Highly flame retardancy, barrier, mechanical and persistent antibacterial polylactic acid film with high-parallel interconnected thousand layered cake architecture.

In this work, a bio-based material (CGP) is obtained by combing chitosan, gelatin and polyvinyl alcohol through a simple solution mixing to simultaneously address polylactic acid film (PLA)' flammability and poor barrier, toughness and antibacterial properties by soaking. The results of open fire testing show that modified PLA films can effectively prolong the combustion time, improve the thermal stability and reduce the release of heat in the cone calorimeter test. For the PLA sample after soaking for 5 times (PLA-5) in particular, it can reduce the peak heat release rate (pHRR) and total heat release (THR) values to 85.8 kW/m2 and 1.3 MJ/m2 from the values of 129.5 kW/m2 and 1.8 MJ/m2 for PLA, respectively. Structural analysis suggests that CGP primarily operates in the condensed phase by forming physical barriers. Meanwhile, the modified PLA films can exhibit superior barrier effects, which indicate the oxygen transmission rate value of PLA-5 decreases to 0.9 cm3/(m2·day) from the 392.5 cm3/(m2·day) of raw PLA film. Moreover, the PLA-5 also have excellent toughness (the value increased to 200.5 % from 31.0 %) and persistent antibacterial effects (it still has 100 % sterilization after 500 days).

Three-Dimensional Optothermal Manipulation of Light-Absorbing Particles in Phase-Change Gel Media.

Rational manipulation and assembly of discrete colloidal particles into architected superstructures have enabled several applications in materials science and nanotechnology. Optical manipulation techniques, typically operated in fluid media, facilitate the precise arrangement of colloidal particles into superstructures by using focused laser beams. However, as the optical energy is turned off, the inherent Brownian motion of the particles in fluid media impedes the retention and reconfiguration of such superstructures. Overcoming this fundamental limitation, we present on-demand, three-dimensional (3D) optical manipulation of colloidal particles in a phase-change solid medium made of surfactant bilayers. Unlike liquid crystal media, the lack of fluid flow within the bilayer media enables the assembly and retention of colloids for diverse spatial configurations. By utilizing the optically controlled temperature-dependent interactions between the particles and their surrounding media, we experimentally exhibit the holonomic microscale control of diverse particles for repeatable, reconfigurable, and controlled colloidal arrangements in 3D. Finally, we demonstrate tunable light-matter interactions between the particles and 2D materials by successfully manipulating and retaining these particles at fixed distances from the 2D material layers. Our experimental results demonstrate that the particles can be retained for over 120 days without any change in their relative positions or degradation in the bilayers. With the capability of arranging particles in 3D configurations with long-term stability, our platform pushes the frontiers of optical manipulation for distinct applications such as metamaterial fabrication, information storage, and security.

Synchronous and Fully Steerable Active Particle Systems for Enhanced Mimicking of Collective Motion in Nature.

The collective motion observed in living active matter, such as fish schools and bird flocks, is characterized by its dynamic and complex nature, involving various moving states and transitions. By tailoring physical interactions or incorporating information exchange capabilities, inanimate active particles can exhibit similar behavior. However, the lack of synchronous and arbitrary control over individual particles hinders their use as a test system for the study of more intricate collective motions in living species. Herein, a novel optical feedback control system that enables the mimicry of collective motion observed in living objects using active particles is proposed. This system allows for the experimental investigation of the velocity alignment, a seminal model of collective motion (known as the Vicsek model), in a microscale perturbed environment with controllable and realistic conditions. The spontaneous formation of different moving states and dynamic transitions between these states is observed. Additionally, the high robustness of the active-particle group at the critical density under the influence of different perturbations is quantitatively validated. These findings support the effectiveness of velocity alignment in real perturbed environments, thereby providing a versatile platform for fundamental studies on collective motion and the development of innovative swarm microrobotics.

Hypothermal opto-thermophoretic tweezers.

