Periodic event-based sliding mode tracking control of Euler-Lagrange systems with dynamic triggering.

In this article, we propose the design of a robust tracking controller of perturbed Euler-Lagrange systems (ELSs) based on dynamic event-triggered (DET) sliding mode control (SMC) with periodic evaluation of triggering rule. To ensure robustness, we employ the SMC technique and introduce a dynamic periodic event-triggering strategy to reduce communication frequency significantly. This strategy involves the incorporation of an auxiliary dynamic variable to formulate the event-triggering condition, leading to the generation of sparser triggering instants. An upper bound of the sampling period is also obtained in this design to facilitate the periodic assessment of the event-triggered strategy, alleviating the need for continuous verification of the event condition. This technique is more economical with respect to communication resources and practical than its continuous counterpart due to the relaxation of continuous measurements. The stability of the closed loop system is established using Lyapunov analysis within the dynamically triggered event-based SMC framework. The necessary switching gain for maintaining the stable motion of the sliding variable is derived with the help of Lyapunov analysis. The tracking error is shown to be ultimately bounded, and Zeno-behaviour is excluded to ensure finite sampling. A comparative analysis based on simulation results is included to highlight the effectiveness of the proposed scheme, especially in reducing the network usage in the transient phase of the response while achieving comparable steady-state behaviour. Ultimately, we validate the effectiveness of the proposed algorithm by simulating a two-link manipulator and experimentally implementing it with a one-link manipulator.

Nanocomposites of Fe(II)-Based Metallo-Supramolecular Polymer and a Layered Inorganic-Organic Hybrid for Improved Electrochromic Materials.

Fe-based metallo-supramolecular polymer (polyFe), composed of Fe(II) ions and bis(terpyridyl)benzene, is known as a good electrochromic (EC) material. For the first time, to improve the EC properties, we prepared nanocomposites comprising polyFe and a layered inorganic-imidazoline covalently bonded hybrid (LIIm) by simply mixing them in methanol and then examined the effect of the nanocomposition on EC properties. The obtained blue/purple-colored composites (polyFe/LIIm composites) were demonstrated by scanning electron microscopy (SEM) to comprise a structure of LIIm nanoparticles coated with amorphous polyFe. Interestingly, X-ray diffraction (XRD) measurements suggested that there was no intercalation of polyFe in the interlayer space of LIIm. Ultraviolet-visible (UV-vis) spectroscopy measurements demonstrated that light absorption close to 600 nm was attributed to metal-to-ligand charge transfer (MLCT) from the Fe(II) ion to the bisterpyridine ligand and was influenced by LIIm in the composites. The composites exhibited a pair of redox waves, assigned to the redox between Fe(II) and Fe(III), in the cyclic voltammograms; moreover, the composites were estimated to be diffusion controlled. Thin composite films demonstrated reversible EC changes, triggered by the redox reaction of the metal. Furthermore, the results show that the nano-scale composition of the metallo-supramolecular polymers with LIIm can effectively improve the memory properties without reducing the contrast in transmittance (ΔT) of 70-76% in EC changes after applying 1.2 V vs. Ag/Ag+. The EC properties varied with varying ratios (3/0.1, 0.5, 1, and 5) of the polyFe/LIIm, and the ratio of 3/1 exhibited the longest memory and largest MLCT absorption peak among composites. The results show that the polyFe/LIIm composites are useful EC materials for dimming glass applications, such as smart windows.

Control allocation based fault tolerant control of descriptor system with actuator saturation.

