Dye-sensitized solar cells under ambient light powering machine learning: towards autonomous smart sensors for the internet of things

The field of photovoltaics gives the opportunity to make our buildings ‘‘smart’’ and our portable devices “independent”, provided effective energy sources can be developed for use in ambient indoor conditions. To address this important issue, ambient light photovoltaic cells were developed to power autonomous Internet of Things (IoT) devices, capable of machine learning, allowing the on-device implementation of artificial intelligence. Through a novel co-sensitization strategy, we tailored dye-sensitized photovoltaic cells based on a copper(ii/i) electrolyte for the generation of power under ambient lighting with an unprecedented conversion efficiency (34%, 103 μW cm⁻² at 1000 lux; 32.7%, 50 μW cm⁻² at 500 lux and 31.4%, 19 μW cm⁻² at 200 lux from a fluorescent lamp). A small array of DSCs with a joint active area of 16 cm² was then used to power machine learning on wireless nodes. The collection of 0.947 mJ or 2.72 × 10¹⁵ photons is needed to compute one inference of a pre-trained artificial neural network for MNIST image classification in the employed set up. The inference accuracy of the network exceeded 90% for standard test images and 80% using camera-acquired printed MNIST-digits. Quantization of the neural network significantly reduced memory requirements with a less than 0.1% loss in accuracy compared to a full-precision network, making machine learning inferences on low-power microcontrollers possible. 152 J or 4.41 × 10²⁰ photons required for training and verification of an artificial neural network were harvested with 64 cm² photovoltaic area in less than 24 hours under 1000 lux illumination. Ambient light harvesters provide a new generation of self-powered and “smart” IoT devices powered through an energy source that is largely untapped.

Indoor light harvesters enable machine learning on fully autonomous IoT devices at 2.72 × 10¹⁵ photons per inference.     

Progress,highlights and perspectives on NiO in perovskite photovoltaics

The power conversion efficiency (PCE) of NiO based perovskite solar cells has recently hit a record 22.1% with a hybrid organic–inorganic perovskite composition and a PCE above 15% in a fully inorganic configuration was achieved. Moreover, NiO processing is a mature technology, with different industrially attractive processes demonstrated in the last few years. These considerations, along with the excellent stabilities reported, clearly point towards NiO as the most efficient inorganic hole selective layer for lead halide perovskite photovoltaics, which is the topic of this review. NiO optoelectronics is discussed by analysing the different doping mechanisms, with a focus on the case of alkaline and transition metal cation dopants. Doping allows tuning the conductivity and the energy levels of NiO, improving the overall performance and adapting the material to a variety of perovskite compositions. Furthermore, we summarise the main investigations on the NiO/perovskite interface stability. In fact, the surface of NiO is commonly oxidised and reactive with perovskite, also under the effect of light, thermal and electrical stress. Interface engineering strategies should be considered aiming at long term stability and the highest efficiency. Finally, we present the main achievements in flexible, fully printed and lead-free perovskite photovoltaics which employ NiO as a layer and provide our perspective to accelerate the improvement of these technologies. Overall, we show that adequately doped and passivated NiO might be an ideal hole selective layer in every possible application of perovskite solar cells.

The power conversion efficiency of NiO based perovskite solar cells has recently hit a record 22.1%. Here, the main advances are reviewed and the role of NiO in the next breakthroughs is discussed.     

Local probe investigation of electrocatalytic activity

As the world energy crisis remains a long-term challenge, development and access to renewable energy sources are crucial for a sustainable modern society. Electrochemical energy conversion devices are a promising option for green energy supply, although the challenge associated with electrocatalysis have caused increasing complexity in the materials and systems, demanding further research and insights. In this field, scanning probe microscopy (SPM) represents a specific source of knowledge and understanding. Thus, our aim is to present recent findings on electrocatalysts for electrolysers and fuel cells, acquired mainly through scanning electrochemical microscopy (SECM) and other related scanning probe techniques. This review begins with an introduction to the principles of several SPM techniques and then proceeds to the research done on various energy-related reactions, by emphasizing the progress on non-noble electrocatalytic materials.

Investigation of electrocatalytic materials with scanning probe techniques (SECM, SICM, SECCM and AFM) for energy storage and conversion devices.     

