Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Excited-state absorption of meso-tetrasulfonatophenyl porphyrin: Effects of pH and micelles

The influence of the environment on the excited state transitions of meso-tetrakis(p-sulfonatophenyl) porphyrin (TPPS) is reported. TPPS was investigated in protonated and non-protonated forms, and in the presence of the cationic cetyltrimethylammonium bromide (CTAB) micelles. The singlet excited-state absorption spectra were measured by using the white-light continuum Z-scan technique and the triplet–triplet absorption spectra were acquired employing an association of laser flash photolysis and Z-scan techniques. Our results show that the perseveration of the molecular symmetry, upon excitation, depends on the state of multiplicity of the molecules, as well as on the environment and structural characteristics of the porphyrin. Additionally, it was observed that for excited molecules, the ring distortion caused by the protonation of porphyrin ring has great influence on the changes observed for the symmetry and vibronic structure. The results clearly show that the porphyrin investigated is a promising candidate for optical limiting applications for all investigated environments.     

A unified critical state model for geomaterials with an application to tunnelling

This paper is prepared in honour of Professor E.T. Brown for his outstanding contributions to rock mechanics and geotechnical engineering and also for his personal influence on the first author's research career in geomechanics and geotechnical engineering. As a result, we have picked a topic that reflects two key research areas in which Professor E.T. Brown has made seminal contributions over a long and distinguished career. These two areas are concerned with the application of the critical state concept to modelling geomaterials and the analysis of underground excavation or tunnelling in geomaterials.Partially due to Professor Brown's influence, the first author has also been conducting research in these two areas over many years. In particular, this paper aims to describe briefly the development of a unified critical state model for geomaterials together with an application to cavity contraction problems and tunnelling in soils.     

Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

A lightweight autonomous MAV for indoor search and rescue

Micro Aerial Vehicles (MAVs) have great potentials to be applied for indoor search and rescue missions. In this paper, we propose a modular lightweight design of an autonomous MAV with integrated hardware and software. The MAV is equipped with the 2D laser scanner, camera, mission computer and flight controller, running all the computation onboard in real time. The onboard perception system includes a laser‐based SLAM module and a custom‐designed visual detection module. A dual Kalman filter design provides robust state estimation by multiple sensor fusion. Specifically, the fusion module provides robust altitude measurement in the circumstance of surface changing. In addition, indoor‐outdoor transition is explicitly handled by the fusion module. In order to efficiently navigate through obstacles and adapt to multiple tasks, a task tree‐based mission planning method is seamlessly integrated with path planning and control modules. The MAV is capable of searching and rescuing victims from unknown indoor environments effectively. It was validated by our award‐winning performance at the 2017 International Micro Air Vehicle Competition (IMAV 2017), held in Toulouse, France. The performance video is available on https://youtu.be/8H19ppS_VXM .     

Flame characteristics of premixed H2-air mixtures explosion venting in a spherical container through a duct

The explosion venting duct can effectively reduce the hazard degree of a gas explosion and conduct the venting energy to the safe area. To investigate the flame quantitative propagation law of explosion venting with a duct, the effects of hydrogen fraction and explosion venting duct length on jet flame propagation characteristics of premixed H₂-air mixtures were analyzed through experiment and simulation. The experiment results under initial conditions of room temperature and 1 atm show that when hydrogen fraction was high enough, part of the unburned hydrogen was mixed with air again to reach an ignitable concentration, resulting in the secondary combustion was easier produced and the duration of the secondary flame increased. With the increase of venting duct length, the flame front distance and propagation velocity increased. Meanwhile, the spatial distribution of pressure field and temperature field, and the propagation process and mechanism of the flame venting with a duct were analyzed using FLUENT software. The variation of the pressure wave and the pressure reflection oscillation law in the explosion venting duct was captured. Therefore, in the industrial explosion venting design with a duct, the hazard caused by the coupling of venting pressure and venting flame under different fractions should be considered comprehensively.     