Optical tweezers have profound importance across fields ranging from manufacturing to biotechnology. However, the requirement of refractive index contrast and high laser power results in potential photon and thermal damage to the trapped objects, such as nanoparticles and biological cells. Optothermal tweezers have been developed to trap particles and biological cells via opto-thermophoresis with much lower laser powers. However, the intense laser heating and stringent requirement of the solution environment prevent their use for general biological applications. Here, we propose hypothermal opto-thermophoretic tweezers (HOTTs) to achieve low-power trapping of diverse colloids and biological cells in their native fluids. HOTTs exploit an environmental cooling strategy to simultaneously enhance the thermophoretic trapping force at sub-ambient temperatures and suppress the thermal damage to target objects. We further apply HOTTs to demonstrate the three-dimensional manipulation of functional plasmonic vesicles for controlled cargo delivery. With their noninvasiveness and versatile capabilities, HOTTs present a promising tool for fundamental studies and practical applications in materials science and biotechnology.

Multimodal Optothermal Manipulations along Various Surfaces.

Optical tweezers have provided tremendous opportunities for fundamental studies and applications in the life sciences, chemistry, and physics by offering contact-free manipulation of small objects. However, it requires sophisticated real-time imaging and feedback systems for conventional optical tweezers to achieve controlled motion of micro/nanoparticles along textured surfaces, which are required for such applications as high-resolution near-field characterizations of cell membranes with nanoparticles as probes. In addition, most optical tweezers systems are limited to single manipulation modes, restricting their broader applications. Herein, we develop an optothermal platform that enables the multimodal manipulation of micro/nanoparticles along various surfaces. Specifically, we achieve the manipulation of micro/nanoparticles through the synergy between the optical and thermal forces, which arise due to the temperature gradient self-generated by the particles absorbing the light. With a simple control of the laser beam, we achieve five switchable working modes [i.e., tweezing, rotating, rolling (toward), rolling (away), and shooting] for the versatile manipulation of both synthesized particles and biological cells along various substrates. More interestingly, we realize the manipulation of micro/nanoparticles on rough surfaces of live worms and their embryos for localized control of biological functions. By enabling the three-dimensional control of micro/nano-objects along various surfaces, including topologically uneven biological tissues, our multimodal optothermal platform will become a powerful tool in life sciences, nanotechnology, and colloidal sciences.

Optothermal rotation of micro-/nano-objects.

Due to its contactless and fuel-free operation, optical rotation of micro-/nano-objects provides tremendous opportunities for cellular biology, three-dimensional (3D) imaging, and micro/nanorobotics. However, complex optics, extremely high operational power, and the applicability to limited objects restrict the broader use of optical rotation techniques. This Feature Article focuses on a rapidly emerging class of optical rotation techniques, termed optothermal rotation. Based on light-mediated thermal phenomena, optothermal rotation techniques overcome the bottlenecks of conventional optical rotation by enabling versatile rotary control of arbitrary objects with simpler optics using lower powers. We start with the fundamental thermal phenomena and concepts: thermophoresis, thermoelectricity, thermo-electrokinetics, thermo-osmosis, thermal convection, thermo-capillarity, and photophoresis. Then, we highlight various optothermal rotation techniques, categorizing them based on their rotation modes (i.e., in-plane and out-of-plane rotation) and the thermal phenomena involved. Next, we explore the potential applications of these optothermal manipulation techniques in areas such as single-cell mechanics, 3D bio-imaging, and micro/nanomotors. We conclude the Feature Article with our insights on the operating guidelines, existing challenges, and future directions of optothermal rotation.

Hypothermal opto-thermophoretic tweezers.

Optical tweezers have profound importance across fields ranging from manufacturing to biotechnology. However, the requirement of refractive index contrast and high laser power results in potential photon and thermal damage to the trapped objects, such as nanoparticles and biological cells. Optothermal tweezers have been developed to trap particles and biological cells via opto-thermophoresis with much lower laser powers. However, the intense laser heating and stringent requirement of the solution environment prevent their use for general biological applications. Here, we propose hypothermal opto-thermophoretic tweezers (HOTTs) to achieve low-power trapping of diverse colloids and biological cells in their native fluids. HOTTs exploit an environmental cooling strategy to simultaneously enhance the thermophoretic trapping force at sub-ambient temperatures and suppress the thermal damage to target objects. We further apply HOTTs to demonstrate the three-dimensional manipulation of functional plasmonic vesicles for controlled cargo delivery. With their noninvasiveness and versatile capabilities, HOTTs present a promising tool for fundamental studies and practical applications in materials science and biotechnology.

