One of the greenest and promising ways to solve the problem of freshwater crisis is surface solar steam generation from seawater. A great number of photothermal materials with multi-component and multi-layered delicate yet complex structures often suffer from either low evaporation rate or high energy loss. Here, this work presents a single component foam evaporator with steam generation rate of up to 4.32 kg m-2 h-1 under 1 sun irradiation. The evaporator is constructed from an aniline oligomer as a single light-absorbing component, covalent linked with polyethylene glycol to form a monolithic polymer foam. Floating on the seawater, the foam has absorbance of 99.5% over the entire solar spectral range and low thermal conductivity (0.0077 W K-1m-1) that effectively retains heat in the material and at the interface. After 3 months of continuous outdoor natural sunlight irradiation, the evaporator maintains a stable and durable evaporation rate. Moreover, the materials have good mechanical properties (7.48 MPa young's modulus and 57.38% elongation at break) and excellent chemical resistance in 10 common organic solvents and aqueous solutions of pH = 1 to 14. This study provides a new system and strategy for desalination, steam power generation, treatment of polluted water and sewage, etc.
Incorporating flexible insulating polymers is a straightforward strategy to enhance the mechanical properties of rigid conjugated polymers, enabling their use in flexible electronic devices. However, maintaining electronic characteristics simultaneously is challenging due to the poor miscibility between insulating polymers and conjugated polymers. This study introduces the carboxylation of insulating polymers as an effective strategy to enhance miscibility with conjugated polymers via surface energy modulation and hydrogen bonding. The carboxylated elastomer, synthesized via a thiol-ene click reaction, closely matches the surface energy of the conjugated polymer. This significantly improves the mechanical properties, achieving a high crack-onset strain of 21.48%, surpassing that (5.93%) of the unmodified elastomer:conjugated polymer blend. Upon incorporating the carboxylated elastomer into PM6:L8-BO-based organic solar cells, an impressive power conversion efficiency of 19.04% is attained, which top-performs among insulating polymer-incorporated devices and outperforms devices with unmodified elastomer or neat PM6:L8-BO. The superior efficiency is attributed to the optimized microstructures and enhanced crystallinity for efficient and balanced charge transport, and suppressed charge recombination. Furthermore, flexible devices with 5% carboxylated elastomer exhibit superior mechanical stability, retaining ≈88.9% of the initial efficiency after 40 000 bending cycles at a 1 mm radius, surpassing ≈83.5% for devices with 5% unmodified elastomer.
Nickel oxide (NiOx ) has garnered considerable attention as a prospective hole-transporting layer (HTL) in organic solar cells (OSCs), offering a potential solution to the stability challenges posed by traditional HTL, PEDOT:PSS, arising from acidity and hygroscopicity. Nevertheless, the lower work function (WF) of NiOx relative to donor polymers reduces charge injection efficiency in OSCs. Herein, NiOx nanoparticles are tailored through rare earth doping to optimize WF and the impact of ionic radius on their electronic properties is explored. Lanthanum (La3+ ) and yttrium (Y3+ ) ions, with larger ionic radii, are effectively doped at 1 and 3%, respectively, while scandium (Sc3+ ), with a smaller ion radius, allows enhanced 5% doping. Higher doping ratios significantly enhance WF of NiOx . A 5% Sc3+ doping raises WF to 4.99 eV from 4.77 eV for neat NiOx while maintaining high conductivity. Consequently, using 5% Sc-doped NiOx as HTL improves the power conversion efficiency (PCE) of OSCs to 17.13%, surpassing the 15.64% with the neat NiOx . Further enhancement to 18.42% is achieved by introducing the reductant catechol, outperforming the PEDOT:PSS-based devices. Additionally, when employed in a ternary blend system (D18:N3:F-BTA3), an impressive PCE of 19.18 % is realized, top-performing among reported OSCs utilizing solution-processed inorganic nanoparticles.
