Indeno[1,2,3,4-pqra]Perylene: A Medium-Sized Aromatic Hydrocarbon Exhibiting Full-Range Visible-Light Absorption

We report the synthesis and properties of indeno[1,2,3,4-pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon-carbon bonds. The synthetic route through two-fold C−H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium-sized aromatic hydrocarbon with the composition C₂₄H₁₂ that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO-LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron-withdrawing subunit (benzoaceanthrylene) and an electron-donating subunit (perylene). The electronic properties of indenoperylene were modulated via post-functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near-infrared-responsive and redox-active materials.     

Ultrafast Excited State Relaxation Dynamics of New Fuchsine- a Triphenylmethane Derivative Dye

An all-inclusive investigation of the ultrafast excited state relaxation dynamics of a triphenylmethane derivative molecule, New Fuchsine (NF), using a combined approach of density functional theory (DFT), femtosecond transient absorption spectroscopy (fs-TAS), and photoluminescence spectroscopy is presented in this work. The DFT calculations confirmed the formation of twisted molecular structure in the excited state of NF in ethanol solution with bond rotation of ≈86°. TAS measurements of NF solution exhibited ultrafast ground state-recovery pathway via a conical intersection confirming an ultrafast structural reorientation. On the contrary, TAS measurements of NF thin-film exhibited a longer excited-state lifetime suggesting a hindered molecular twisted state formed as an intermediate step. Photophysical kinetic models are proposed to globally fit the fs-TAS data establishing the twisted intramolecular charge transfer (TICT) state mediated ground state recovery for NF in solution and thin film, respectively. Temperature-dependent photoluminescence study of NF film provided a clear insight into the effect of rotational motion of phenyl rings in NF molecules over the TICT mediated emission.     

Remarkable Size Effect on Photophysical and Nonlinear Optical Properties of All-Carboatomic Rings,Cyclo[18]carbon and Its Analogues

Inspired by recent experimental observation of molecular morphology and theoretical predictions of multiple properties of cyclo[18]carbon, we systematically studied the photophysical and nonlinear optical properties of cyclo[2N]carbons (N=3–15) allotropes through density functional theory. This work unveils the unusual optical properties of the sp-hybridized carbon rings with different sizes. The remarkable size dependence of the optical properties of these systems and their underlying nature are profoundly explored, and the relevance between aromaticity and optical properties are highlighted. The extrapolation curves fitted for energy level of frontier molecular orbitals, maximum absorption wavelength, and (hyper)polarizability of considered carbon rings are presented, which can be used to reliably predict corresponding properties for arbitrarily large carbon rings. The findings in this study will facilitate the exploration of potential application of cyclocarbons in the field of optical materials.     

Experimental study on age and gender differences in microscopic movement characteristics of students

Campus security has aroused many concerns from the whole society. Stampede is one of the most frequent and influential accidents in campus. Studies on pedestrian dynamics especially focusing on students are essential for campus security, which are helpful to improve facility design and emergency evacuation strategy. In this paper, primary and middle school students were recruited to participate in the single-file experiments. The microscopic movement characteristics,including walking speed, headway, gait characteristics(step length, step frequency and swaying amplitude) and their relations were investigated. Age and gender differences in the headway-speed diagram and space requirements were analyzed by statistical tests. The results indicated that the impacts of age and gender were significant. There were three stages for the influence of gender on the headway-speed diagram for both age groups. The impacts on students' space requirements were consistent for different age and gender groups. But the impacts of age and gender on free-flow speed were affected by each other. Due to the connection of walking speed and gait characteristics, the comparisons of gait characteristics between different ages and genders were performed to understand the corresponding differences in speed more deeply. The results showed that differences in step length and swaying amplitude between males and females were significant for both age groups. The effect of gender on step frequency was significant for primary students. But for middle school students,whether gender had significant impact on step frequency was not clear here because of the large P-value. Besides, the influence of age on gait characteristics changed with gender.     

Dynamic Modeling of the Feed Drive System of a CNC Metal Cutting Machine

Studying the vibrational behavior of feed drive systems is important for enhancing the structural performance of computer numerical control (CNC) machines. The preload on the screw and nut position have a great influence on the vibration characteristics of the feed drive as two very important operational conditions. Rotational acceleration of the screw also affects the performance of the CNC feed drive when machining small parts. This paper investigates the influence of preload and nut position on the vibration characteristics of the feed drive system of a CNC metal cutting machine in order to be able to eliminate an observed resonance occurred at high rotational speeds of the screw, corresponding to high feed rates. Additionally, rational structural parameters of the feed drive system are selected in order to increase the rotational acceleration for improving the performance of the CNC machine. Experiments and analyses showed that by selecting specific parameters of feed drive system and simultaneously applying a certain value of preload, a 97% increase in rotational acceleration and 30% time reduction considering the vibration resistance at high rotational speeds can be achieved.     

