Photomechanical Research Articles

Impact of halogen⋯halogen interaction on the mechanical motion of a 3D Pb(II) coordination polymer of elusive topology.

Herein, we report the synthesis of a Pb(II) based three-dimensional coordination polymer (3D CP), [Pb(DCTP)]n (1) [H2DCTP = 2,5-dichloroterephthalic acid] with an unprecedented topology, which exhibits a photomechanical effect wherein crystals show jumping upon UV irradiation. The Pb(II) CP forms a type II Cl⋯Cl interaction, which weakens further upon UV irradiation to resolve the anisotropic mechanical strain. The work presented here could be a beacon to the nascent field of photoactuating smart materials.

Easy Processable Photomechanical Thin Film Involving a Photochromic Diarylethene and a Thermoplastic Elastomer in Supramolecular Interaction.

A novel supramolecular photoactuator in the form of a thin film of centimetric size has been developed as an alternative to traditional liquid crystal elastomers (LCE) involving azobenzene (AZO) units or photochromic microcrystals. This thin film is produced through spin coating without the need for alignment or crosslinking. The photoactuator combines a photochromic dithienylethene (DTE) functionalized with ureidopyrimidinone (UPy) units, and a telechelic thermoplastic elastomer, also functionalized with UPy, allowing quadruple hydrogen bonding between the two components. Upon alternating ultraviolet (UV) and visible light exposure, the film exhibits reversible bending and color changes, studied using displacement and absorption tracking setups. For the first time, the photomechanical effect (PME) is quantitatively correlated with photochromism, showing that DTE units drive the movement under both UV (photocyclization) and visible (photoreversion) light. In situ illumination techniques reveal that the PME arises from photoinduced strain within 160 nm UPy-bonded DTE domains, which expand and contract by approximately 50% under UV and visible light, respectively. The semicrystalline nature of the elastomer and a robust supramolecular network connecting both components are critical in converting microscopic photostrain into macroscopic actuation.

Contrast-enhanced excimer laser stepwise approach during PCI for resistant coronary lesions.

The treatment of resistant coronary lesions (RCL) is a great challenge for interventional cardiologists. The excimer laser coronary atherectomy (ELCA) is a plaque modification tool based on a main mechanism of photomechanical effect leading to mechanical disruption of the plaque. Contrast dye injection during laser delivery has demonstrated to enhance its power. To evaluate the effectiveness and safety of the contrast-enhanced ELCA by a stepwise approach in the treatment of RCLs. We retrospectively examined consecutive patients undergoing contrast-enhanced ELCA-assisted PCI between 2018 and 2021 at two Italian sites. RCLs were defined as novo or in-stent undilatable/uncrossable with conventional balloons (SC/NC balloon). The primary endpoint was ELCA technical success defined as the laser catheter crossing the entire length of the target lesion established by angiographic evidence of the catheter tip in the artery distal to the stenosis. We enrolled 114 patients who underwent contrast-enhanced ELCA-assisted PCI: 58% of the patients had acute coronary syndrome while the left anterior descending artery was the target vessel in 42.1% of cases. The target lesion was most commonly in-stent (56.2%). The 0.9 mm ELCA catheter tip was employed in 89.5% of cases. The most used frequency/fluency profile was 70/70 (39.5%). The use of contrast-enhanced ELCA was associated with high technical, procedural, and clinical success rates (97.4%, 93.7%, and 90.1%, respectively). The contrast-enhanced ELCA seems to be a safe and effective treatment option for the management of both de novo and in-stent-resistant coronary lesions.