OBJECTIVE: To explore the clinical characteristics and genetic etiology of three children with Menkes disease. METHODS: Three children who had presented at the Children's Medical Center, the Affiliated Hospital of Guangdong Medical University from January 2020 to July 2022 were selected as the study subjects. Clinical data of the children were reviewed. Genomic DNA was extracted from peripheral blood samples of the children, their parents and sister of child 1. Whole exome sequencing (WES) was carried out. Candidate variants were verified by Sanger sequencing, copy number variation sequencing (CNV-seq), and bioinformatic analysis. RESULTS: Child 1 was a 1-year-and-4-month male, and children 2 and 3 were monozygotic twin males aged 1-year-and-10-month. The clinical manifestations of the three children have included developmental delay and seizures. WES showed that child 1 has harbored a c.3294+1G>A variant of the ATP7A gene. Sanger sequencing confirmed that his parents and sister did not carry the same variant, suggesting that it was de novo. Children 2 and 3 had carried a c.77266650_77267178del copy number variation. CNV-seq results showed that their mother has carried the same variant. By searching the HGMD, OMIM and ClinVar databases, the c.3294+1G>A was known to be pathogenic. No carrier frequency has been recorded in the 1000 Genomes, ESP, ExAC and gnomAD databases. Based on the Standards and Guidelines for the Interpretation of Sequence Variants: A Joint Consensus Recommendation of the American College of Medical Genetics and Genomics (ACMG), the ATP7A gene c.3294+1G>A variant was predicted to be pathogenic. The c.77266650_77267178del variant has involved exons 8 to 9 of the ATP7A gene. ClinGen online system score for it was 1.8, which was also considered to be pathogenic. CONCLUSION: The c.3294+1G>A and c.77266650_ 77267178del variants of the ATP7A gene probably underlay the Menkes disease in the three children. Above finding has enriched the mutational spectrum of Menkes disease and provided a basis for clinical diagnosis and genetic counseling.
Copper-Transporting ATPases , Menkes Kinky Hair Syndrome , Humans , Male , Computational Biology , Copper-Transporting ATPases/genetics , DNA Copy Number Variations , Exons , Menkes Kinky Hair Syndrome/genetics , Mutation , Peptide Fragments , Seizures , Infant
With the exponentially rapid development of solar-driven interfacial evaporation, evaporators with both high evaporation efficiency and recyclability are highly desirable to alleviate resource waste and environmental problems but remain challenging. Here, a monolithic evaporator was developed based on a dynamic disulfide vitrimer (a covalently cross-linked polymer network with associative exchangeable covalent bonds). Two types of solar absorbers, carbon nanotubes and oligoanilines, were simultaneously introduced to enhance the optical absorption. A high evaporation efficiency of 89.2% was achieved at 1 sun (1 kW m-2). When the evaporator was applied to solar desalination, it shows self-cleaning performance with long-term stability. Drinkable water with low ion concentrations satisfying the drinkable water levels of the World Health Organization and a high output (8.66 kg m-2, 8 h per day) was obtained, revealing great potential for practical seawater desalination. Moreover, a high-performance film material was obtained from the used evaporator via simple hot-pressing, indicating excellent fully closed-loop recyclability of the evaporator. This work provides a promising platform for high-efficiency and recyclable solar-driven interfacial evaporators.
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a widely used hole transporting layer (HTL) in organic solar cells (OSCs), but its acidity severely reduces the stability of devices. Until now, very few HTLs were developed to replace PEDOT:PSS toward stable and high-performance OSCs. Herein, a new cobalt-lanthanum (Co-La) inorganic system was reported as HTL to show a high conversion efficiency (PCE) of 18.82 %, which is among the top PCEs in binary OSCs. Since electron-rich outer shell of La atom can interact with Co atom to form charge transfer complex, the work function and conductivity of the Co-La system could be simultaneously enhanced compared to Co or La-based HTLs. This Co-La system could also be applied into other OSCs to show high performance. All these results demonstrate that binary Co-La systems as HTL can efficiently tackle the issue in hole transporting and show powerful application in OSCs to replace PEDOT:PSS.