Optothermal rotation of micro-/nano-objects in liquids.

Controllable rotation of micro-/nano-objects provides tremendous opportunities for cellular biology, three-dimensional (3D) imaging, and micro/nanorobotics. Among different rotation techniques, optical rotation is particularly attractive due to its contactless and fuel-free operation. However, optical rotation precision is typically impaired by the intrinsic optical heating of the target objects. Optothermal rotation, which harnesses light-modulated thermal effects, features simpler optics, lower operational power, and higher applicability to various objects. In this Feature Article, we discuss the recent progress of optothermal rotation with a focus on work from our research group. We categorize the various rotation techniques based on distinct physical mechanisms, including thermophoresis, thermoelectricity, thermo-electrokinetics, thermo-osmosis, thermal convection, and thermo-capillarity. Benefiting from the different rotation modes (i.e., in-plane and out-of-plane rotation), diverse applications in single-cell mechanics, 3D bio-imaging, and micro/nanomotors are demonstrated. We conclude the article with our perspectives on the operating guidelines, existing challenges, and future directions of optothermal rotation.

Light-driven single-cell rotational adhesion frequency assay.

The interaction between cell surface receptors and extracellular ligands is highly related to many physiological processes in living systems. Many techniques have been developed to measure the ligand-receptor binding kinetics at the single-cell level. However, few techniques can measure the physiologically relevant shear binding affinity over a single cell in the clinical environment. Here, we develop a new optical technique, termed single-cell rotational adhesion frequency assay (scRAFA), that mimics in vivo cell adhesion to achieve label-free determination of both homogeneous and heterogeneous binding kinetics of targeted cells at the subcellular level. Moreover, the scRAFA is also applicable to analyze the binding affinities on a single cell in native human biofluids. With its superior performance and general applicability, scRAFA is expected to find applications in study of the spatial organization of cell surface receptors and diagnosis of infectious diseases. Supplementary Information: The online version contains supplementary material available at 10.1186/s43593-022-00020-4.

Programmable Multimodal Optothermal Manipulation of Synthetic Particles and Biological Cells.

Optical manipulation of tiny objects has benefited many research areas ranging from physics to biology to micro/nanorobotics. However, limited manipulation modes, intense lasers with complex optics, and applicability to limited materials and geometries of objects restrict the broader uses of conventional optical tweezers. Herein, we develop an optothermal platform that enables the versatile manipulation of synthetic micro/nanoparticles and live cells using an ultralow-power laser beam and a simple optical setup. Five working modes (i.e., printing, tweezing, rotating, rolling, and shooting) have been achieved and can be switched on demand through computer programming. By incorporating a feedback control system into the platform, we realize programmable multimodal control of micro/nanoparticles, enabling autonomous micro/nanorobots in complex environments. Moreover, we demonstrate in situ three-dimensional single-cell surface characterizations through the multimodal optothermal manipulation of live cells. This programmable multimodal optothermal platform will contribute to diverse fundamental studies and applications in cellular biology, nanotechnology, robotics, and photonics.

Investigating water/oil interfaces with opto-thermophoresis.

Charging of interfaces between water and hydrophobic media is a mysterious feature whose nature and origin have been under debate. Here, we investigate the fundamentals of the interfacial behaviors of water by employing opto-thermophoretic tweezers to study temperature-gradient-induced perturbation of dipole arrangement at water/oil interfaces. With surfactant-free perfluoropentane-in-water emulsions as a model interface, additional polar organic solvents are introduced to systematically modify the structural aspects of the interface. Through our experimental measurements on the thermophoretic behaviors of oil droplets under a light-generated temperature gradient, in combination with theoretical analysis, we propose that water molecules and mobile negative charges are present at the water/oil interfaces with specific dipole arrangement to hydrate oil droplets, and that this arrangement is highly susceptible to the thermal perturbation due to the mobility of the negative charges. These findings suggest a potential of opto-thermophoresis in probing aqueous interfaces and could enrich understanding of the interfacial behaviors of water.

Universal optothermal micro/nanoscale rotors.

