Azimuthal Dipolar Rotor Arrays on Surfaces

A set of dipolar molecular rotor compounds was designed, synthesized and adsorbed as self-assembled 2D arrays on Ag(111) surfaces. The title molecules are constructed from three building blocks: (a) 4,8,12-trioxatriangulene (TOTA) platforms that are known to physisorb on metal surfaces such as Au(111) and Ag(111), (b) phenyl groups attached to the central carbon atom that function as pivot joints to reduce the barrier to rotation, (c) pyridine and pyridazine units as small dipolar units on top. Theoretical calculations and scanning tunneling microscopy (STM) investigations hint at the fact that the dipoles of neighboring rotors interact through space through pairs of energetically favorable head-to-tail arrangements.     

Give or Take: Effects of Electron-Accepting/-Withdrawing Groups in Red-Fluorescent BODIPY Molecular Rotors

Mapping microviscosity, temperature, and polarity in biosystems is an important capability that can aid in disease detection. This can be achieved using fluorescent sensors based on a green-emitting BODIPY group. However, red fluorescent sensors are desired for convenient imaging of biological samples. It is known that phenyl substituents in the β position of the BODIPY core can shift the fluorescence spectra to longer wavelengths. In this research, we report how electron-withdrawing (EWG) and -donating (EDG) groups can change the spectral and sensory properties of β-phenyl-substituted BODIPYs. We present a trifluoromethyl-substituted (EWG) conjugate with moderate temperature sensing properties and a methoxy-substituted (EDG) molecule that could be used as a lifetime-based polarity probe. In this study, we utilise experimental results of steady-state and time-resolved fluorescence, as well as quantum chemical calculations using density functional theory (DFT). We also explain how the energy barrier height (Ea) for non-radiative relaxation affects the probe’s sensitivity to temperature and viscosity and provide appropriate Ea ranges for the best possible sensitivity to viscosity and temperature.     

Chaotic motions of a rigid rotor in short journal bearings

In the present paper the conditions that give rise to chaotic motions in a rigid rotor on short journal bearings are investigated and determined. A suitable symmetry was given to the rotor, to the supporting system, to the acting system of forces and to the system of initial conditions, in order to restrict the motions of the rotor to translatory whirl. For an assigned distance between the supports, the ratio between the transverse and the polar mass moments of the rotor was selected conveniently small, with the aim of avoiding conical instability. Since the theoretical analysis of a system's chaotic motions can only be carried out by means of numerical investigation, the procedure here adopted by the authors consists of numerical integration of the rotor's equations of motion, with trial and error regarding the three parameters that characterise the theoretical model of the system: m, the half non-dimensional mass of the rotor, , the modified Sommerfeld number relating to the lubricated bearings, and , the dimensionless value of rotor unbalance. In the rotor's equations of motion, the forces due to the lubricating film are written under the assumption of isothermal and laminar flow in short bearings. The number of numerical trials needed to find the system's chaotic responses has been greatly reduced by recognition of the fact that chaotic motions become possible when the value of the dimensionless static eccentricity % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbnL2yY9% 2CVzgDGmvyUnhitvMCPzgarmWu51MyVXgaruWqVvNCPvMCG4uz3bqe% fqvATv2CG4uz3bIuV1wyUbqee0evGueE0jxyaibaieYlf9irVeeu0d% Xdh9vqqj-hEeeu0xXdbba9frFf0-OqFfea0dXdd9vqaq-JfrVkFHe9% pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaaca% qabeaadaabauaaaOqaaiabew7aLnaaBaaaleaacaWGZbaabeaaaaa!4046!\[\varepsilon _s \] is greater than 0.4. In these conditions, non-periodic motions can be obtained even when rotor unbalance values are not particularly high (=0.05), whereas higher values (>0.4) make the rotor motion periodic and synchronous with the driving rotation. The present investigation has also identified the route that leads an assigned rotor to chaos when its angular speed is varied with prefixed values of the dimensionless unbalance . The theoretical results obtained have then been compared with experimental data. Both the theoretical and the experimental data have pointed out that in the circumstances investigated chaotic motions deserve more attention, from a technical point of view, than is normally ascribed to behaviours of this sort. This is mainly because such behaviours are usually considered of scarce practical significance owing to the typically bounded nature of chaotic evolution. The present analysis has shown that when the rotor exhibits chaotic motions, the centres of the journals describe orbits that alternate between small and large in an unpredictable and disordered manner. In these conditions the thickness of the lubricating film can assume values that are extremely low and such as to compromise the efficiency of the bearings, whereas the rotor is affected by inertia forces that are so high as to determine severe vibrations of the supports.Nomenclature C radial clearance of bearing (m) - D diameter of bearing (m) - e dimensional eccentricity of journal (m) - e _s value of e corresponding to the static position of the journal - E dimensional static unbalance of rotor (m) - f _x, f _y =F _x/(P), F _y/(P): non-dimensional components of fluid film force - F _x, F _y dimensional components of fluid film force (N) - g acceleration of gravity (m/s²) - L axial length of bearing (m) - m % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbnL2yY9% 2CVzgDGmvyUnhitvMCPzgarmWu51MyVXgaruWqVvNCPvMCG4uz3bqe% fqvATv2CG4uz3bIuV1wyUbqee0evGueE0jxyaibaieYlf9irVeeu0d% Xdh9vqqj-hEeeu0xXdbba9frFf0-OqFfea0dXdd9vqaq-JfrVkFHe9% pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaaca% qabeaadaabauaaaOqaaiabg2da9maalaaabaGaeqyYdC3aaWbaaSqa% beaacaaIYaaaaaGcbaGaeqyYdC3aa0baaSqaaGabciaa-bdaaeaaca% WFYaaaaaaakiabg2da9maalaaabaGaeqyYdC3aaWbaaSqabeaacaaI% YaaaaOGaam4qaaqaaiabeo8aZjaadEgaaaaaaa!4C14!\[ = \frac{{\omega ^2 }}{{\omega _0^2 }} = \frac{{\omega ^2 C}}{{\sigma g}}\]: half non-dimensional mass of rotor - M half mass of rotor (kg) - n angular speed of rotor (in r.p.m.=60/2) - t time     