Ultrathin organic solar cells (OSCs) with both high power conversion efficiency (PCE) and operational stability are of great significance for the industrial applications but still challenging. Here, a polyimide (PI) substrate for high-performance and stable ultrathin OSCs, which is physically crosslinked via strong hydrogen bonds (denoted as HB-PI) to enhance the mechanical, thermal, solvent-resistant, and UV filtering properties (with a cut-off wavelength of 376 nm), is synthesized. An ultrathin flexible transparent composite electrode (FTCE, ≈7 µm) is fabricated via semi-embedding AgNWs in the HB-PI substrate. The FTCE possesses excellent optoelectronic property, smooth surface, and high mechanical stability simultaneously. Based on this FTCE, an ultrathin OSC is constructed with a PCE of 13.52% (average of 13.22%). Moreover, the ultrathin OSC shows outstanding mechanical stability (PCE decreased by less than 4% after 1000 bending cycles at a small bending radius of 0.5 mm) and superior UV light stability (no evident PCE degradation after irradiation under UV light for 10 h). This work will provide a new avenue for fabricating high-performance and stable ultrathin OSCs.
Ultraflexible organic solar cells (OSCs) with both high power conversion efficiency (PCE) and good mechanical robustness are still challenging, in which flexible transparent composite electrodes (FTCEs, substrate-cum-electrodes) play critical roles. Here, an ultrathin FTCE (â¼9 µm) via semi-embedding a silver nanowire electrode in a colorless polyimide (CPI) substrate was developed, which simultaneously possessed outstanding performance such as low square resistance (Rsq â¼ 12.7 Ω sq-1), high optical transmittance (T550 â¼ 86.3%), smooth surface (root-mean-square â¼ 0.32 nm), and excellent thermal, mechanical, and solution producing stability. Prior to the FTCE fabrication, four CPI samples with the number-average molecular weight ranging from 35.9 to 177.5 kDa were prepared and their optical, mechanical, and thermal properties were studied in detail. Moreover, the effect of the molecular weight on the minimum thickness that can withstand the following solution production of ultraflexible OSCs was investigated, which revealed that the molecular weight of CPI here should be above 81.4 kDa. Based on the FTCE, an ultraflexible OSC with a high PCE value of 14.37% and outstanding mechanical robustness was constructed, in which the PCE could still maintain above 96% of its initial value after 1000 bending cycles at a bending radius of 0.5 mm.
Adding insulating polymers to conjugated polymers is an efficient strategy to tailor their mechanical properties for flexible organic electronics. In this work, we selected two insulating polymers as additives for high-performance photoactive layers and investigated the mechanical and photovoltaic properties in organic solar cells (OSCs). The insulating polymers were found to reduce the electron mobilities in the photoactive layers, and hence the power conversion efficiencies were significantly decreased. More importantly, we found that the insulating polymers exhibited negative effect on the mechanical properties of the photoactive layers, with reduced Young's modulus and low crack onset strains. Further studies revealed that the insulating polymers had poor miscibility with the photoactive layers, providing large domains and more cavities in blend thin films, which act as negative effect for the tensile test. The studies indicate that rational selection of insulating polymers, especially enhancing the non-covalent interaction with the photoactive layers, will be critically important for the stretchable OSCs.