Realizing enhanced lithotripsy efficiency using 700 W peak power thulium-doped fiber laser

Despite its widespread use in laser lithotripsy, the Ho:YAG solid-state laser suffers from limited parameter combinations, poor beam quality, and low photoelectric conversion efficiency. The development of 2.0 μm fiber laser technology has positioned the thulium-doped fiber laser (TFL) as a superior alternative to the Ho:YAG laser in lithotripsy. The TFL excels because of its high-water absorption coefficient, all-fiber structure and pump modulation flexibility. However, the peak power reported for TFL in lithotripsy remains at most 500 W. This study presented a quasi-continuous wave (QCW) TFL featuring a wide tunable range of pulse width and pulse repetition rates, and a peak power of 700 W to realize enhanced ablation efficiency. A high-speed camera was used to acquire the laser-induced cavitation bubble images for the analysis of the interaction mechanism of a high peak power QCW TFL pulse with water and stones. While the synergistic action of photothermal and photomechanical effects constituted the mechanism of TFL lithotripsy, the laser-induced bubble channel was a prerequisite for TFL noncontact effective lithotripsy, with bubble length and width markedly influencing stone ablation rates. Ablation experiments on uric acid and calcium oxalate monohydrate stones conducted with various parameter combinations at a peak power of 700 W yielded rates of 8.9 mg/s for uric acid stones and 7.5 mg/s for calcium oxalate monohydrate stones. A comparison with prior findings confirmed that a high peak power TFL could notably improve stone ablation rates.

A comparison of the isostructural [Co(NH3)5NO2]XNO3 and [Co(NH3)5ONO]XNO3, X = Cl- or Br- in relation to nitro-nitrito linkage isomerization and photomechanical effects.

A new photoactive cobalt coordination compound, [Co(NH3)5NO2]BrNO3 (I), was obtained. Its crystal structure was shown to be isostructural with previously known [Co(NH3)5NO2]ClNO3 (II) for which linkage isomerization accompanied with mechanical response of the crystal has been already reported. Single crystals of I are transformed into nitrito isomer [Co(NH3)5ONO]BrNO3 (III) on irradiation with blue light (λ = 465 nm) without being destroyed. The crystal structure of III was also solved using single-crystal X-ray diffraction and compared with previously known [Co(NH3)5ONO]ClNO3 (IV). A detailed comparison of the structures of I, II, III and IV, including unit-cell parameters, the distribution of free space (in particular, reaction cavities around the nitro ligand), the lengths of hydrogen bonds, coordination and Voronoi-Dirichlet polyhedra has been performed. Single-crystal X-ray diffraction data were complemented with IR spectra. The effect of the replacement of Cl- by Br- on the crystal structure and on the nitro-nitrito photoisomerization is discussed.

Performance and oxidation mechanism of VUV photo–Fenton in simultaneous removal of Ni-EDTA and hypophosphite: decomplexation, low-valent phosphorous oxidation and DFT calculation

The photo–Fenton process offers a promising alternative for the oxidation of complex heavy metals. However, the potential influence of coexisting substrates may be overlooked. The •OH radicals generated in the photo–Fenton process ensure superior oxidation ability. In this study, we used a vacuum ultraviolet (VUV) light-assisted photo–Fenton (VPF) process to explore its performance in the synergistic oxidation of Ni-ethylenediaminetetraacetic acid (EDTA) and coexisting hypophosphite, typical pollutants in electroless nickel plating (ENP) wastewater. Based on electron spin resonance (ESR) and DMSO-probing results, •OH was the predominant reactive oxygen species, and VPF possessed the highest •OH concentration compared to other photochemical processes under identical conditions (pH, Fe, H2O2). Enhanced •OH generation in VPF was attributed to various photochemical reactions, including photo–Fenton, UV/H2O2, and VUV/H2O. Consequently, VPF exhibited efficient Ni-EDTA decomplexation and hypophosphite oxidation. Notably, the evolution and rate-limiting steps during hypophosphite oxidation were demonstrated by experimental results and density functional theory calculations. Hypophosphite was initially oxidized to phosphite, which subsequently oxidized to phosphate. The oxidation of phosphite could be considered the rate-limiting step as it exhibits higher energy barriers than hypophosphite oxidation. Adequate •OH generation in the VPF process could overcome this energy barrier, indicating its potential for application in pollutant removal and resource recovery from ENP wastewater.

Photoinduced Puffing with Large Volume Expansion and Photomechanical Motions induced by Topochemical [4+4] Reactions in Molecular Crystal Solvates.

