular rotors suffer from undesirable sensitivity to temperature. Overall, besides reporting a viscosity probe with remarkable properties, the results obtained expand the general understanding of molecular rotors and show a way to use the knowledge of their molecular action mechanism for augmenting their viscosity-sensing properties. 相似文献
33.
34.
Two new complexes of [Mn(2-MPyzCI)2Cl2].H2O (1) and [Mn(2-MPyzCI)2(H2O)2](NO3)2 (2) were synthesized from the reaction of MnX2.4H2O (X=Cl? and NO3?) with 2-cyanopyrazine in methanolic solution. The chelating methyl pyrazine-2-carboximidate (2-MPyzCI) ligand is formed via the methanolysis of 2-cyanopyrazine. Although coordination environment around manganes(II) ions is similar, but these complexes are different in geometrical position of 2-MPyzCI ligands. As both compounds are synthesized under the same reaction conditions, the only difference between these two complexes are counter ions and changing of geometrical position of ligands can be considered as a result of influence of the counter-anions on the molecular structures. 相似文献
35.
The biodegradability of phtalic acid esters in marine and freshwater environments was characterized by their binding free energy with corresponding degrading enzymes. According to comprehensive biodegradation effects weights, the binding free energy values were converted into dimensionless efficacy coefficient using ratio normalization method. Then, considering comprehensive dual biodegradation effects value and the structural parameters of PAEs in both marine and freshwater environments, a 3D-QSAR pharmacophore model was constructed, five PAE derivatives (DBP−COOH, DBP−CHO, DBP−OH, DINP−NH2, and DINP−NO2) were screened out based on their environmental friendliness, functionality and stability. The prediction of biodegradation effects on five PAE derivatives by biodegradation models in marine and freshwater environment increased by 15.90 %, 15.84 %, 27.21 %, 12.33 %, and 8.32 %, and 21.57 %, 15.21 %, 20.99 %, 15.10 %, and 9.74 %, respectively. By simulating the photodegradation path of the PAE derivative molecular, it was found that DBP−OH can generate .OH and provides free radicals for the photodegradation of microplastics in the environment. 相似文献
36.
37.
Luyao Tong Pengcheng Li Fupeng Li Yongjia Wang Qingfeng Li Fanxin Liu 《中国物理C(英文版)》2020,44(7):074103-074103-8
By incorporating an iso spin-dependent form of the momentum-dependent potential in the ultra-relativistic quantum molecular dynamics(UrQMD) model,we systematically investigate effects of the neutron-proton effective mass splitting m*_(n-p)=m*_n-m*_p/m and the density-dependent nuclear symmetry energy E_(sym)(ρ) on the elliptic flow v_2 in~(197)Au+~(197) Au collisions at beam energies from 0.09 to 1.5 GeV/nucleon.It is found that at higher beam energies(≥0.25 GeV/nucleon) with the approximately 75 MeV difference in slopes of the two different E_(sym)(ρ),and the variation of m*_(n-p) ranging from-0.03 to 0.03 at saturation density with isospin asymmetry δ=(ρ_n-ρ_p)/ρ-0.2,the E_(sym)(ρ) has a stronger influence on the difference in v_2 between neutrons and protons,i.e.,v_2~n-v_2~p,than m*_(n-p) has.Meanwhile,at lower beam energies(≤0.25 GeV/nucleon),v_2~n-v_2~p is sensitive to both the E_(sym)(ρ) and the m*_(n-p).Moreover,the influence of m*_(n-p) on v_2~n-v_2~p is more evident with the parameters of this study when using the soft,rather than stiff,symmetry energy. 相似文献
38.