Owing to the advantages of being lightweight and compatible with surfaces with different deformations, flexible organic solar cells (OSCs) have broad scopes of applications, including wearable electronics and portable devices. Most flexible OSCs focus on the two-component bulk-heterojunction (BHJ) photo-active layers, but they usually suffer from degradation problems both in efficiency and mechanical durability derived from the limited phase stability under mechanical and thermal stress. Whereas, single-component organic solar cells (SCOSCs) based on the double-cable conjugated polymer are supposed to possess excellent mechanical robustness and long-term stability. Here, the first flexible SCOSCs based on a double-cable polymer are fabricated on a transparent silver nanowires (AgNWs) electrode on a plastic foil. Impressively, the obtained flexible SCOSCs exhibited a power conversion efficiency (PCE) of 7.21%. The flexible SCOSCs are further demonstrated to possess superior mechanical robustness (>95% retention after 1000 bending cycles) and storage stability (>97% retention after 430 h in nitrogen atmosphere) compared to several BHJ-type flexible OSCs. The pseudo-free-standing tensile test and morphology investigation are conducted to reveal the distinction in mechanical durability of the single-component polymer film and the BHJ-type films. Besides, ultraflexible SCOSCs are also fabricated, indicating the application prospect and superiority in flexible devices and wearable electronic products.
The development of nonfullerene small molecular acceptors (NF-SMAs) has dominated the improvement of efficiencies for organic solar cells and the near-infrared (NIR) absorption is the primary feature of NF-SMAs compared with fullerene derivatives. In this article, a series of acceptor-donor-acceptor-structured NF-SMAs (named CPICs) containing 4H-cyclopenta[1,2-b : 5,4-b']dithiophene (CPDT) electron donor and F-substituted 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2FIC) as electron acceptor were designed and synthesized. With the increase of CPDT units, the elongated conjugations broadened the absorption range of the acceptors and tuned their energy levels sequentially. Therefore, their charge-transporting polarities switched from electron-only type to bipolar mode in organic field-effect transistors. Moreover, these changes also influenced the voltages, current densities, and eventual PCEs of their corresponding cells. When blending with PBDB-T, a champion efficiency of 10.01% was achieved in CPIC-2 based cells. This work demonstrated the importance of absorptions, suitable energy levels and charge transports in improving the efficiencies of organic solar cells.
ConspectusConjugated polymers for application in organic solar cells (OSCs) have been developed from poly(phenylenevinylene) to poly(3-hexylthiophene) and then to "donor-acceptor" structures, providing power conversion efficiencies (PCEs) over 18% when blending with the electron acceptor as a two-component photoactive layer. Besides, graft-structural double-cable conjugated polymers that use an electron donor as conjugated backbones and an electron acceptor as pendant side units are one kind of conjugated polymer, in which charge carriers are generated in a single polymer. Therefore, double-cable conjugated polymers can be used as a single photoactive layer in single-component OSCs (SCOSCs). The covalently linked electron donor and acceptor enable double-cable polymers to maintain stable microstructures during long-term operation compared to two-component systems, which is very important for OSCs toward large-area applications. However, SCOSCs based on double-cable conjugated polymers provided PCEs below 3% in a long period, which is lagging far behind PCEs of two-component OSCs. The key reason for this is the limited number of chemical structures and the difficulty to tune the morphology in these polymers.In this Account, we provide an overview about our efforts on developing new double-cable conjugated polymers with rylene diimides as side units, and how to realize high PCEs in SCOSC devices. The studies start from developing a "functionalization-polymerization" method to synthesize the polymers containing rylene diimide acceptors, so that large amounts of double-cable conjugated polymers with distinct physical and electrochemical properties were obtained. Then, we will discuss how to control the nanophase separation in the crystalline region and optimize the miscibility in the amorphous region of double-cable polymers, simultaneously facilitating exciton dissociation and charge transport. With these efforts, a high PCE of 8.4% has been obtained, representing the record PCE in SCOSCs. In addition, the physical process and the stability of SCOSCs will be discussed. We hope that this account will inspire many innovative studies in this field and push the PCEs of SCOSCs to a new stage.