In this work, we report the first example of two crystal solvates of an anthracene-benzhydrazide based molecule (Ant) that display very distinct photo-responsive behaviour when 365 or 405 nm or visible light is illuminated. For the first time, the crystal hydrate that has water molecule in the lattice (hereafter named as Ant-H2O) display fascinating puffing behavior with large volume expansion upto 50 % accompanied with surface modulation when illuminated with 405 nm light, a phenomenon very much similar to the rice or popcorn puffing by thermal treatment. Utilizing the properties of photoconverted Ant-H2O crystals, we have demonstrated their application in photoinduced enhanced liquid absorption using various liquids/solutions. The other crystal solvate having DMF in the crystal lattice (hereafter named as Ant-DMF) responds to 405 nm light by bending, twisting, chopping, jumping or splitting etc. The chopping of Ant-DMF crystal was also observed under ambient/white light but at a slower rate compared to 405 nm light. Single crystal X-ray diffraction study reveals that the photoinduced puffing and photomechanical effects of these materials are rooted to the topochemical [4+4] cycloaddition reaction between the anthracene moieties that facilitate molecular packing change assisted by the reconfiguration of intermolecular non-covalent interactions involving lattice trapped solvent molecules.

2 + 2] cycloaddition and its photomechanical effects on 1D coordination polymers with reversible amide bonds and coordination site regulation

Photo-responsive materials can convert light energy into mechanical energy, with great application potential in biomedicine, flexible electronic devices, and bionic systems.

Photomechanical effect in “side-chain” polyimides with low content of azopyridine chromophore

Photomechanical effect in “side-chain” polyimides with low content of azopyridine chromophore

Laser ablation on vascular diseases: mechanisms and influencing factors.

Vascular diseases, such as venous insufficiency and coronary artery diseases, have been threatening the health of people. Efficient treatment with proper postoperative care is required to relieve the pain of the patients. Traditionally, venous insufficiency is treated with ligation and stripping, an open surgery whose complication rate cannot be ignored. Coronary artery disease is often treated with balloon angioplasty during which undilatable lesions may be encountered, limiting the efficacy of this approach. With advances in laser photonics and percutaneous coronary intervention procedure, laser ablation is emerging as an alternative and adjunctive therapy for these diseases. Endovenous laser ablation has the advantages of high success rate, low complication risk, and fast postoperative recovery. Laser ablation in arteries can handle uncrossable or undilatable lesions with a low incidence of serious complications. In this review, previously published research concerning vascular diseases and their therapies are analyzed in order to provide a clear explanation of the mechanisms and merits of laser ablation. For endovenous laser ablation, the main mechanisms are steam bubbles, heat conduction, and heat pipe, and three main influencing factors are wavelength, fiber types, and laser energy density. For excimer laser coronary atherectomy, the main mechanisms are photochemical, photothermal, and photomechanical effects, and three main influencing factors are catheter, medium, and laser parameters.

Mechanical Effects of Elastic Crystals Driven by Natural Sunlight and Force

AbstractFlexible crystals that can capture solar energy and convert it into mechanical energy are promising for a wide range of applications such as information storage and actuators, but obtaining them remains a challenge. Herein, an elastic crystal of a barbiturate derivative was found to be an excellent candidate, demonstrating plastic bending behavior under natural sunlight irradiation. 1H NMR and high‐resolution mass spectrum data of microcrystals before and after light irradiation demonstrated that light‐induced [2+2] cycloaddition was the driving force for the photomechanical effects. Interestingly, the crystals retained elastic bending even after light irradiation. This is the first report of flexible crystals that can be driven by natural sunlight and that have both photomechanical properties and elasticity. Furthermore, regulation of the passive light output direction of the crystals and transport of objects by applying mechanical forces and light was demonstrated.

Mechanical Effects of Elastic Crystals Driven by Natural Sunlight and Force.