This paper deals with the design of active fault-tolerant control (FTC) system based on control allocation (CA) technique for the uncertain descriptor system (DS) with actuator saturation. This work assumes that a fault detection unit is available to estimate the actuator fault. The proposed CA technique is responsible to redistribute the control effort to the healthy actuators taking the advantage of actuator redundancy of the DS. The so-called virtual control law is designed based on a variable gain super twisting sliding mode algorithm (VGSTSMA) to meet the admissibility criteria of continuous control input for the DS. This VGSTSMA based control strategy is designed based on the generalized regular form (GRF) of DS ensuring the robustness against the actuator faults, error in the fault estimation, and the external uncertainties. The CA scheme developed here is applicable to the DS even with a full rank input matrix which is different from the traditional design where it generally deals with the system with rank deficient input matrix. Furthermore, a static control redistribution mechanism is introduced to handle the actuator saturation which is responsible to re-allocate the excess control efforts to the available healthy actuators in the face of actuator saturation. Finally, a dual-pipe heat exchanger unit, modeled as DS, is simulated with proposed CA-based FTC such that the system can follow the time varying and constant reference trajectories in a situation of actuator faults and saturation. The simulation results are compared with the CA-based FTC where virtual control is designed based on super-twisting algorithm (STA) and with the traditional pseudo inverse-CA-based FTC to establish the superiority of the proposed scheme.

Design of event-based sliding mode controller with logarithmic quantized state measurement and delayed control update.

This paper concerns with the robust stabilization of a perturbed linear time-invariant (LTI) single-input single-output (SISO) system based on event-based/ event-triggered sliding mode control (SMC) with logarithmic quantized state measurement. This technique is expected to reduce communication traffic in control networks with the assurance of robust stability against the quantization error and external perturbations. In practice, delay is inevitable in the control computation during the implementation of the control law. The proposed event-triggering mechanism is analysed for the two scenarios: with delay and without delay in control computation. The robust stability of the uncertain system is ensured with the external disturbances, the error introduced by the quantization process and delay encountered in control computation with the proposed event-based SMC. The lower bound of minimum inter event execution time is derived to ensure the Zeno free behaviour. To show the effect of delay on the triggering mechanism, the maximum bound of the delay is obtained to guarantee the Zeno free behaviour with the robust stability of the closed loop system. An example of a mechanical system is simulated and results are shown to validate the effectiveness of the proposed methodology.

Stepwise introduction of three different transition metals in metallo-supramolecular polymer for quad-color electrochromism.

Metallo-supramolecular polymers (MSPs) show unique electrochemical and optical properties, that are different to organic polymers, caused by electronic interactions between metals and ligands. For the development of quad-color electrochromic materials, here we report the stepwise introduction of three different transition metal ions into an MSP, utilizing the different complexation abilities of the transition metals. An MSP with Os(II), Ru(II), and Fe(II) (polyOsRuFe) was synthesized via a stepwise synthetic route through the formation of an Os(II) complex first, followed by the introduction of Ru(II) to the Os(II) complex, and finally the attachment of Fe(II) to the Os(II)-Ru(II) complex to produce the polymer. This synthetic procedure was extended to fabricate MSPs that comprised Co(II)/Ru(II)/Os(II) and Zn(II)/Ru(II)/Os(II). The synthesized MSPs showed a broad optical and electrochemical window due to the coupling of three heterometallic segments into the polymer. Introducing acetate anion as the counter anion greatly enhanced the solubility of polyOsRuFe in methanol. A thin film of polyOsRuFe was prepared on ITO/glass by spin-coating the methanol solution, and its reversible quad-color electrochromism was demonstrated.

Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II).

A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2':6',2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI-TOF mass spectrometry, UV-Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311-577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications.

Ni(II)-Based Metallosupramolecular Polymer with Carboxylic Acid Groups: A Stable Platform for Smooth Imidazole Loading and the Anhydrous Proton Channel Formation.

