Light-driven C-H activation mediated by 2D transition metal dichalcogenides.

C-H bond activation enables the facile synthesis of new chemicals. While C-H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C-H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C-C coupling mediated by 2D TMDCs to promote C-H activation and carbon dots synthesis. Our results shed light on 2D materials for C-H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.

Advancing materials science through next-generation machine learning.

For over a decade, machine learning (ML) models have been making strides in computer vision and natural language processing (NLP), demonstrating high proficiency in specialized tasks. The emergence of large-scale language and generative image models, such as ChatGPT and Stable Diffusion, has significantly broadened the accessibility and application scope of these technologies. Traditional predictive models are typically constrained to mapping input data to numerical values or predefined categories, limiting their usefulness beyond their designated tasks. In contrast, contemporary models employ representation learning and generative modeling, enabling them to extract and encode key insights from a wide variety of data sources and decode them to create novel responses for desired goals. They can interpret queries phrased in natural language to deduce the intended output. In parallel, the application of ML techniques in materials science has advanced considerably, particularly in areas like inverse design, material prediction, and atomic modeling. Despite these advancements, the current models are overly specialized, hindering their potential to supplant established industrial processes. Materials science, therefore, necessitates the creation of a comprehensive, versatile model capable of interpreting human-readable inputs, intuiting a wide range of possible search directions, and delivering precise solutions. To realize such a model, the field must adopt cutting-edge representation, generative, and foundation model techniques tailored to materials science. A pivotal component in this endeavor is the establishment of an extensive, centralized dataset encompassing a broad spectrum of research topics. This dataset could be assembled by crowdsourcing global research contributions and developing models to extract data from existing literature and represent them in a homogenous format. A massive dataset can be used to train a central model that learns the underlying physics of the target areas, which can then be connected to a variety of specialized downstream tasks. Ultimately, the envisioned model would empower users to intuitively pose queries for a wide array of desired outcomes. It would facilitate the search for existing data that closely matches the sought-after solutions and leverage its understanding of physics and material-behavior relationships to innovate new solutions when pre-existing ones fall short.

Tuning Multipolar Mie Scattering of Particles on a Dielectric-Covered Mirror.

Optically resonant particles are key building blocks of many nanophotonic devices such as optical antennas and metasurfaces. Because the functionalities of such devices are largely determined by the optical properties of individual resonators, extending the attainable responses from a given particle is highly desirable. Practically, this is usually achieved by introducing an asymmetric dielectric environment. However, commonly used simple substrates have limited influences on the optical properties of the particles atop. Here, we show that the multipolar scattering of silicon microspheres can be effectively modified by placing the particles on a dielectric-covered mirror, which tunes the coupling between the Mie resonances of microspheres and the standing waves and waveguide modes in the dielectric spacer. This tunability allows selective excitation, enhancement, suppression, and even elimination of the multipolar resonances and enables scattering at extended wavelengths, providing transformative opportunities in controlling light-matter interactions for various applications. We further demonstrate with experiments the detection of molecular fingerprints by single-particle mid-infrared spectroscopy and with simulations strong optical repulsive forces that could elevate the particles from a substrate.

Optical Actuation of Nanoparticle-Loaded Liquid-Liquid Interfaces for Active Photonics.

Liquid-liquid interfaces hold the potential to serve as versatile platforms for dynamic processes, due to their inherent fluidity and capacity to accommodate surface-active materials. This study explores laser-driven actuation of liquid-liquid interfaces with and without loading of gold nanoparticles and further exploits the laser-actuated interfaces with nanoparticles for tunable photonics. Upon laser exposure, gold nanoparticles were rearranged along the interface, enabling the reconfigurable, small-aperture modulation of light transmission and the tunable lensing effect. Adapting the principles of optical and optothermal tweezers, we interpreted the underlying mechanisms of actuation and modulation as a synergy of optomechanical and optothermal effects. Our findings provide an analytical framework for understanding microscopic interfacial behaviors, contributing to potential applications in tunable photonics and interfacial material engineering.

