Search Results (45)

Photochromic molecules, capable of reversible isomerization under specific light irradiation, are pivotal for developing advanced photo-responsive materials. Azobenzene derivatives, in particular, are renowned for their significant conformational change, excellent reversibility, and high photostability. This study presents a novel cyclic diazo compound (CDTA) comprising two azobenzene units connected via flexible glycol chains. The photo-responsive behavior of CDTA doped into the liquid crystal 4-cyano-4′-octylbiphenyl (8CB) was systematically investigated. The composite exhibits a pronounced photo-induced phase transition from a liquid crystalline to an isotropic state under 365 nm UV irradiation, accompanied by a reversible change in light transmittance. The response kinetics were found to be highly dependent on temperature and dopant concentration. At 35 °C, the UV response time was accelerated to 6.8 s, attributed to the transition of the host 8CB from a smectic to a nematic phase. Furthermore, the composite demonstrated dual responsiveness: optical switching under UV light and electrical switching under an applied field in its nematic state. This work elucidates the interaction between molecular structure and photo-response in a liquid crystalline matrix, offering insights for designing next-generation smart windows and adaptive optical devices. Full article

The emergence of advanced low-dimensional materials of the graphene family opens up unique opportunities for energy-efficient and fast processing of electrical and optical signals in a wide spectral range from ultraviolet to infrared. Non-volatile resistive states in memristors based on two-dimensional (2D) crystals, 1D nanoribbons, and 0D quantum dots are accessible for control by light and an electric field due to polarization and rearrangement of sp²-sp³ hybridization of carbon atoms, as well as due to photoinduced phase transitions. Two-dimensional materials possess unique structural and electronic properties required for the development of highly efficient nanoenergy memristor devices for low-energy information technology. This article discusses memristors and photomemristors based on graphene, graphene oxide, diamane, and chalcogenide semiconductors such as MoS₂, WSe₂, MoS_2−xO_x, which are structurally similar to graphene and have a 2D layered structure. Memristors based on graphene and graphene oxide, bigraphene, and diamane, fabricated using localized electron irradiation, exhibit nonlinear behavior and well-controlled memristive states associated with sp²-sp³ transitions of carbon atoms under low-power conditions. The review highlights the dual role of graphene as an active material and electrode, as well as the redox control mechanism. Due to a well-controlled redox process, graphene-based devices exhibit the dynamic behavior required for neuromorphic computing directly in the sensor, reducing the energy and time costs associated with data processing. Neuromorphic computing in a photomemristor-based sensor enables the creation of a compact nano-energy system for real-time information recognition in a wide spectral range, similar to biological vision, for use in self-driving cars, personalized medicine, and other applications. Full article

The stimulated assembly/disassembly of particles is a technique allowing for precise spatial and temporal control over the resulting structures to be realized. The application of a photosensitive liquid crystal (LC) allows the use of a photo-initiated order–disorder transition for the ordering and redistribution of dispersed nanoparticles. The semiconductor quantum dots (QDs) among them are useful for the imaging of such redistribution through simple luminescent microscopy with excitation by laser radiation at a wavelength of 532 nm. Doping the LC matrix with azo-chromophore molecules allowed us to localize the light-driven phase transition of the LC from the organized to the isotropic phase inside the spot, illuminated by ultraviolet (UV) light through a slit. The phase transition leads to a redistribution of the QDs within the matrix, followed by QD-rich region formation. After the termination of UV illumination, the QDs were found to form droplets in the region where UV illumination resulted in a homogeneous distribution of the QDs. The translation of the sample through the UV-illuminated spot resulted in QD accumulation inside the isotropic phase at the borders of the isotropic phase. The results obtained provide a good agreement with the model calculations of nanoparticle diffusion at the LC phase–isotropic liquid interface. Full article