Surface modification of liquid metal as an effective approach for deformable electronics and energy devices

The fields of flexible or stretchable electronics and energy devices, reconfigurable and compliant soft robotics, wearable e-textiles or health-care devices have paid significant attention to the need of deformable conductive electrodes due to its critical role in device performances. Gallium-based liquid metals, such as the eutectic gallium–indium (EGaIn) being an electrically conductive liquid phase at room temperature, have attracted immense interests as a promising candidate for deformable conductor. However, in the case of bulk liquid metal, there are several limitations such as the need of encapsulation, dispersion in a polymer matrix, or accurate patterning. For these reasons, the preparation of liquid metal particles in harnessing the properties in a non-bulk form and surface modification is crucial for the success of incorporating liquid metal into functional devices. Herein, we discuss the current progress in chemical surface modification and interfacial manipulations of liquid metal particles. The physical and chemical properties of the surface modification-assisted liquid metal polymer composite are also reviewed. Lastly, the applications of the surface-modified liquid metal particles such as flexible electrode, soft robotics, energy storage or harvester, thermal conductor, dielectric sensor, and bioelectronics are discussed, and the corresponding perspectives of deformable electronics and energy devices are provided. In particular, we focus on the functionalization method or requirement of liquid metal particles in each application. The challenging issues and outlook on the applications of surface-modified liquid metal particles are also discussed.

In this review, we summarize the recent progress in chemical surface modification and interfacial manipulations of liquid metal particles and discuss the modification method or requirement of liquid metal particles in emerging applications.     

A photo-regulated aptamer sensor for spatiotemporally controlled monitoring of ATP in the mitochondria of living cells

Fluorescent aptamer sensors have shown enormous potential for intracellular imaging of small molecule metabolites. Since metabolites distribute differently at different subcellular locations and their concentrations and locations fluctuate with time, methods are needed for spatiotemporally controlled monitoring of these metabolites. Built upon previous success in temporal control of aptamer-based sensors, we herein report an aptamer sensor containing a photocleavable linker and using DQAsomes to target mitochondria for spatiotemporally controlled monitoring of ATP in the mitochondria of living cells. The photocleavable modification on the DNA ATP aptamer sensor can prevent sensor activation before reaching mitochondria and the sensor can then be activated upon light irradiation. The sensor has a detection limit of 3.7 μM and high selectivity against other nucleotides, allowing detection of ATP concentration fluctuations in mitochondria induced by Ca²⁺ or oligomycin. This work represents the first successful delivery of a DNA aptamer sensor to mitochondria, providing a new platform for targeted delivery to subcellular organelles for monitoring energy producing processes, as well as mitochondrial dysfunction-related diseases in different cells.

A photo-regulated ATP sensor coupled with cationic DQAsomes is developed for spatiotemporally controlled imaging of ATP in the mitochondria of living cells.     

Self-charging power system for distributed energy: beyond the energy storage unit

Power devices for the smart sensor networks of Internet of things (IoT) are required with minimum or even no maintenance due to their enormous quantities and widespread distribution. Self-charging power systems (SCPSs) refer to integrated energy devices with simultaneous energy harvesting, power management and effective energy storage capabilities, which may need no extra battery recharging and can sustainably drive sensors. Herein, we focus on the progress made in the field of nanogenerator-based SCPSs, which harvest mechanical energy using the Maxwell displacement current arising from the variation in the surface-polarized-charge-induced electrical field. Prototypes of different nanogenerator-based SCPSs will be overviewed. Finally, challenges and prospects in this field will be discussed.

Recent progresses and future prospects on nanogenerator-based self-charging power systems (SCPSs) are discussed with this perspective.     

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

Extremely low-frequency phonon material and its temperature- and photo-induced switching effects

Atomic vibrations due to stretching or bending modes cause optical phonon modes in the solid phase. These optical phonon modes typically lie in the frequency range of 10² to 10⁴ cm⁻¹. How much can the frequency of optical phonon modes be lowered? Herein we show an extremely low-frequency optical phonon mode of 19 cm⁻¹ (0.58 THz) in a Rb-intercalated two-dimensional cyanide-bridged Co–W bimetal assembly. This ultralow frequency is attributed to a millefeuille-like structure where Rb ions are very softly sandwiched between the two-dimensional metal–organic framework, and the Rb ions slowly vibrate between the layers. Furthermore, we demonstrate temperature-induced and photo-induced switching of this low-frequency phonon mode. Such an external-stimulation-controllable sub-terahertz (sub-THz) phonon crystal, which has not been reported before, should be useful in devices and absorbers for high-speed wireless communications such as beyond 5G or THz communication systems.