转杯速度与成纱质量关系的研究

本文探讨了国产转杯纺纱器的转杯速度与成纱质量的关系,采用经过优化的转杯、隔离盘和假捻盘进行纺纱。试验结果表明,随着转杯速度的提高,成纱质量基本上呈下降趋势。但在杯速为50000 r/min 左右时,成纱质量的几项主要指标最佳。这对于合理设计转杯速度具有一定的参考价值。     

Dipolar Rotors Orderly Aligned in Mesoporous Fluorinated Organosilica Architectures

New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p‐divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 10⁸ Hz at 325 K), as detected by solid‐state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I₂ vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl‐fluoro‐phenylene rotors, affecting their motion and the dielectric properties.     

传递矩阵－多项式法的改进及其应用

本文提出一种计算转子－滑动轴承－挤压油膜阻尼器转子系统的阻尼固有频率及稳定性的方法，即将传递矩奉多项式法改进后，应用于这类具有分叉结点的系统，直接得到系统的特征多项式，然后用Ｂａｉｒｓｔｏｗ－Ｎｅｗｔｏｎ僻因子法求出全部特征根。本方法具有占内存少、计算速度快、数值稳定等特点，文中对一转子模型进行了计算，其结果与实测基本相符。     

Dynamics of coupled systems

A survey in the form of a review of the author’s research results in the area of dynamics of coupled rotations and coupled systems is presented. The theorem on the existence of a trigger of the coupled singularities and the separatrix in the form of the number eight is presented with a few examples of coupled rotations of the simple systems with debalances. Also, a survey of models and dynamics of coupled systems composed of a number of deformable bodies (plates, beams or belts) with different properties of materials and discrete layer properties is presented and mathematically described. The constitutive stress–strain relations for materials of the coupled sandwich structure elements are presented for different properties: elastic, viscoelastic and creeping. The characteristic modes of the coupled system vibrations are obtained and analyzed for different kinds of materials and structure composition. The visualization of the characteristic numbers and modes and eigenamplitude forms are presented. Structural analysis of sandwich structure vibrations is done.     

Solid-state luminescence of Au(I) complexes with external stimuli-responsive properties

In the last decade, the field of stimuli-responsive luminescent materials have been intensely emerged because of the high potential application to functional sensors or photoelectronic devices. In particular, luminescent molecular crystals constructed from Au(I) complexes have produced a wide range of examples of luminescent alterations when some external stimulations, such as heat, mechanical stress, vapor (or solvents), were applied to the solid samples. In this review, we describe the recent progress through a summary of the reported Au(I) complexes based on their utilized stimuli-responsive mechanisms, which are categorized in crystal phase transitions (“crystal-to-amorphous”, “crystal-to-crystal” and “single-crystal-to-single-crystal” transitions) and molecular rotation in crystalline media, respectively.     

An Ultrafast Molecular-Rotor-Based Fluorescent Turn-On Sensor for the Perrhenate Anion in Aqueous Solution

Devising sensors for the perrhenate anion in aqueous media is extremely challenging, and has seldom been reported in the literature. Herein, we report a fluorescence turn-on sensor for the perrhenate anion in aqueous media based on the aggregation-induced emission of a popular ultrafast molecular rotor dye, Thioflavin-T. The selective response towards the perrhenate anion has been rationalized in terms of matching water affinity, with the weakly hydrated perrhenate anion spontaneously forming a contact ion pair with the weakly hydrated ultrafast molecule-rotor-based organic cation, Thioflavin-T, which in turn leads to an aggregate assembly that provides a fluorescence turn-on response towards perrhenate. The sensing response of Thioflavin-T has been found to be quite selective towards the perrhenate anion when tested against anions that are ubiquitously present in the environment, such as chloride, nitrate, and sulfate anions. The formation of self-assembled Thioflavin-T aggregates has also been investigated by time-resolved emission and temperature-dependent measurements.     

Enhancing the Viscosity-Sensitive Range of a BODIPY Molecular Rotor by Two Orders of Magnitude

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.