Rotation of micro/nano-objects is important for micro/nanorobotics, three-dimensional imaging, and lab-on-a-chip systems. Optical rotation techniques are especially attractive because of their fuel-free and remote operation. However, current techniques require laser beams with designed intensity profile and polarization or objects with sophisticated shapes or optical birefringence. These requirements make it challenging to use simple optical setups for light-driven rotation of many highly symmetric or isotropic objects, including biological cells. Here, we report a universal approach to the out-of-plane rotation of various objects, including spherically symmetric and isotropic particles, using an arbitrary low-power laser beam. Moreover, the laser beam is positioned away from the objects to reduce optical damage from direct illumination. The rotation mechanism based on opto-thermoelectrical coupling is elucidated by rigorous experiments combined with multiscale simulations. With its general applicability and excellent biocompatibility, our universal light-driven rotation platform is instrumental for various scientific research and engineering applications.

Self-Limiting Opto-Electrochemical Thinning of Transition-Metal Dichalcogenides.

Two-dimensional monolayer and few-layer transition-metal dichalcogenides (TMDs) are promising for advanced electronic and photonic applications due to their extraordinary optoelectronic and mechanical properties. However, it has remained challenging to produce high-quality TMD thin films with controlled thickness and desired micropatterns, which are essential for their practical implementation in functional devices. In this work, a self-limiting opto-electrochemical thinning (sOET) technique is developed for on-demand thinning and patterning of TMD flakes at high efficiency. Benefiting from optically enhanced electrochemical reactions, sOET features a low operational optical power density of down to 70 µW µm-2 to avoid photodamage and thermal damage to the thinned TMD flakes. Through selective optical excitation with different laser wavelengths based on the thickness-dependent band gaps of TMD materials, sOET enables precise control over the final thickness of TMD flakes. With the capability of thickness control and site-specific patterning, our sOET offers an effective route to fabricating high-quality TMD materials for a broad range of applications in nanoelectronics, nanomechanics, and nanophotonics.

Liquid Optothermoelectrics: Fundamentals and Applications.

Liquid thermoelectricity describes the redistribution of ions in an electrolytic solution under the influence of temperature gradients, which leads to the formation of electric fields. The thermoelectric field is effective in driving the thermophoretic migration of charged colloidal particles for versatile manipulation. However, traditional macroscopic thermoelectric fields are not suitable for particle manipulations at high spatial resolution. Inspired by optical tweezers and relevant optical manipulation techniques, we employ laser interaction with light-absorbing nanostructures to achieve subtle heat management on the micro- and nanoscales. The resulting thermoelectric fields are exploited to develop new optical technologies, leading to a research field known as liquid optothermoelectrics. This Invited Feature Article highlights our recent works on advancing fundamentals, technologies, and applications of optothermoelectrics in colloidal solutions. The effects of light irradiation, substrates, electrolytes, and particles on the optothermoelectric manipulations of colloidal particles along with their theoretical limitations are discussed in detail. Our optothermoelectric technologies with the versatile capabilities of trapping, manipulating, and pulling colloidal particles at low optical power are finding applications in microswimmers and nanoscience. With its intricate interfacial processes and tremendous technological promise, optothermoelectrics in colloidal solutions will remain relevant for the foreseeable future.

Enhancing Single-Molecule Fluorescence Spectroscopy with Simple and Robust Hybrid Nanoapertures.

Plasmonic nanoapertures have found exciting applications in optical sensing, spectroscopy, imaging, and nanomanipulation. The subdiffraction optical field localization, reduced detection volume (~attoliters), and background-free operation make them particularly attractive for single-particle and single-molecule studies. However, in contrast to the high field enhancements by traditional "nanoantenna"-based structures, small field enhancement in conventional nanoapertures results in weak light-matter interactions and thus small enhancement of spectroscopic signals (such as fluorescence and Raman signals) of the analytes interacting with the nanoapertures. In this work, we propose a hybrid nanoaperture design termed "gold-nanoislands-embedded nanoaperture" (AuNIs-e-NA), which provides multiple electromagnetic "hotspots" within the nanoaperture to achieve field enhancements of up to 4000. The AuNIs-e-NA was able to improve the fluorescence signals by more than 2 orders of magnitude with respect to a conventional nanoaperture. With simple design and easy fabrication, along with strong signal enhancements and operability over variable light wavelengths and polarizations, the AuNIs-e-NA will serve as a robust platform for surface-enhanced optical sensing, imaging, and spectroscopy.