Photo-induced bond linkage isomerization (BLI) in metal–nitrosyl compounds provides a molecular mechanism for controlling light-induced changes in refractive index and phase modulation. In this study, the ground and metastable states of a series of Ru–NO complexes and their Au₂₀, Ag₂₀, and mixed Au₁₀Ag₁₀ nanocluster hybrids were investigated by DFT and TDDFT calculations. The photochemical rearrangement between the linear, side-on, and O-bound forms of Ru–NO was examined together with their electronic transitions, oscillator strengths, and characteristic vibrational shifts. From these data, parameters describing radiative efficiency, non-radiative coupling, and metastable-state stability were derived to identify compounds with favorable properties for holography and photonic applications. Particular attention was given to the [(Salen)Ru(NO)(HS)@Au₂₀] complex, which shows a strong red-to-NIR response and balanced stability among its linkage isomers. Frequency-dependent polarizabilities α(ω) were calculated for its ground and metastable states and compared with those of the classical holographic material [Fe(CN)₅NO]²⁻ (nitroprusside). The refractive-index changes derived from α(ω) reveal that the Au₂₀–salen hybrid produces a much larger and more strongly wavelength-dependent Δn(λ) than nitroprusside. At 635 nm, the modulation reaches approximately 0.06 for the hybrid, compared with 0.02 for nitroprusside. This enhancement reflects the cooperative effect of the Ru–NO chromophore and the Au₂₀ nanocluster, which amplifies both polarizability and optical dispersion. The results demonstrate that coupling molecular photo-linkage isomerism with nanoplasmonic environments can significantly improve the performance of molecular systems for holography and optical-phase applications. Full article

Vanillin photoinduced deprotonation was evaluated and analyzed. Vibronic states and transitions were computationally investigated. Optimizations and vertical electron transitions in the gas phase and with the continuum solvation model were computed using the time-dependent density functional theory. Static absorption and emission (photostatic optical) spectra were statistically averaged over the excited instantaneous molecular conformers fluctuating on quantum–classical molecular dynamic trajectories. Photostatic optical spectra were generated using the hybrid quantum–classical molecular dynamics for explicit solvent models. Conical intersection searching and nonadiabatic molecular dynamics simulations defined potential energy surface propagations, intersections, dissipations, and dissociations. The procedure included mixed-reference spin–flip excitations for both procedures and trajectory surface hopping for photodynamics. Insignificant structural deformations vs. hydroxyl bond cleavage followed by deprotonation were demonstrated starting from different initial structural conditions, which included optimized, transition state, and several other important fluctuating configurations in various environments. Vanillin electronic structure changes were illustrated and analyzed at the key points on conical intersection and nonadiabatic molecular dynamics trajectories by investigating molecular orbital symmetry and electron density difference. The hydroxyl group decomposed on transition to a σ-molecular orbital localized on the elongated O–H bond. Full article

New bulk chalcogenides from the system (GeTe₆)_1−xCu_x, where x = 5, 10, 15 and 20 mol%, have been synthesized. The structure and composition of the materials were studied using X-ray powder diffraction (XRD) and energy-dispersive spectroscopy (EDS). Scanning electron microscopy (SEM) was applied to analyze the surface morphology of the samples. Some thermal characteristics such as the glass transition, crystallization and melting temperature and some physico-chemical properties such as the density, compactness and molar and free volumes were also determined. The XRD patterns show sharp diffraction peaks, indicating that the synthesized new bulk materials are crystalline. The following four crystal phases were determined: Te, Cu, CuTe and Cu₂GeTe₃. The results from the EDS confirmed the presence of Ge, Te and Cu in the bulk samples in concentrations in good correspondence with those theoretically determined. A layered thin-film material based on Ge₁₄Te₈₁Cu₅, which exhibits lower network compactness compared to the other synthesized new chalcogenides, and the azo polymer PAZO was fabricated, and the kinetics of the photoinduced birefringence at 444 nm was measured. The results indicated an increase in the maximal induced birefringence for the layered structure in comparison to the non-doped azo polymer film. Full article