Flexible crystals that can capture solar energy and convert it into mechanical energy are promising for a wide range of applications such as information storage and actuators, but obtaining them remains a challenge. Herein, an elastic crystal of a barbiturate derivative was found to be an excellent candidate, demonstrating plastic bending behavior under natural sunlight irradiation. 1 H NMR and high-resolution mass spectrum data of microcrystals before and after light irradiation demonstrated that light-induced [2+2] cycloaddition was the driving force for the photomechanical effects. Interestingly, the crystals retained elastic bending even after light irradiation. This is the first report of flexible crystals that can be driven by natural sunlight and that have both photomechanical properties and elasticity. Furthermore, regulation of the passive light output direction of the crystals and transport of objects by applying mechanical forces and light was demonstrated.

Guard Cell-Inspired Ion Channels: Harnessing the Photomechanical Effect via Supramolecular Assembly of Cross-Linked Azobenzene/Polymers.

Stimuli-responsive ion nanochannels have attracted considerable attention in various fields because of their remote controllability of ionic transportation. For photoresponsive ion nanochannels, however, achieving precise regulation of ion conductivity is still challenging, primarily due to the difficulty of programmable structural changes in confined environments. Moreover, the relationship between noncontact photo-stimulation in nanoscale and light-induced ion conductivity has not been well understood. In this work, a versatile design for fabricating guard cell-inspired photoswitchable ion channels is presented by infiltrating azobenzene-cross-linked polymer (AAZO-PDAC) into nanoporous anodic aluminum oxide (AAO) membranes. The azobenzene-cross-linked polymer is formed by azobenzene chromophore (AAZO)-cross-linked poly(diallyldimethylammonium chloride) (PDAC) with electrostatic interactions. Under UV irradiation, the trans-AAZO isomerizes to the cis-AAZO, causing the volume compression of the polymer network, whereas, in darkness, the cis-AAZO reverts to the trans-AAZO, leading to the recovery of the structure. Consequently, the resultant nanopore sizes can be manipulated by the photomechanical effect of the AAZO-PDAC polymers. By adding ionic liquids, the ion conductivity of the light-driven ion nanochannels can be controlled with good repeatability and fast responses (within seconds) in multiple cycles. The ion channels have promising potential in the applications of biomimetic materials, sensors, and biomedical sciences.

A Photomechanical Film in which Liquid Crystal Design Shifts the Absorption into the Visible Light Range.

Liquid crystalline polymer networks (LCN) with azobenzene monomers bend reversibly under UV-light irradiation, combining photomechanical and photothermal effects. However, the harmful nature of UV-light limits their use in biology and soft robotics. Although visible light-absorbing tetra-ortho-fluoro-substituted azobenzenes exist, liquid crystalline monomers have never been prepared. Previously, such azobenzenes were added as photoactive additives (up to 10%) to otherwise passive liquid crystalline polymer networks. In this work, a molecular design of a liquid crystalline, polymerizable azobenzene switchable by visible light is presented. The monomer assembles in a highly fluid nematic phase, but polymerizes in a layered smectic C phase. The films are produced solely from the monomer without additional liquid crystalline components and are actuated with visible light. Bending experiments in air and under water differentiate photomechanical and photothermal effects. Remarkably, a 60µm splay aligned film maintains its deformation for hours, slowly reverting over days. Monomer liquid crystallinity is characterized using differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), and polarized optical microscopy (POM); polymer films are analyzed using WAXS and DSC on a homogeneously aligned film. The synthetic procedure is high yielding and polymer film fabrication is scalable, which enables the use of safe and efficient photomechanical LCNs in soft robotics, engineering and biology.