The Ni(II)-based metallosupramolecular polymer with carboxylic acid groups (polyNi) was synthesized via a 1:1 complexation of Ni(II) salt with (4,4'-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis(pyridine-2,6-dicarboxylic acid) for the first time. The divalent state of Ni(II) in the polymer was confirmed by the X-ray absorption fine structure analysis. Smooth loading of imidazole molecules into polyNi proceeded with the help of the carboxylic acid groups to form the imidazole-loaded polyNi (polyNi-Im). Thermogravimetric analysis of polyNi-Im revealed that approximately three imidazole molecules were incorporated per repeating unit of polyNi. The Fourier transform infrared spectrum of polyNi-Im showed a new peak at 3219 cm-1, which shows an ∼73 cm-1 enhancement to -N-H of pristine imidazole. The peak suggests the formation of an imidazolium cation in the polymer. Powder X-ray diffraction indicated no degradation of the polymer structure during the imidazole loading because the diffraction pattern of polyNi-Im was almost the same as that of polyNi except for the presence of peaks corresponding to the imidazole molecules. Interestingly, the scanning electron microscopy measurement showed a large morphological change to uniform spherical particles by loading imidazole to the polymer. PolyNi-Im exhibited good proton conductivity (1.05 × 10-2 mS/cm) at a high temperature (120 °C), which is around 7 orders of magnitude higher than that of pristine polyNi because of the proton conduction pathway formation along the polymer chains by the incorporated imidazole molecules.

Dual-Branched Dense Hexagonal Fe(II)-Based Coordination Nanosheets with Red-to-Colorless Electrochromism and Durable Device Fabrication.

Highly dense hexagonal Fe(II)-based coordination nanosheets (CONASHs) were designed by dual-branching, at the metal-coordination moieties and the tritopic ligands, which successfully obtained a liquid/liquid interface by the complexation of Fe(II) ions and the tritopic bidentate ligands. The 1:1 complexation was confirmed by titration. The obtained Fe(II)-based nanosheets were fully characterized by small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). A monolayer of the sheets was obtained, employing the Langmuir-Blodgett (LB) method, and the determined thickness was ∼2.5 nm. The polymer nanosheets exhibited red-to-colorless electrochromism because the electrochemical redox transformation between Fe(II) and Fe (III) ions controlled the appearance/disappearance of the metal (ion)-to-ligand charge-transfer (MLCT) absorption. The poor π-conjugation in the tritopic ligands contributed to the highly colorless electrochromic state. A solid-state device, with the robust polymer film, exhibited excellent electrochromic (EC) properties, with high optical contrast (ΔT > 65%) and high durability after repeated color changes for >15 000 cycles, upon applying low-operating voltages (+1.5/0 V).

Constructing Alternated Heterobimetallic [Fe(II)/Os(II)] Supramolecular Polymers with Diverse Solubility for Facile Fabrication of Voltage-Tunable Multicolor Electrochromic Devices.

Metallo-supramolecular polymer (MSP)-based electrochromic devices (ECDs) have drawn much attention because of their variable colors and attractive electrochromic (EC) properties. However, fabrication of voltage-tunable multicolor ECDs using single MSP is yet hard to realize. We anticipated alternate introduction of two different redox-active metal ions in an MSP combined with the adjustment of counteranions could be a solution to fabricate multicolor ECDs. The heterometals will induce color variability upon voltage alteration, and counteranions will help to tune the solubility of MSP in different solvents. In an attempt to fulfill this target, we have synthesized four heterobimetallic supramolecular polymers (HBPs) having different counteranions (BF4-, Cl-, PF6-, and OAc-), in which Fe(II) and Os(II) are alternately complexed by two terpyridine units. To apply as EC material, the HBPs should be soluble in methanol and insoluble in acetonitrile for the preparation of EC film as well as ECDs. However, among the HBPs, only HBP-OAc is found to meet this requirement. The EC behaviors of the spray-coating film of HBP-OAc on an indium tin oxide (ITO)-coated glass substrate are investigated in terms of maximum transmittance contrast, coloration voltage, response time, coloration efficiency, and operational stability, which exhibits reversible multicolor electrochromism (the initial purple color of the film is changed to violet followed by greenish-yellow) upon alteration of the voltage from 0.0 to 0.7 V [required to oxidize the Os(II) ion] and to 1.0 V [required to oxidize the Fe(II) ion]. The film is also integrated into a laminated ECD by using lithium-based gel electrolyte. Finally, as a proof-of-concept, a prototype voltage-tunable multicolor EC display (6 cm × 2.5 cm) is fabricated by using a designed image containing a flower, leaves, and a flower pot, which exhibits six different types of multicolor image upon application of tunable voltages.