Extremely low-frequency optical phonon mode in Rb-intercalated two-dimensional cyanide-bridged Co–W bimetal assembly and its temperature- and photo-induced switching effect.     

Supramolecular strategies in artificial photosynthesis

Artificial photosynthesis is a major scientific endeavor aimed at converting solar power into a chemical fuel as a viable approach to sustainable energy production and storage. Photosynthesis requires three fundamental actions performed in order; light harvesting, charge-separation and redox catalysis. These actions span different timescales and require the integration of functional architectures developed in different fields of study. The development of artificial photosynthetic devices is therefore inherently complex and requires an interdisciplinary approach. Supramolecular chemistry has evolved to a mature scientific field in which programmed molecular components form larger functional structures by self-assembly processes. Supramolecular chemistry could provide important tools in preparing, integrating and optimizing artificial photosynthetic devices as it allows precise control over molecular components within such a device. This is illustrated in this perspective by discussing state-of-the-art devices and the current limiting factors – such as recombination and low stability of reactive intermediates – and providing exemplary supramolecular approaches to alleviate some of those problems. Inspiring supramolecular solutions such as those discussed herein will incite expansion of the supramolecular toolbox, which eventually may be needed for the development of applied artificial photosynthesis.

This review describes supramolecular strategies for optimization and integration of components needed for the fundamentals of artificial photosynthesis: light harvesting, charge-separation and catalysis, which are relevant for solar-to-fuel devices.     

Selectively detecting attomolar concentrations of proteins using gold lined nanopores in a nanopore blockade sensor

Disease diagnosis at earlier stages requires the development of ultrasensitive biosensors for detecting low-abundance biomarkers in complex biological fluids within a reasonable time frame. Here, we demonstrate the development of an ultrasensitive nanopore blockade biosensor that can rapidly diagnose a model protein biomarker, prostate-specific antigen (PSA) with high selectivity. The solid-state nanopores have gold located only along the length of the nanopore whilst the rest of the membrane is silicon nitride. The orthogonal use of materials allows nanopore arrays with a different surface chemistry inside the nanopore relative to the rest of the membrane to be fabricated. The importance of this differential surface chemistry is it can improve the detection limit of nanopore blockade sensors in quantitative analysis. Based on such functionalized nanopore devices, nanopore blockade sensors lower the limit of detection by an order of magnitude and enable ultrasensitive detection of PSA as low as 80 aM. The findings from this study open new opportunities for nanopore sensors in further developments including optical detection and ultralow detection limit biosensing at complex biological fluids.

Selective detection of attomolar proteins was achieved using gold lined nanopores in a nanopore blockade sensor.     

Design of BODIPY dyes as triplet photosensitizers: electronic properties tailored for solar energy conversion,photoredox catalysis and photodynamic therapy

BODIPYs are renowned fluorescent dyes with strong and tunable absorption in the visible region, high thermal and photo-stability and exceptional fluorescence quantum yields. Transition metal complexes are the most commonly used triplet photosensitisers, but, recently, the use of organic dyes has emerged as a viable and more sustainable alternative. By proper design, BODIPY dyes have been turned from highly fluorescent labels into efficient triplet photosensitizers with strong absorption in the visible region (from green to orange). In this perspective, we report three design strategies: (i) halogenation of the dye skeleton, (ii) donor–acceptor dyads and (iii) BODIPY dimers. We compare pros and cons of these approaches in terms of optical and electrochemical properties and synthetic viability. The potential applications of these systems span from energy conversion to medicine and key examples are presented.

BODIPYs offer a versatile platform to build organic triplet photosensitisers for PDT, TTA upconversion and photocatalysis. Tuning their properties provides the opportunity of replacing heavy-metal complexes and can lead to improved sustainability.     