Application of Picosecond Laser in Dermatology

ABSTRACT Background: Lasers are one of the most important treatment modalities in dermatology. Lasers interact with chromophores through several mechanisms that depend on fluence and pulse durations. Early lasers worked by photothermal interaction with pulse durations of 1 microsecond to 1 second. A picosecond laser is developed to confine photothermal effects and produce photomechanical effects and plasma induction. Purpose: To understand the mechanism of action and application of picosecond lasers for dermatological disorders. Review: Non-fractional picosecond lasers work by photomechanical interaction. Photomechanical interaction happens when pulse duration is less than inertial confinement time, causing fractures of chromophores with lower energy, or “cold ablation”. Fractional picosecond lasers work by laser-induced optical breakdown (LIOB). In LIOB, accelerated seed electrons cause an electron avalanche that produce a collection of free electrons called plasma, which ablates tissues. LIOB in the skin is always followed by photodisruption. In LIOB, vacuoles and debris were eliminated transdermally and dermal collagen and elastin increased. Picosecond laser may be applied in disorders requiring destruction of chromophores and for collagen and elastin disorders. It is currently the first-line treatment for tattoo removal (Nevus of Ota and Acquired Bilateral Nevus of Ota-like macules, or ABNOM). It has good efficacy and safety for solar lentigines, freckles, and cafe-au-lait macules (CALM). It is an additional treatment for moderate to severe melasma and hypertrophic scars, in combination with other treatments. The fractional picosecond laser showed moderate improvement and low risk of postinflammatory hyperpigmentation (PIH) for atrophic acne scars and produced improvement in striae alba.

BC02 Efficacy and safety of picosecond Nd-YAG laser for tattoo removal in Asian patients: a way to look forward

Abstract Picosecond neodymium-doped yttrium aluminium garnet (Nd-YAG) lasers have emerged as the leading technology for tattoo removal due to their shorter pulse lengths and are considered better than other nanosecond lasers. The aim was to study the efficacy and adverse effects of a picosecond quality-switched (QS) Nd-YAG laser in a case series of 15 Asian patients for tattoo removal. Fifteen patients with black- and blue-coloured tattoos were recruited for tattoo removal. All were treated with a 1064-picosecond QS Nd-YAG laser. A single session with one pass was performed using a spot size of 4 mm, a fluence of 0.5–1 J cm–2 and a frequency of 6–10 Hz. The parameters were adjusted based on the size and type of tattoo and the patient’s skin type. Patients were treated at 4–6-weekly intervals. The clearance of pigmentation and local reactions was evaluated based on clinical photographs and dermoscopy, done at each sitting. At the end, both patients and physician assessed the clearance of tattoo. For patient assessment, a visual analogue scale (VAS) was used. To assess the efficacy of laser treatment by the physician, the tattoo removal rate was scored on a 5-point (0–4) scale (4: ≥ 70% removal, excellent improvement; 3: ≥ 50% and < 70%, marked improvement; 2: ≥ 30% and < 50%, moderate improvement; 1: ≥ 10% and < 30%, mild improvement and 0: < 10%, no effect). Patients were asked to assess their satisfaction (0 = dissatisfactory, 10 = satisfactory) and pain (0 = no pain, 10 = worst pain) using the VAS. Clinical photographs were assessed both by the patients and the physicians. Four women and 11 men were included (aged 30–45 years). At the end of treatment, all patients had > 75% clearance and seven obtained almost complete clearance. Thus, all patients had an excellent response. The average patient-reported score for satisfaction was 8.2 and 2.5 for pain. The average score was 4.4 for the number of sessions. A few adverse effects, including erythema, blistering and crusting, were observed. Picosecond lasers allow for the most effective delivery of thermal radiation to tattoo particles through more specific photothermal and photomechanical effects than traditional nanosecond lasers. They also have an additional effect of minimizing the collateral damage to the surrounding dermis and epidermis. Thus, a picosecond laser is a safe and effective method for tattoo removal in Asian people.

Illuminating the photomechanical effect: Exploring the relationship between electron-hole excitation and deformation mechanisms in nanotwinned boron carbide

The photomechanical effect, a phenomenon in which electron-hole (e-h) excitation from light illumination influences the plastic deformation of semiconductors, remains poorly understood at the microscopic level. In this study, we employ constrained density-functional theory simulations to investigate the interaction between e-h excitation and twin boundaries in nanotwinned boron carbide (${\mathrm{B}}_{4}\mathrm{C}$) and their impact on deformation mechanisms. Our findings reveal that excited e-h pairs reduce both the critical displacement (or critical shear strain) and shear strength of nanotwinned ${\mathrm{B}}_{4}\mathrm{C}$ under shear-induced failure. This reduction stems from the redistribution of electrons and holes near the twin boundary, weakening the B--C bond connecting adjacent icosahedra and leading to cage destabilization and failure. Notably, e-h excitation alters the deformation mechanism of asymmetric twins while exacerbating that of symmetric twins. These simulation results offer a physical explanation for the observed softening effects in nanotwinned materials under e-h excitation, thereby contributing to the understanding of the photomechanical effect.

