Influence of the image charge effect on the hydrogen-like impurity-bound polaron in a spherical quantum dot in the presence of an electric field

We have investigated the influence of an external electric field on the binding energies and polaronic shifts of the ground and some first few excited states of a hydrogenic impurity in a spherical quantum dot by taking into account the image charge effect. By using Landau–Pekar variational method the general analytical expression is obtained for the impurity bound-polaron energies. It has been numerically identified the conditions (electric field, nominal radius of quantum dot, etc.) in which the bound-polaron states can be existence in GaAs quantum dot. We have shown that the polaronic shifts in the binding energy of 1s-like state are the same in cases with and without image charge effect while they for 2s-like state are not coincide and have different monotonic behavior versus confinement potential. Electron–phonon interaction lifts the degeneracy of the 2px-, 2py-, and 2pz-like states of a donor impurity and reduces their binding energies.     

Solvent and pH Effects on the Fluorescence of 7-(Dimethylamino)-2-Fluorenesulfonate

A novel water-soluble solvatochromic molecule, 7-(dimethylamino)-2-fluorenesulfonate (2,7-DAFS), was prepared by a three-step reaction from 2-nitrofluorene in good overall yield. The pH and solvent effects on the UV-VIS absorption and fluorescence spectra of 2,7-DAFS have been studied. Protonation of the dimethylamino group switches the absorption from intramolecular charge-transfer (ICT) to π → π* transition. The ground state pKa value of 2,7-DAFS was determined as 4.51. The fluorescence spectrum of the excited basic form, *(DAFS), shows a structureless single band with a large Stokes shift, whereas that of the acidic form, *(⁺HDAFS), exhibits a structured band with a small Stokes shift. The emission intensities of the basic and acidic forms versus pH/Ho plots show stretched sigmoidal curves and indicate that (1) the rate of deprotonation of *(⁺HDAFS) is comparable to the fluorescence decay of the species, and (2) the efficient proton-induced quenching of *(DAFS) fluorescence occurs. The pKa* was estimated as −1.7 from the fluorescence titration curve. The fluorescence maximum of *(DAFS) is blue-shifted as the polarity of solvent decreases. However, no clear dependency of the emission intensity and spectral half width, and thus fluorescence quantum yield, on the solvent polarity was revealed. It appears that the fluorescence sensitivity of 2,7-DAFS is 15 ∼ 25 times greater than the sensitivity of a widely utilized fluorescent probe, 5-(dimethylamino)-1-naphthalenesulfonate. This higher sensitivity, together with the ease of derivatization, would provide the fluorene-based fluorescent molecules significant advantages for a variety of applications.     

Mathematical model of electromigration allowing the deviation from electroneutrality

The structure of the double layer on the boundary between solid and liquid phases is described by various models, of which the Stern–Gouy–Chapman model is still commonly accepted. Generally, the solid phase is charged, which also causes the distribution of the electric charge in the adjacent diffuse layer in the liquid phase. We propose a new mathematical model of electromigration considering the high deviation from electroneutrality in the diffuse layer of the double layer when the liquid phase is composed of solution of weak multivalent electrolytes of any valence and of any complexity. The mathematical model joins together the Poisson equation, the continuity equation for electric charge, the mass continuity equations, and the modified G-function. The model is able to calculate the volume charge density, electric potential, and concentration profiles of all ionic forms of all electrolytes in the diffuse part of the double layer, which consequently enables to calculate conductivity, pH, and deviation from electroneutrality. The model can easily be implemented into the numerical simulation software such as Comsol. Its outcome is demonstrated by the numerical simulation of the double layer composed of a charged silica surface and an adjacent liquid solution composed of weak multivalent electrolytes. The validity of the model is not limited only to the diffuse part of the double layer but is valid for electromigration of electrolytes in general.     

The Impact of C2 Insertion into a Carbazole Donor on the Physicochemical Properties of Dibenzo[a,j]phenazine-Cored Donor–Acceptor–Donor Triads

Novel electron donor–acceptor–donor (D-A-D) compounds comprising dibenzo[a,j]phenazine as the central acceptor core and two 7-membered diarylamines (iminodibenzyl and iminostilbene) as the donors have been designed and synthesized. Investigation of their physicochemical properties revealed the impact of C₂ insertion into well-known carbazole electron donors on the properties of previously reported twisted dibenzo[a,j]phenazine-core D-A-D triads. Slight structural modification caused a drastic change in conformational preference, allowing unique photophysical behavior of dual emission derived from room-temperature phosphorescence and triplet–triplet annihilation. Furthermore, electrochemical analysis suggested sigma-dimer formation and electrochemical polymerization on the electrode. Quantum chemical calculations also rationalized the experimental results.     