Enhanced catalytic reaction at an air–liquid–solid triphase interface

Gaseous reactant involved heterogeneous catalysis is critical to the development of clean energy, environmental management, health monitoring, and chemical synthesis. However, in traditional heterogeneous catalysis with liquid–solid diphase reaction interfaces, the low solubility and slow transport of gaseous reactants strongly restrict the reaction efficiency. In this minireview, we summarize recent advances in tackling these drawbacks by designing catalytic systems with an air–liquid–solid triphase joint interface. At the triphase interface, abundant gaseous reactants can directly transport from the air phase to the reaction centre to overcome the limitations of low solubility and slow transport of the dissolved gas in liquid–solid diphase reaction systems. By constructing a triphase interface, the efficiency and/or selectivity of photocatalytic reactions, enzymatic reactions, and (photo)electrochemical reactions with consumption of gaseous reactants oxygen, carbon dioxide, and nitrogen are significantly improved.

Gaseous reactant involved liquid–solid diphase interface reactions can be significantly enhanced using rationally designed and constructed air–liquid–solid triphase systems.     

Merging C(sp3)–H activation with DNA-encoding

DNA-encoded library (DEL) technology has the potential to dramatically expedite hit identification in drug discovery owing to its ability to perform protein affinity selection with millions or billions of molecules in a few experiments. To expand the molecular diversity of DEL, it is critical to develop different types of DNA-encoded transformations that produce billions of molecules with distinct molecular scaffolds. Sequential functionalization of multiple C–H bonds provides a unique avenue for creating diversity and complexity from simple starting materials. However, the use of water as solvent, the presence of DNA, and the extremely low concentration of DNA-encoded coupling partners (0.001 M) have hampered the development of DNA-encoded C(sp³)–H activation reactions. Herein, we report the realization of palladium-catalyzed C(sp³)–H arylation of aliphatic carboxylic acids, amides and ketones with DNA-encoded aryl iodides in water. Notably, the present method enables the use of alternative sets of monofunctional building blocks, providing a linchpin to facilitate further setup for DELs. Furthermore, the C–H arylation chemistry enabled the on-DNA synthesis of structurally-diverse scaffolds containing enriched C(sp³) character, chiral centers, cyclopropane, cyclobutane, and heterocycles.

DNA-compatible C(sp³)–H activation reactions of aliphatic carboxylic acids, amides, and ketones were developed for efficient access to DEL synthesis.     

Smart sensors in environmental/water quality monitoring using IoT and cloud services

The growing social awareness and consequent concern for the environment has driven environmental analytical chemistry to a position of great prominence. In recent times, this position has translated into taking advantage of the great benefits provided by cloud computing and the Internet of Things (IoT), which are especially appropriate when devices such as chemical sensors are used. The use of such sensors is very common when in situ monitoring of environmental parameters is performed, but until recently, it was limited to the deployment of a small number of sensors. Currently, this approach has given way to genuine smart sensing systems (for instance, fully consolidated wireless sensor networks) that are able to provide a substantial amount of information. This type of sensor (the so-called smart sensor) is fundamentally characterized by (a) low consumption, versatility, and autonomy, (b) ease of integration with cloud solutions, (c) durability and reliability of IoT platforms and sensors, and (d) easy installation and deployment of sensor nodes. For all these reasons, and given the increasing importance and use of this type of device, a revision of the recent literature relating the development of smart sensors with environmental issues has been conducted, with major contributions being discussed, most notably those addressing the continuous in-line monitoring of water quality.     

Strain visualization for strained macrocycles

Strain has a unique and sometimes unpredictable impact on the properties and reactivity of molecules. To thoroughly describe strain in molecules, a computational tool that relates strain energy to reactivity by localizing and quantifying strain was developed. Strain energy is calculated local to every coordinate in the molecule and areas of higher strain are shown experimentally to be more reactive. Not only does this tool directly compare strain energy in parts of the same molecule, but it also computes total strain to give a full picture of molecular strain energy. It is freely available to the public on GitHub under the name StrainViz and much of the workflow is automated to simplify use for non-experts. Unique insight into the reactivity of curved aromatic molecules and strained alkyne bioorthogonal reagents is described within.

Strain has a unique and sometimes unpredictable impact on the properties and reactivity of molecules.     