Ionic transport in nano- to sub-nano-scale pores is highly dependent on translocation barriers and potential wells. These features in the free-energy landscape are primarily the result of ion dehydration and electrostatic interactions. For pores in atomically thin membranes, such as graphene, other factors come into play. Ion dynamics both inside and outside the geometric volume of the pore can be critical in determining the transport properties of the channel due to several commensurate length scales, such as the effective membrane thickness, radii of the first and the second hydration layers, pore radius, and Debye length. In particular, for biomimetic pores, such as the graphene crown ether we examine here, there are regimes where transport is highly sensitive to the pore size due to the interplay of dehydration and interaction with pore charge. Picometer changes in the size, e.g., due to a minute strain, can lead to a large change in conductance. Outside of these regimes, the small pore size itself gives a large resistance, even when electrostatic factors and dehydration compensate each other to give a relatively flat—e.g., near barrierless—free energy landscape. The permeability, though, can still be large and ions will translocate rapidly after they arrive within the capture radius of the pore. This, in turn, leads to diffusion and drift effects dominating the conductance. The current thus plateaus and becomes effectively independent of pore-free energy characteristics. Measurement of this effect will give an estimate of the magnitude of kinetically limiting features, and experimentally constrain the local electromechanical conditions. 相似文献
39.
Sidra Amin Aneela Tahira Amber R. Solangi Raffaello Mazzaro Zafar Hussain Ibupoto Almas Fatima Alberto Vomiero 《Electroanalysis》2020,32(5):1052-1059
Nickel oxide (NiO) nanostructures are employed in the basic medium for the oxidation of ethanol. A variety of NiO nanostructures are synthesized by wet chemical growth method, using different hydroxide (OH?) ion sources, particularly from ammonia, hexamethylenetetramine, urea and sodium hydroxide. The use of urea as (OH?) ion source results in flower‐like NiO structures composed by extremely thin nanowalls (thickness lower than 10 nm,), which demonstrated to be the most active for ethanol oxidation. All the samples exhibit NiO cubic phase, and no other impurity was detected. The cyclic voltammetry (CV) curves of NiO nanostructures were found linear over the concentration range 0.1–3.5 mM (R2=0.99) of ethanol, with the limit of detection estimated to be 0.013 mM for ethanol. The NiO nanostructures exhibit a selective signal towards ethanol oxidation in the presence of different members of alcohol family. The proposed NiO nanostructures showed a significant practicality for the reproducible and sensitive determination of ethanol from brandy, whisky, mixture of brandy and rum, and vodka samples. The nanomaterial was used as a surface modifying agent for the glassy carbon electrode and it showed a stable electro‐oxidation activity for the ethanol for 16 days. These findings indicate that the presented NiO nanomaterial can be applied in place of noble metals for ethanol sensing and other environmental applications (like fuel cells). 相似文献
40.
Octadecanuclear Gear Wheels by Self‐Assembly of Self‐Assembled “Double Saddle”‐Type Coordination Entities: Molecular “Rangoli” 下载免费PDF全文
Hareesha Dasary Dr. Rajamony Jagan Prof. Dr. Dillip Kumar Chand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1499-1507
A series of self‐assembled “double saddle”‐type trinuclear complexes of [Pd3L′3 L 2] formulation have been synthesized by complexation of a series of cis‐protected palladium(II) components with a slightly divergent “E‐shaped” non‐chelating tridentate ligand, 1,1′‐(pyridine‐3,5‐diyl)bis(3‐(pyridin‐3‐yl)urea ( L ). The cis‐protecting agents L′ employed in the study are ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), and 1,10‐phenanthroline (phen), for 1 , 2 , 3 , and 4 , respectively. The crystal structures of [Pd3(tmeda)3( L )2](NO3)6 ( 2 ), [Pd3(bpy)3( L )2](NO3)6 ( 3 ), and [Pd3(phen)3( L )2](NO3)6 ( 4 ) unequivocally support the new architecture. Two of the “double saddle”‐type complexes ( 3 and 4 ) are suitably crafted with π surfaces at the strategically located cis‐protecting sites to facilitate intermolecular π–π interactions in the solid state. As a consequence, six units of the 3 (or 4 ) are assembled, by means of six‐pairs of π–π stacking interactions, in a circular geometry to form an octadecanuclear molecular ring of [(Pd3L′3 L 2)6] composition. The overall arrangement of the rings in the crystal packing is equated with the traditional Indian art form rangoli. 相似文献