This paper focuses on the switching and modulation techniques of terahertz waves, develops ${\mathrm{VO}}_2$ thin-film materials with an SPP structure, and uses terahertz time-domain spectroscopy (THz-TDS) to study the semiconductor–metal phase transition characteristics of ${\mathrm{VO}}_2$ thin films, especially the photoinduced semiconductor–metal phase transition characteristics of silicon-based ${\mathrm{VO}}_2$ thin films. The optical modulation characteristics of silicon-based ${\mathrm{VO}}_2$ thin films to terahertz waves under different light excitation modes, such as continuous light irradiation at different wavelengths and femtosecond pulsed laser irradiation, were analyzed. Combining the optical modulation characteristics of silicon-based ${\mathrm{VO}}_2$ thin films with the filtering characteristics of SPP structures, composite structures of ${\mathrm{VO}}_2$ thin films with metal hole arrays, composite structures of ${\mathrm{VO}}_2$ thin films with metal block arrays, and silicon-based ${\mathrm{VO}}_2$ microstructure arrays were designed. The characteristics of this dual-function device were tested experimentally. The experiment proves that the ${\mathrm{VO}}_2$ film material with an SPP structure has a transmission rate dropping sharply from 32% to 1% under light excitation; the resistivity changes by more than six orders of magnitude, and the modulation effect is remarkable. By applying the SPP structure to the ${\mathrm{VO}}_2$ material, the material can simultaneously possess modulation and filtering functions, enhancing its optical performance in the terahertz band. Full article

The development of photoactive molecules for photothermal energy storage is a focus of research in solar energy utilization technology. Azobenzene photoswitch has emerged as a promising candidate for solar energy conversion and storage due to its unique photoisomerization characteristics. Nonetheless, a majority of azobenzene-based molecular photothermal systems have a significant drawback: they depend on ultraviolet light for E-to-Z isomerization to store photon energy rather than visible light, which seriously hinders the development of azobenzene photoswitch in practical solar energy utilization applications. In this study, an azobenzene photothermal molecule that can effectively store visible-light photon energy was design and synthesized, which includes a tetra-ortho-chlorinated azo structure as the “head” part and an alkyl chain at para-position as the “tail” part. The ultraviolet–visible and ¹H NMR spectrum indicated that the obtained tetra-ortho-chlorinated azobenzene photothermal molecule could effectively absorb and store photon energy under 550 nm irradiation and release the stored energy upon 430 nm light irradiation. The storage energy density of the charged azobenzene photothermal molecule was determined to be 13.50 kJ/mol through differential scanning calorimetry and 28.21 kJ/mol via density functional theory theoretical calculations. This discrepancy was ascribed to the 64% Z-isomer yield harvesting during the charging process. Furthermore, the obtained tetra-ortho-chlorinated azobenzene exhibited long-term energy storage (approximately 11 days of half-life) and cyclic stability (100 cycles). Notably, the E-isomer of tetra-ortho-chlorinated azobenzene exhibited a high degree of supercooling, which may be advantageous for use in extremely low-temperature environments. Full article

The transition between the inflammatory phase and the proliferative phase is critical for wound healing. However, the development of proper switchers that can regulate this transition is facing great challenges. Macrophages play versatile roles in all wound healing phases because they can readily switch from pro-inflammatory M1 phenotypes to anti-inflammatory M2 phenotypes in response to different microenvironment stimuli. Herein, taking advantage of enhanced electron transfer by coupling MoS₂ with a highly conductive activated carbon fiber (ACF) network, a MoS₂-ACF heterojunction structure was constructed as a macrophage M1-M2 phenotype switcher (MAPS) for regulating inflammation–proliferation transition to accelerate wound healing. In the early stages of wound repair, MAPS-mediated photothermal effects with near-infrared laser irradiation could promote macrophage reprogramming to the M1 phenotype, which can expedite inflammation. NIR photo-induced hyperthermia, together with M1 macrophages, directly and indirectly kills bacteria. Later, during the healing process, the MAPS could further reprogram macrophages towards the M2 phenotype via its inherent reactive oxygen species (ROS) scavenging ability to resolve inflammation, promoting cell proliferation. Therefore, MoS₂-ACF heterojunction structures provide a new strategy to modulate inflammation–proliferation transition by rebalancing the immuno-environmental equilibrium of macrophage M1/M2 phenotypes. Full article