Electrochromic Os-based metallo-supramolecular polymers: electronic state tracking by in situ XAFS, IR, and impedance spectroscopies.

In this study, the electronic states of Os-based metallo-supramolecular polymers (poly(OsL)2+) during electrochromism were tracked by in situ X-ray absorption fine structure (XAFS), infrared (IR), and impedance spectroscopies. The XAFS spectra suggested electronic charge migration in the polymer, and the in situ spectra revealed reversible changes caused by electrochemical redox reactions. The IR spectra of the polymers showed an IVCT band, and we also confirmed the reversible changes by applying a voltage to the redox cell. During the impedance measurements, we found a drastic decrease in the charge transfer resistance (R CT) of the polymer films near the electrochemical redox potential.

Robust control of HIV infection by antiretroviral therapy: a super-twisting sliding mode control approach.

Acquired immune deficiency syndrome is an epidemic infectious disease which is caused by the human immunodeficiency virus (HIV) and that has proliferated across worldwide. It has been a matter of concern for the scientific community to develop an antiretroviral therapy, which will prompt a rapid decline in viral abundance. With this motivation, this study proposes the design of a robust super twisting sliding mode controller based on output information for an uncertain HIV infection model. The control objective is to decrease the concentration of infected CD4+ T cells to a specified level by drug administration using only the output information of the uncertain HIV infection model which is total CD4+ T cell concentration. The robust output-feedback controller has been developed in combination with a robust exact differentiator, functioning as an observer. The reported analysis demonstrates that the approach proposed here is capable of ensuring robust performance under several operating conditions, measurement and modelling error, parametric uncertainties and external disturbances and the simulation results prove the proficiency of the controller proposed.

Construction of Coordination Nanosheets Based on Tris(2,2'-bipyridine)-Iron (Fe2+) Complexes as Potential Electrochromic Materials.

The coordination nanosheets (CONASHs) are emerging as a new class of functional two-dimensional materials, which are one of the most active research areas of chemistry and physics in this decade. Despite the success of various structural and functional CONASHs, the development of a new molecular structure to discover alluring functional CONASHs remains challenging. Herein, we report successful preparation of two novel CONASHs (NBP1 and NBP2) through coordination between one of the unexplored molecular frameworks of bis(2,2'-bipyridine)-based ligands (BP1 and BP2) and Fe2+ ions. Using a liquid-liquid interface as a platform, large-scale thin films of multilayer CONASHs have been prepared without any support, which can be deposited onto any desired substrate. Detailed characterization of the CONASHs using various microscopic and spectroscopic techniques reveals homogeneous and flat morphology of nanometer thickness with the quantitative formation of tris(2,2'-bipyridine)-Fe2+ complex motifs in the nanosheet frameworks. The color of the films has been tuned from blue to magenta by the suitable molecular design of the ligands. Owing to the insolubility of the CONASH films in any solvent and the presence of redox-active Fe2+, we explore the functionality of these nanostructured thin films deposited on indium tin oxide as electrochromic materials. The CONASHs exhibit color-to-colorless and color-to-color electrochromic transitions with attractive response times, switching stabilities, and coloration efficiencies. Finally, we demonstrate solid-state electrochromic devices of the CONASHs operated at a potential range of +2.5 to -2.5 V, which are electrochemically stable for several switching cycles, suggesting that these CONASHs are potential electrochromic materials for next-generation display applications.

Electrochromic Os(II)-Based Metallo-Supramolecular Polymers.