Mo掺杂调控电子结构增强NiS电催化固氮性能

以泡沫镍为骨架,通过水热法制备了Mo掺杂的NiS多级纳米花状结构(Mo-NiS)。在偏压为-0.7 V(vs RHE)下,2 h内,0.83 Mo-NiS(制备时钼、镍物质的量之比为0.83)的电催化固氮速率平均可达4.21μg·cm~(-2)·h~(-1),法拉第效率平均为18%。XPS测试和DFT计算表明,Mo掺杂增加了Ni活性位点周围的电子云密度,提高了电荷传输速率,促使*NNH_2到*N能垒大幅度降低,从而提升了电催化固氮效率。     

Tailoring the polarity of polymer shell on BaTiO_3 nanoparticle surface for improved energy storage performance of dielectric polymer nanocomposites

Nanocomposites comprising flexible polymers and high dielectric constant inorganic nanoparticles are considered to be one of the promising candidates for electrostatic capacitor dielectrics.However,the effect of interfacial property on electrical ene rgy storage of dielectric polymer nanocomposites is still not clear.Herein,the role of the polarity of the interfacial region is investigated.For this purpose,three polymers with different polarity,polymethyl methacrylate(PMMA),polyglycidyl methacrylate,and polymethylsulfonyl ethyl methacrylate(PMSEMA) are attached onto BaTi03(BT) na noparticle surface via surface-initiated reversible addition-fragmentation chain transfer polymerization.It is found that the polarity of shell polymers shows an apparent effect on the dielectric and energy storage of dielectric polymer nanocomposites.For example,PMSEMA@BT(shell polymer possesses the highest polarity)increases dielectric loss and decreases the breakdown strength of the nanocomposites,leading to lower ene rgy storage capability.However,PMMA@BT(shell polymer possesses the lowest polarity) can induce higher breakdown strength of the nanocomposites.As a result,the PMMA@BT nanocomposite exhibits the highest electrical energy sto rage capability among the three nanocomposites.This re search provides new insight into the design of core-shell nanofillers for dielectric energy storage applications.     

Non-contact in-situ pulsed electro acoustic method for the analysis of charge transport in irradiated space-used polymers

The characterization of dielectric materials in space environment requires to understand and predict their electric behaviour, taking into account ionisation, and ageing effect (through electron or UV radiation, thermal cycling, …)For this purpose, new methods have been developed for the characterisation and qualification of space materials and satellite structure. These studies led initially to the development of dedicated facilities for the simulation of representative irradiation conditions. This work is focused on a new non-disturbing technique for the measurement of charge distribution within space irradiated polymers. This technique named PEA (Pulsed Electro-Acoustic) has been implemented in the irradiation facility for in-situ and real time measurement during irradiation and relaxation of polymer materials. Implementation and validation of this technique are presented and discussed in this paper.     

Surface charge dynamics studied by the temporal evolution of the corona charging current

The decay of surface charges deposited on the dielectric material by the partial discharge (PD) activity has a great impact on the repetition of partial discharges. In this work, the effect of dielectric placed on the surface of ground electrode in a needle-plane configuration on the discharge activity was investigated, with the application of a periodic negative step voltage. The charge decay mechanisms on a corona charged dielectric surface were investigated based on a comparison between experiments and a FEM-based numerical model. The comparison indicates that the surface charges may decay due to different mechanisms depending on the applied stress.     

In situ X‐ray data collection and structure phasing of protein crystals at Structural Biology Center 19‐ID

A prototype of a 96‐well plate scanner for in situ data collection has been developed at the Structural Biology Center (SBC) beamline 19‐ID, located at the Advanced Photon Source, USA. The applicability of this instrument for protein crystal diffraction screening and data collection at ambient temperature has been demonstrated. Several different protein crystals, including selenium‐labeled, were used for data collection and successful SAD phasing. Without the common procedure of crystal handling and subsequent cryo‐cooling for data collection at T = 100 K, crystals in a crystallization buffer show remarkably low mosaicity (<0.1°) until deterioration by radiation damage occurs. Data presented here show that cryo‐cooling can cause some unexpected structural changes. Based on the results of this study, the integration of the plate scanner into the 19‐ID end‐station with automated controls is being prepared. With improvement of hardware and software, in situ data collection will become available for the SBC user program including remote access.