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have recently become attractive candidate substrates for surface-enhanced Raman spectroscopy (SERS) owing to their atomically flat surfaces and adjustable electronic properties. Herein, large-scale 2D 1T′- and 2H-MoTe₂ films were prepared using a chemical vapor deposition method. We found that phase structure plays an important role in the enhancement of the SERS performances of MoTe₂ films. 1T′-MoTe₂ films showed a strong SERS effect with a detection limit of 1 × 10⁻⁹ M for the R6G molecule, which is one order of magnitude lower than that of 2H-MoTe₂ films. We demonstrated that the SERS sensitivity of MoTe₂ films is derived from the efficient photoinduced charge transfer process between MoTe₂ and adsorbed molecules. Moreover, a prohibited fish drug could be detected by using 1T′-MoTe₂ films as SERS substrates. Our study paves the way to the development and application of high-performance SERS substrates based on TMD phase engineering. Full article

Harnessing the photoinduced phase transitions in organic crystals, especially the changes in shape and structure across various dimensions, offers a fascinating avenue for exact spatiotemporal control, which is crucial for developing future smart devices. In our study, we report a new photoactive molecular crystal made from (E)-2-(3-phenyl-allylidene)malonate ((E)-PADM). When exposed to ultraviolet (UV) light at 365 nm, this compound experiences an E-to-Z photoisomerization in liquid solution and a crystal-to-liquid phase transition in solid crystals. Remarkably, nanoscopic crystalline rods boost their melting rate and degree compared to bulk crystals, indicating that miniaturization enhances the photoinduced melting effect. Our results demonstrate a simple approach to rapidly drive molecular crystals into liquids via photochemical reactions and phase transitions. Full article

Photoisomerizable molecules in liquid crystals (LCs) allow for photoinduced phase transitions, facilitating applications in a wide variety of photoresponsive materials. In contrast to the widely investigated azobenzene structure, research on the photoinduced phase-transition behavior of imine-based LCs is considerably limited. We herein report the thermal and photoinduced phase-transition behaviors of photoisomerizable imine-based LC dimers with twist–bend nematic (N_TB) phases. We synthesize two homologous series of ester- and thioether-linked N-(4-cyanobenzylidene)aniline-based bent-shaped LC dimers with an even number of carbon atoms (n = 2, 4, 6, 8, and 10) in the central alkylene spacers, namely, CBCOOnSBA(CN) and CBOCOnSBA(CN), possessing oppositely directed ester linkages, C=OO and OC=O, respectively. Their thermal phase-transition behavior is examined using polarizing optical microscopy and differential scanning calorimetry. All dimers form a monotropic N_TB phase below the temperature of the conventional nematic (N) phase upon cooling. Remarkably, the N_TB phases of CBCOOnSBA(CN) (n = 2, 4, 6, and 8) and CBOCOnSBA(CN) (n = 6 and 8) supercool to room temperature and vitrify without crystallization. In addition, the phase-transition temperatures and entropy changes of CBCOOnSBA(CN) are lower than those of CBOCOnSBA(CN) at the same n. Under UV light irradiation, the N_TB and N phases transition to the N and isotropic phases, respectively, and reversibly return to their initial LC phases when the UV light is turned off. Full article