This work presents the preparation of a series of novel Os(II)-based metallo-supramolecular polymers (polyOss: linear polyOsL1100% and hyperbranched polyOsL1x% L2y% ) that show a broad absorption spanning 312 to 677 nm and a low Os(II)/(III) redox potential of 0.94 V. The electrochromic properties of a polyOs film cast on an ITO substrate is investigated. The change in transmittance (ΔT) of polyOsL1100% is 49.9%, and the switching times for coloration (t c ) and bleaching (t b ) are 0.70 and 0.82 s, respectively. The introduction of a 10% branching structure (polyOsL190% L210% ) further enhanced the electrochromic performance with ΔT = 59.4%, t c  = 0.41 s, and t b  = 0.54 s. The coloration efficiency (η) increased from 396.1 to 467.5 cm2  C-1 upon branching. A solid-state electrochromic device with polyOsL1100% is successfully fabricated to use the polymer for potential applications.

Charge-Transfer-Induced Fluorescence Quenching of Anthracene Derivatives and Selective Detection of Picric Acid.

2,6-Divinylpyridine-appended anthracene derivatives flanked by two alkyl chains at the 9,10-position of the core have been designed, synthesized, and characterized by NMR, MALDI-TOF, FTIR, and single-crystal XRD. These anthracene derivatives are able to recognize picric acid (2,4,6-trinitrophenol, PA) selectively down to parts per billion (ppb) level in aqueous as well as nonaqueous medium. Fluorescence emission of these derivatives in solution is significantly quenched by adding trace amounts of PA, even in the presence of other competing analogues, such as 2,4-dinitrophenol (2,4-DNP), 4-nitrophenol (NP), nitrobenzene (NB), benzoic acid (BA), and phenol (PH). The high sensitivity of these derivatives toward PA is considered as a combined effect of the proton-induced intramolecular charge transfer (ICT) as well as electron transfer from the electron-rich anthracene to the electron-deficient PA. Moreover, visual detection of PA has been successfully demonstrated in the solid state by using different substrates.

Vice versa donor acceptor fluorene-ferrocene alternate copolymer: a twisted ribbon for electrical switching.

Two donor-acceptor type copolymers (PFFC-1 and PFFC-2) containing ferrocene and fluorene moieties have been successfully synthesized to evaluate the redox triggered optical and electronic properties. Interestingly, PFFC-1 shows a twisted ribbon-like morphology at the liquid interface and switches to a micellar structure on oxidation.

Amphiphilic and Thermoresponsive Conjugated Block Copolymer with Its Solvent Dependent Optical and Photoluminescence Properties: Toward Sensing Applications.

Herein, we present a new class of amphiphilic, thermoresponsive rod-coil conjugated block copolymer having regioregular poly(3-hexyl thiophene) and poly(N-isopropylacrylamide). Optical and luminescence properties of theses polymers significantly depend on the self-assembled nanostructures formed in different solvent and are easily tailored by chnaging the solvent composition or external stimuli like heat. Unique optical and electronic properties of this block copolymer are believed to make it promising for applications like sensor, fluorescence thermometer, optoelectronic, and bioelectronics devices.

Fluorene-based chemodosimeter for "turn-on" sensing of cyanide by hampering ESIPT and live cell imaging.

A new salicylaldehyde appended fluorene-based chemodosimeter (FSal) has been designed by taking consideration of the special nucleophilicity of cyanide ion. FSal shows selective affinity towards CN- over other anions (namely F-, Br-, NO3 -, ClO4 -, N3 -, H2PO4 -, AcO-, I-, Cl-, and NO2 -) through turn-on fluorescence with a minimum detection limit of 0.06 ppm. The turn-on fluorescence of the FSal-CN complex resulting from hampering ESIPT is also supported by DFT and TDDFT calculations. Biological compatibility and live cell imaging of this unique probe have also been explored.