Pathways to increase the dissymmetry in the interaction of chiral light and chiral molecules

The dissymmetric interaction between circularly polarised (CP) light and chiral molecules is central to a range of areas, from spectroscopy and imaging to next-generation photonic devices. However, the selectivity in absorption or emission of left-handed versus right-handed CP light is low for many molecular systems. In this perspective, we assess the magnitude of the measured chiroptical response for a variety of chiral systems, ranging from small molecules to large supramolecular assemblies, and highlight the challenges towards enhancing chiroptical activity. We explain the origins of low CP dissymmetry and showcase recent examples in which molecular design, and the modification of light itself, enable larger responses. Our discussion spans spatial extension of the chiral chromophore, manipulation of transition dipole moments, exploitation of forbidden transitions and creation of macroscopic chiral structures; all of which can increase the dissymmetry. Whilst the specific strategy taken to enhance the dissymmetric interaction will depend on the application of interest, these approaches offer hope for the development and advancement of all research fields that involve interactions of chiral molecules and light.

This perspective explores the dissymmetric interaction between circularly polarised (CP) light and chiral molecules. Such interactions are central to many applications from next generation displays to asymmetric photochemical synthesis.     

Beyond generative models: superfast traversal,optimization, novelty,exploration and discovery (STONED) algorithm for molecules using SELFIES

Inverse design allows the generation of molecules with desirable physical quantities using property optimization. Deep generative models have recently been applied to tackle inverse design, as they possess the ability to optimize molecular properties directly through structure modification using gradients. While the ability to carry out direct property optimizations is promising, the use of generative deep learning models to solve practical problems requires large amounts of data and is very time-consuming. In this work, we propose STONED – a simple and efficient algorithm to perform interpolation and exploration in the chemical space, comparable to deep generative models. STONED bypasses the need for large amounts of data and training times by using string modifications in the SELFIES molecular representation. First, we achieve non-trivial performance on typical benchmarks for generative models without any training. Additionally, we demonstrate applications in high-throughput virtual screening for the design of drugs, photovoltaics, and the construction of chemical paths, allowing for both property and structure-based interpolation in the chemical space. Overall, we anticipate our results to be a stepping stone for developing more sophisticated inverse design models and benchmarking tools, ultimately helping generative models achieve wider adoption.

Interpolation and exploration within the chemical space for inverse design.     

Molecularly-tunable nanoelectrode arrays created by harnessing intermolecular interactions

Intermolecular interactions play a critical role in the binding strength of molecular assemblies on surfaces. The ability to harness them enables molecularly-tunable interfacial structures and properties. Herein we report the tuning of the intermolecular interactions in monolayer assemblies derived from organothiols of different structures for the creation of nanoelectrode arrays or ensembles with effective mass transport by a molecular-level perforation strategy. The homo- and hetero-intermolecular interactions can be fully controlled, which is demonstrated not only by thermodynamic analysis of the fractional coverage but also by surface infrared reflection absorption and X-ray photoelectron spectroscopic characterizations. This understanding enables controllable electrochemical perforation for the creation of ensembles or arrays of channels across the monolayer thickness with molecular and nanoscale dimensions. Redox reactions on the nanoelectrode array display molecular tunability with a radial diffusion characteristic in good agreement with theoretical simulation results. These findings have implications for designing membrane-type ion-gating, electrochemical sensing, and electrochemical energy storage devices with molecular level tunability.

Intermolecular interactions in monolayer assembly are harnessed for creating molecularly-tunable nanoelectrode arrays or ensembles.     

Diversified strategy for the synthesis of DNA-encoded oxindole libraries

DNA-encoded library technology (DELT) employs DNA as a barcode to track the sequence of chemical reactions and enables the design and synthesis of libraries with billions of small molecules through combinatorial expansion. This powerful technology platform has been successfully demonstrated for hit identification and target validation for many types of diseases. As a highly integrated technology platform, DEL is capable of accelerating the translation of synthetic chemistry by using on-DNA compatible reactions or off-DNA scaffold synthesis. Herein, we report the development of a series of novel on-DNA transformations based on oxindole scaffolds for the design and synthesis of diversity-oriented DNA-encoded libraries for screening. Specifically, we have developed 1,3-dipolar cyclizations, cyclopropanations, ring-opening of reactions of aziridines and Claisen–Schmidt condensations to construct diverse oxindole derivatives. The majority of these transformations enable a diversity-oriented synthesis of DNA-encoded oxindole libraries which have been used in the successful hit identification for three protein targets. We have demonstrated that a diversified strategy for DEL synthesis could accelerate the application of synthetic chemistry for drug discovery.

Constructing DNA-encoded oxindole libraries by a diversified strategy.