Robotic Nanomanipulation Based on Spatiotemporal Modulation of Optical Gradients.

Robotic nanomanipulation emerges as a cutting-edge technique pivotal for in situ nanofabrication, advanced sensing, and comprehensive material characterization. In this study, we develop an optical robotic platform (ORP) for the dynamic manipulation of colloidal nanoparticles (NPs). The ORP incorporates a human-in-the-loop control mechanism enhanced by real-time visual feedback. This feature enables the generation of custom optical landscapes with adjustable intensity and phase configurations. Based on the ORP, we achieve the parallel and reconfigurable manipulation of multiple NPs. Through the application of spatiotemporal phase gradient-reversals, our platform demonstrates capabilities in trapping, binding, rotating, and transporting NPs across custom trajectories. This presents a previously unidentified paradigm in the realm of in situ nanomanipulation. Additionally, the ORP facilities a "capture-and-print" assembly process, utilizing a strategic interplay of phase and intensity gradients. This process operates under a constant laser power setting, streamlining the assembly of NPs into any targeted configuration. With its precise positioning and manipulation capabilities, underpinned by the spatiotemporal modulation of optical gradients, the ORP will facilitate the development of colloid-based sensors and on-demand fabrication of nanodevices.

Persistent and responsive collective motion with adaptive time delay.

It is beneficial for collective structures to simultaneously have high persistence to environmental noise and high responsivity to nontrivial external stimuli. However, without the ability to differentiate useful information from noise, there is always a tradeoff between persistence and responsivity within the collective structures. To address this, we propose adaptive time delay inspired by the adaptive behavior observed in the school of fish. This strategy is tested using particles powered by optothermal fields coupled with an optical feedback-control system. By applying the adaptive time delay with a proper threshold, we experimentally observe the responsivity of the collective structures enhanced by approximately 1.6 times without sacrificing persistence. Furthermore, we integrate adaptive time delay with long-distance transportation and obstacle-avoidance capabilities to prototype adaptive swarm microrobots. This research demonstrates the potential of adaptive time delay to address the persistence-responsivity tradeoff and lays the foundation for intelligent swarm micro/nanorobots operating in complex environments.

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.

Light-driven C-H activation mediated by 2D transition metal dichalcogenides.

C-H bond activation enables the facile synthesis of new chemicals. While C-H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C-H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C-C coupling mediated by 2D TMDCs to promote C-H activation. Our results shed light on 2D materials for C-H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.

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.

Bubble Printing of Layered Silicates: Surface Chemistry Effects and Picomolar Förster Resonance Energy Transfer Sensing.

The assembly of nanoparticles on surfaces in defined patterns has long been achieved via template-assisted methods that involve long deposition and drying steps and the need for molds or masks to obtain the desired patterns. Control over deposition of materials on surfaces via laser-directed microbubbles is a nascent technique that holds promise for rapid fabrication of devices down to the micrometer scale. However, the influence of surface chemistry on the resulting assembly using such approaches has so far not been studied. Herein, the printing of layered silicate nanoclays using a laser-directed microbubble was established. Significant differences in the macroscale structure of the printed patterns were observed for hydrophilic, pristine layered silicates compared to hydrophobic, modified layered silicates, which provided the first example of how the surface chemistry of such nanoscale objects results in changes in assembly with this approach. Furthermore, the ability of layered silicates to adsorb molecules at the interface was retained, which allowed the fabrication of proof-of-concept sensors based on Förster resonance energy transfer (FRET) from quantum dots embedded in the assemblies to bound dye molecules. The detection limit for Rhodamine 800 sensing via FRET was found to be on the order of 10-12 M, suggesting signal enhancement due to favorable interactions between the dye and nanoclay. This work sets the stage for future advances in the control of hierarchical assembly of nanoparticles by modification of surface chemistry while also demonstrating a quick and versatile approach to achieve ultrasensitive molecular sensors.