Atomistic modeling and rational design of optothermal tweezers for targeted applications.

Optical manipulation of micro/nanoscale objects is of importance in life sciences, colloidal science, and nanotechnology. Optothermal tweezers exhibit superior manipulation capability at low optical intensity. However, our implicit understanding of the working mechanism has limited the further applications and innovations of optothermal tweezers. Herein, we present an atomistic view of opto-thermo-electro-mechanic coupling in optothermal tweezers, which enables us to rationally design the tweezers for optimum performance in targeted applications. Specifically, we have revealed that the non-uniform temperature distribution induces water polarization and charge separation, which creates the thermoelectric field dominating the optothermal trapping. We further design experiments to systematically verify our atomistic simulations. Guided by our new model, we develop new types of optothermal tweezers of high performance using low-concentrated electrolytes. Moreover, we demonstrate the use of new tweezers in opto-thermophoretic separation of colloidal particles of the same size based on the difference in their surface charge, which has been challenging for conventional optical tweezers. With the atomistic understanding that enables the performance optimization and function expansion, optothermal tweezers will further their impacts.

Enhancing Surface Capture and Sensing of Proteins with Low-Power Optothermal Bubbles in a Biphasic Liquid.

Molecular binding in surface-based biosensing is inherently governed by diffusional transport of molecules in solution to surface-immobilized counterparts. Optothermally generated surface microbubbles can quickly accumulate solutes at the bubble-liquid-substrate interface due to high-velocity fluid flows. Despite its potential as a concentrator, however, the incorporation of bubbles into protein-based sensing is limited by high temperatures. Here, we report a biphasic liquid system, capable of generating microbubbles at a low optical power/temperature by formulating PFP as a volatile, water-immiscible component in the aqueous host. We further exploited zwitterionic surface modification to prevent unwanted printing during bubble generation. In a single protein-protein interaction model, surface binding of dispersed proteins to capture proteins was enhanced by 1 order of magnitude within 1 min by bubbles, compared to that from static incubation for 30 min. Our proof-of-concept study exploiting fluid formulation and optothermal add-on paves an effective way toward improving the performances of sensors and spectroscopies.

Optical nanomanipulation on solid substrates via optothermally-gated photon nudging.

Constructing colloidal particles into functional nanostructures, materials, and devices is a promising yet challenging direction. Many optical techniques have been developed to trap, manipulate, assemble, and print colloidal particles from aqueous solutions into desired configurations on solid substrates. However, these techniques operated in liquid environments generally suffer from pattern collapses, Brownian motion, and challenges that come with reconfigurable assembly. Here, we develop an all-optical technique, termed optothermally-gated photon nudging (OPN), for the versatile manipulation and dynamic patterning of a variety of colloidal particles on a solid substrate at nanoscale accuracy. OPN takes advantage of a thin surfactant layer to optothermally modulate the particle-substrate interaction, which enables the manipulation of colloidal particles on solid substrates with optical scattering force. Along with in situ optical spectroscopy, our non-invasive and contactless nanomanipulation technique will find various applications in nanofabrication, nanophotonics, nanoelectronics, and colloidal sciences.

Ultra-fast vapor generation by a graphene nano-ratchet: a theoretical and simulation study.

Vapor generation is of prime importance for a broad range of applications: domestic water heating, desalination and wastewater treatment, etc. However, slow and inefficient evaporation limits its development. In this study, a nano-ratchet, a multilayer graphene with cone-shaped nanopores (MGCN), to accelerate vapor generation has been proposed. By performing molecular dynamics simulation, we found that air molecules were spontaneously transported across MGCN and resulted in a remarkable pressure difference, 21 kPa, between the two sides of MGCN. We studied the dependence of the pressure difference on the ambient temperature and geometry of MGCN in detail. Through further analysis of the diffusive transport, we found that pressure difference depended on the competition between ratchet transport and Knudsen diffusion and it was further found that ratchet transport is dominant. The significant pressure difference could lead to a 15-fold or greater enhancement of vapor generation, which shows the wide applications of this nano-ratchet.