Projective well orders and coanalytic witnesses

We further develop a forcing notion known as Coding with Perfect Trees and show that this poset preserves, in a strong sense, definable P-points, definable tight MAD families and definable selective independent families. As a result, we obtain a model in which $\mathfrak{a}=\mathfrak{u}=\mathfrak{i}={\mathrm{?}}_1<2^{{\mathrm{?}}_0}={\mathrm{?}}_2$, each of $\mathfrak{a}$, $\mathfrak{u}$, $\mathfrak{i}$ has a ${\mathrm{\Pi }}_1^1$ witness and there is a ${\mathrm{\Delta }}_3^1$ well-order of the reals. Note that both the complexity of the witnesses of the above combinatorial cardinal characteristics, as well as the complexity of the well-order are optimal. In addition, we show that the existence of a ${\mathrm{\Delta }}_3^1$ well-order of the reals is consistent with $\mathfrak{c}={\mathrm{?}}_2$ and each of the following: $\mathfrak{a}=\mathfrak{u}<\mathfrak{i}$, $\mathfrak{a}=\mathfrak{i}<\mathfrak{u}$, $\mathfrak{a}<\mathfrak{u}=\mathfrak{i}$, where the smaller cardinal characteristics have co-analytic witnesses.Our methods allow the preservation of only sufficiently definable witnesses, which significantly differs from other preservation results of this type.     

Selective Benzylic CH-Borylations by Tandem Cobalt Catalysis

Metal-catalyzed C?H activations are environmentally and economically attractive synthetic strategies for the construction of functional molecules as they obviate the need for pre-functionalized substrates and minimize waste generation. Great challenges reside in the control of selectivities, the utilization of unbiased hydrocarbons, and the operation of atom-economical dehydrocoupling mechanisms. An especially mild borylation of benzylic CH bonds was developed with the ligand-free pre-catalyst Co[N(SiMe₃)₂]₂ and the bench-stable and inexpensive borylation reagent B₂pin₂ that produces H₂ as the only by-product. A full set of kinetic, spectroscopic, and preparative mechanistic studies are indicative of a tandem catalysis mechanism of CH-borylation and dehydrocoupling via molecular Co^I catalysts.     

染料敏化太阳能电池载流子传输的数值模拟

由于在染料敏化太阳能电池(dye-sensitized solar cell, DSSC)中存在染料弛豫、半导体薄膜中电子与氧化态染料分子发生反应和电子在电解质中与氧化态离子复合等不利反应,利用一个更完善的DSSC载流子传输模型对电池的光电性能进行模拟就显得非常重要。为此,本文基于由多重俘获理论建立的DSSC中的包括电子、染料阳离子、碘化物和三碘化物在内的载流子传输模型,数值模拟得到了不同TiO₂薄膜厚度、不同入射光强度与不同染料分子吸收系数下DSSC的J-V曲线。结果表明,随着TiO₂薄膜厚度的增加,太阳能电池的短路电流密度增大,开路电压减小,光电转换效率先增大后减小。当DSSC的TiO₂薄膜厚度为20 μm时,光电转换效率达到最大值7.41%,同时光电转换效率随入射光强度与染料分子吸收系数的增大均有一定程度提高,其中在吸收系数为4 500 cm^-1时,光电转换效率为6.73%。以上结果可以为改进DSSC的光电性能提供理论指导。     

Application of acoustic methods for a non-destructive evaluation of the elastic properties of several typologies of materials

In solid phase materials, differently from what happens in the fluid phase, elastic waves propagate both through longitudinal and transverse waves. From the speed of propagation of longitudinal and transverse waves, it is possible to evaluate important elastic properties of the solids under study, namely the Young’s modulus, the Poisson’s coefficient, the bulk modulus and the shear modulus. This work suggests an accurate method for measuring wave propagation speeds in homogeneous and non-homogeneous materials with the purpose to evaluate their mechanical properties and the associated uncertainty.First of all, to assess the performance of the proposed methodology, based on the “pulse-echo” technique, in terms of accuracy and precision, measurements of wave propagation speeds have been carried out, in atmospheric conditions, in well-known homogeneous and isotropic materials, such as copper, aluminum, stainless steel and also polymethyl methacrylate (Plexiglas®), Teflon® and optical glass BK7. These results were compared with the values reported in literature (if present), showing how published speed of sound data are very disperse and not so reliable owing to the lack of a precise uncertainty evaluation and of the temperature value associated to the measurement. Then, the same experimental apparatus was used for measuring speed of sound as a function of temperature (from 274.15 to 313.15 K) for 304 stainless steel and oxygen free copper, showing a good accuracy of the results also for temperature conditions far from ambient. Finally, the same procedure was applied to a non-homogeneous solid, obtaining some very preliminary results in typical mediterranean building material, as Carrara marble.