Visible Light‐fueled Mechanical Motions with Dynamic Phosphorescence Induced by Topochemical [2+2] Reactions in Organoboron Crystals

AbstractIn the quest for essential energy solutions towards an ecological friendly future, the transformation of visible light/solar energy into mechanical motions in metal‐free luminescent crystals offers a sustainable choice of smart materials for lightweight actuating, and all‐organic electronic devices. Such green energy‐triggered photodynamic motions with room temperature phosphorescence (RTP) emission in molecular crystals have not been reported yet. Here, we demonstrate three new stoichiometrically different Lewis acid‐base molecular organoboron crystals (PS1, PS2, and PS3), which exhibit rapid photosalient effects (ballistic splitting, moving, and jumping) under both ultraviolet (UV) and visible light associated with quantitative single‐crystal‐to‐single‐crystal (SCSC) [2+2] cycloaddition of preorganized olefins. Furthermore, these systems respond to sunlight and mobile (white) flashlight with a complete SCSC transformation in a relatively slow fashion. Remarkably, all PS1, PS2, and PS3 crystals display visible light‐promoted dynamic green RTP as their emission peaks promptly blue‐shift, due to instantaneous photomechanical effects. Time‐dependent structural mapping of intermediate photoproducts during fast SCSC [2+2] photoreaction, by X‐ray photodiffraction, reveals a rationale for the origin of these photodynamic motions associated with rapid topochemical transformations. The reported light‐driven behavior (mechanical motions, dynamic phosphorescence, and topochemical reactivity), is considered advantageous for the strategic design of stimuli‐responsive multi‐functional crystalline materials.

Visible Light-fueled Mechanical Motions with Dynamic Phosphorescence Induced by Topochemical [2+2] Reactions in Organoboron Crystals.

In the quest for essential energy solutions towards an ecological friendly future, the efficient transformation of visible light/solar energy into mechanical motions in metal-free luminescent crystals offers a sustainable choice of smart materials for lightweight actuating, sensing, and all-organic electronic devices. Such green energy-triggered photodynamic motions with room temperature phosphorescence (RTP) emission in molecular crystals have not been reported yet. Here, we demonstrate three new stoichiometrically different Lewis acid-base molecular organoboron crystals (PS1, PS2, and PS3), which exhibit rapid photosalient effects (ballistic splitting, moving, and jumping) under both UV and visible light associated with quantitative single-crystal-to-single-crystal (SCSC) [2+2] cycloaddition of preorganized olefins. Furthermore, these systems respond to sunlight and mobile (white) flashlight with a complete SCSC transformation in a relatively slow fashion. Remarkably, all PS1, PS2, and PS3 crystals display visible light-promoted dynamic green RTP as their emission peaks promptly blue-shift, due to instantaneous photomechanical effects. Time-dependent structural mapping of intermediate photoproducts during fast SCSC [2+2] photoreaction, by X-ray photodiffraction, reveals a rationale for the origin of these photodynamic motions associated with rapid topochemical transformations. The reported light-driven behavior (mechanical motions, dynamic phosphorescence, and topochemical reactivity), is considered advantageous for the strategic design of stimuli-responsive multi-functional crystalline materials.

Bio-photonics in dentistry: A review

Biophotonics is the new extended branch of photonics, which is the combination of photonics and biology. It is also known as biomedical optics as it has become an important tool for biomedical diagnosis, therapy, monitoring, imaging, and surgery. This branch deals with action of light on biological mattermainly tissue. Three types of laser-tissue interactions are known based on interaction time and active power density. Photochemical, photothermal, photomechanical and photoionization effects.