Observation of Room-Temperature Exciton-Polariton Emission from Wide-Ranging 2D Semiconductors Coupled with a Broadband Mie Resonator.

Two-dimensional exciton-polaritons in monolayer transition metal dichalcogenides (TMDs) exhibit practical advantages in valley coherence, optical nonlinearities, and even bosonic condensation owing to their light-emission capability. To achieve robust exciton-polariton emission, strong photon-exciton couplings are required at the TMD monolayer, which is challenging due to its atomic thickness. High-quality (Q) factor optical cavities with narrowband resonances are an effective approach but typically limited to a specific excitonic state of a certain TMD material. Herein, we achieve on-demand exciton-polariton emission from a wide range of TMDs at room temperature by hybridizing excitons with broadband Mie resonances spanning the whole visible spectrum. By confining broadband light at the TMD monolayer, our one type of Mie resonator on different TMDs enables enhanced light-matter interactions with multiple excitonic states simultaneously. We demonstrate multi-Rabi splittings and robust polaritonic photoluminescence in monolayer WSe2, WS2, and MoS2. The hybrid system also shows the potential to approach the ultrastrong coupling regime.

Advancing optothermal manipulation: decoupling temperature and flow fields in quasi-isothermal microscale streaming.

By decoupling temperature and flow fields through symmetry-correlated laser scan sequences, ISO-FLUCS enables quasi-isothermal optofluidic microscale streaming. This technique offers precise control over fluid manipulation while minimizing thermal damage.

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.

High-Resolution Volumetric Imaging and Classification of Organisms with Standard Optical Microscopy.

Three-dimensional (3D) characterization of organisms is important for the study of cellular phenotypes, structural organization, and mechanotransduction. Existing optical techniques for 3D imaging rely on focus stacking or complex multiangle projection. Focus stacking has deleterious axial resolution due to the one-angle optical projection. Herein, we achieve high-resolution 3D imaging and classification of organisms based on standard optical microscopy coupled to optothermal rotation. Through a seamless fusion of optical trapping and rotation of organisms on a single platform, our technique is applicable to any organism suspended in clinical samples, enabling contact-free and biocompatible 3D imaging. Moreover, when applying deep learning to distinguish different types of biological cells with high similarity, we demonstrate that our platform improves the classification accuracy (96% vs 85%) while using one-tenth the number of training samples compared with conventional deep-learning-based classification.

Optical Manipulation Heats up: Present and Future of Optothermal Manipulation.

Optothermal manipulation is a versatile technique that combines optical and thermal forces to control synthetic micro-/nanoparticles and biological entities. This emerging technique overcomes the limitations of traditional optical tweezers, including high laser power, photon and thermal damage to fragile objects, and the requirement of refractive-index contrast between target objects and the surrounding solvents. In this perspective, we discuss how the rich opto-thermo-fluidic multiphysics leads to a variety of working mechanisms and modes of optothermal manipulation in both liquid and solid media, underpinning a broad range of applications in biology, nanotechnology, and robotics. Moreover, we highlight current experimental and modeling challenges in the pursuit of optothermal manipulation and propose future directions and solutions to the challenges.

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.

Detection and analysis of chiral molecules as disease biomarkers.

The chirality of small metabolic molecules is important in controlling physiological processes and indicating the health status of humans. Abnormal enantiomeric ratios of chiral molecules in biofluids and tissues occur in many diseases, including cancers and kidney and brain diseases. Thus, chiral small molecules are promising biomarkers for disease diagnosis, prognosis, adverse drug-effect monitoring, pharmacodynamic studies and personalized medicine. However, it remains difficult to achieve cost-effective and reliable analysis of small chiral molecules in clinical procedures, in part owing to their large variety and low concentration. In this Review, we describe current and emerging techniques that detect and quantify small-molecule enantiomers and their biological importance.

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.