The synchronization of laser and X-ray sources is essential for time-resolved measurements in the study of ultrafast processes, including photo-induced piezo-effects, shock wave generation, and phase transitions. On the one hand, optical diagnostics (by synchronization of two laser sources) provides information about changes in vibration frequencies, shock wave dynamics, and linear and nonlinear refractive index behavior. On the other hand, optical pump–X-ray probe diagnostics provide an opportunity to directly reveal lattice dynamics. To integrate two approaches into a unified whole, one needs to create a robust method for the synchronization of two systems with different repetition rates up to the MHz range. In this paper, we propose a universal approach utilizing a field-programmable gate array (FPGA) to achieve precise synchronization between different MHz sources such as various lasers and synchrotron X-ray sources. This synchronization method offers numerous advantages, such as high flexibility, fast response, and low jitter. Experimental results demonstrate the successful synchronization of two different MHz systems with a temporal resolution of 250 ps. This enables ultrafast measurements with a sub-nanosecond resolution, facilitating the uncovering of complex dynamics in ultrafast processes. Full article

ZnTiO₃/TiO₂ composite photocatalysts were synthesized via the sol–gel technique, and the impact of varying heat treatment temperatures (470, 570, 670 °C) on their crystalline arrangement, surface morphology, elemental composition, chemical state, specific surface area, optical characteristics, and photocatalytic efficacy was systematically investigated. The outcomes revealed that, as the temperature ascends, pure TiO₂ undergoes a transition from anatase to rutile, ultimately forming a hybrid crystal structure at 670 °C. The incorporation of ZnTiO₃ engenders a reduction in the TiO₂ grain dimensions and retards the anatase-to-rutile phase transition. Consequently, the specimens manifest a composite constitution of anatase and ZnTiO₃. In contrast, for pure TiO₂, the specimen subjected to 670 °C annealing demonstrates superior photocatalytic performance due to its amalgamated crystal arrangement. The degradation efficacy of methylene blue (MB) aqueous solution attains 91% within a 60-min interval, with a calculated first-order reaction rate constant of 0.039 min⁻¹. Interestingly, the ZnTiO₃/TiO₂ composite photocatalysts exhibit diminished photocatalytic activity in comparison to pristine TiO₂ across all three temperature variations. Elucidation of the photocatalytic mechanism underscores that ZnTiO₃ coupling augments the generation of photogenerated charge carriers. Nonetheless, concurrently, it undermines the crystalline integrity of the composite, yielding an excess of amorphous constituents that impede the mobility of photoinduced carriers. This dual effect also fosters escalated recombination of photogenerated charges, culminating in diminished quantum efficiency and reduced photocatalytic performance. Full article

Fully room temperature three-dimensional (3D) shape-reprogrammable, recyclable, and photomobile azobenzene (azo) polymer actuators hold much promise in many photoactuating applications, but their development is challenging. Herein, we report on the efficient synthesis of a series of main-chain azo liquid crystalline polymers (LCPs) with such performances via Michael addition polymerization. They have both ester groups and two kinds of hydrogen bond-forming groups (i.e., amide and secondary amino groups) and different flexible spacer length in the backbones. Such poly(ester-amide-secondary amine)s (PEAsAs) show low glass transition temperatures (T_g ≤ 18.4 °C), highly ordered smectic liquid crystalline phases, and reversible photoresponsivity. Their uniaxially oriented fibers fabricated via the melt spinning method exhibit good mechanical strength and photoinduced reversible bending/unbending and large stress at room temperature, which are largely influenced by the flexible spacer length of the polymers. Importantly, all these fibers can be easily reprogrammed under strain at 25 °C into stable fiber springs capable of showing a totally different photomobile mode (i.e., unwinding/winding), mainly owing to the presence of low T_g and both dynamic hydrogen bonding and stable crystalline domains (induced by the uniaxial drawing during the fiber formation). They can also be recycled from a solution at 25 °C. This work not only presents the first azo LCPs with 3D shape reprogrammability, recyclability, and photomobility at room temperature, but also provides some important knowledge of their structure–property relationship, which is useful for designing more advanced photodeformable azo polymers. Full article