Flow state monitoring of gas-water two-phase flow using multi-Gaussian mixture model based on canonical variate analysis

As a highly complex and time-varying process, gas-water two-phase flow is commonly encountered in industries. It has a variety of typical flow states and transition flow states. Accurate identification and monitoring of flow states is not only beneficial to further study of two-phase flow but also helpful for stable operation and economic efficiency of process industry. Combining canonical variate analysis (CVA) and Gaussian mixture model (GMM), a strategy called multi-CVA-GMM is proposed for flow state monitoring in gas-water two-phase flow. CVA is used to extract flow state features from the perspective of correlation between historical data and future data, which solves the cross correlation and temporal correlation of multi-sensor measurement data. GMM calculates the possibility that the current flow state belongs to each typical flow pattern and judges the current flow state by probability indicators. It is conducive to follow-up use of Bayesian inference probability and Mahalanobis distance-based (BID) indicator for flow state monitoring, which avoids repeated traversal of multiple CVA-GMM models and improves the efficiency of the monitoring process. The probability indicators can also be used to analyze transition flow states. The method combining the probabilistic idea of GMM with the deterministic idea of multimodal modeling can accurately identify the current flow state and effectively monitor the evolution of flow state. The multi-CVA-GMM method is validated by using the measured data of the horizontal flow loop of gas-water two-phase flow experimental facility, and its effectiveness is proved.     

On the capacity of the state‐dependent interference relay channel

This paper considers the state‐dependent interference relay channel (SIRC) in which one of the two users may operate as a secondary user and the relay has a noncausal access to the signals from both users. For discrete memoryless SIRC, we first establish the achievable rate region by carefully merging Han‐Kobayashi rate splitting encoding technique, superposition encoding, and Gelfand‐Pinsker encoding technique. Then, based on the achievable rate region that we derive, the capacity of the SIRC is established in many different scenarios including (a) the weak interference regime, (b) the strong interference regime, and (c) the very strong interference regime. This means that our capacity results contain all available known results in the literature. Next, the achievable rate region and the associated capacity results are also evaluated in the case of additive Gaussian noise. Additionally, many numerical examples are investigated to show the value of our theoretical derivations.     

Controlled Secure Direct Communication Protocol via the Three-Qubit Partially Entangled Set of States

In this paper, we first re-examine the previous protocol of controlled quantum secure direct communication of Zhang et al.’s scheme, which was found insecure under two kinds of attacks, fake entangled particles attack and disentanglement attack. Then, by changing the party of the preparation of cluster states and using unitary operations, we present an improved protocol which can avoid these two kinds of attacks. Moreover, the protocol is proposed using the three-qubit partially entangled set of states. It is more efficient by only using three particles rather than four or even more to transmit one bit secret information. Given our using state is much easier to prepare for multiqubit states and our protocol needs less measurement resource, it makes this protocol more convenient from an applied point of view.     

High-rate capability of carbon-coated micron-sized hexagonal TT-Nb2O5 composites for lithium-ion battery

With excellent specific capacity, superior cycle stability, safety and strong practical, Nb₂O₅ has been considered as one of the prospective anode materials for lithium-ion batteries (LIBs). However, current study suggests that Nb₂O₅ electrode materials for LIBs still face the vital issues of low electrical conductivity and poor rate performance. Therefore, carbon-coated TT-Nb₂O₅ materials are designed and synthesized through solid state method in this work, which present high specific capacity (228 mA h g^?1 at 0.2C), satisfactory rate properties (107 mA h g^?1 at 20 C). The outstanding electrochemical property can not only give the credit to the pseudocapacitance effect of TT-Nb₂O₅, but also attribute to introduction of carbon. The homogeneous carbon-coated materials enhance the electrical conductivity, increase the electron transmission speed and alleviate particle crushing. This research not only offers a new method for preparing excellent electrode materials, but also provides a kind of excellent anode material with prospective application for LIBs.