Covalent adaptable networks (CANs) represent a novel covalently cross-linked polymer that is capable of being reprocessed and recycled relying on reversible covalent bond structures and present exceptional opportunities in a wide range of prospective applications. However, it is genuinely difficult to fabricate bulk CAN blocks with solid-core geometries that possess complex shapes or multiple materials, which are crucial in cutting-edge fields such as soft robotics, flexible electronic devices and biomedical engineering. Here we report a welding technique to strategically construct complex and heterogeneous 3D CAN structures by utilizing a solder doped with magnetic nanoparticles. The solder is able to induce a bond exchange reaction at the interface between the to-be-welded pieces. Using this method, not only CAN bulks with the same materials can be welded to form complex geometries, distinctive bulks with different physical properties and chemical compositions can also be connected to fabricate multimaterial devices. Besides, this method can be used to repair damaged CAN materials and efficiently recycle scrap CAN materials, which can effectively save resources and protect the environment. The universality and robustness of this strategy is expected to promote CAN application in broader functional polymer fields.
Liquid-crystalline elastomers (LCEs) are excellent soft actuator materials for a wide range of applications, especially the blooming area of soft robotics. For entirely soft LCE robots to exhibit high dexterity and complicated performance, several components are typically required to be integrated together in one single robot body. Here, we show that seamless multicomponent/multimaterial three-dimensional (3D) LCE robots can be created via simultaneously welding and aligning LCE materials with different chemical compositions and physical properties without other additives such as tapes and glues (just like metal welding). Both welding and aligning of the LCE materials rely on thermal polymerization of preformed LCE films with reactive acrylate groups. This method provides an easy way to robustly fabricate arbitrary 3D desirable geometries with strongly stable reversible actuations and multifunctionalities, which greatly enlarges and benefits the future applications and manufacturing of LCE soft robots.
Thermal reprogrammability is essential for new-generation large dry soft actuators, but the realization sacrifices the favored actuation performance. The contradiction between thermal reprogrammability and stability hampers efforts to design high-performance soft actuators to be robust and thermally adaptable. Now, a strategy has been developed that relies on repeatedly switching on/off thermal reprogrammability in liquid-crystalline elastomer (LCE) actuators to resolve this problem. By post-synthesis swelling, a latent siloxane exchange reaction can be induced in the common siloxane LCEs (switching on), enabling reprogramming into on-demand 3D-shaped actuators; by switching off the dynamic network by heating, actuation stability is guaranteed even at high temperature (180 °C). Using partially black-ink-patterned LCEs, selectively switching off reprogrammability allows integration of completely different actuation modes in one monolithic actuator for more delicate and elaborate tasks.
Widely used traditional thermosets are good candidates for construction of 3D soft actuators because of their excellent stability; however, it is generally acknowledged that they cannot be reprocessed. The time-temperature equivalence principle enables reprocessing of traditional liquid crystalline epoxy thermosets (LCETs) into 3D soft actuators. Even though the transesterification reaction of LCETs is extremely slow, it is fast enough to induce a topology rearrangement and subsequent reprocessing when prolonging the transesterification time according to aforementioned principle. Therefore, LCETs can be aligned by a simple procedure. The alignment is quite stable at high temperature and remains after more than 1000 heating-cooling actuation cycles. The resulting 3D soft actuators are remouldable, reprogrammable, reconfigurable, weldable, self-healable, recyclable, and stable, which is impossible for any traditional thermosets and is therefore a compelling advance in terms of the applications open to 3D soft actuators.
Toward a sustainable society, soft actuators driven by environmentally friendly energy from nature are of great social and economic significance. Meanwhile, recyclability, repeated reconfiguration for other use, and complex three-dimensional (3D) geometries are also essential for mitigating the energy crisis and practical application demands. Here, we integrate all of the above features in one actuator using vitrimers with exchangeable disulfide links. By reconfiguration, welding, patterning, and kirigami techniques, complex 3D actuators can be easily fabricated, which can be repeatedly reconfigured for other applications to save cost in new material preparation. These actuators operate synergistically with the day-night rhythm of humidity and sunlight without the need of extra energy input.
Vitrimer-based liquid-crystalline elastomers (LCEs) exhibit great advantages over the traditional LCEs due to their inherent processability to realize monodomain alignment and construction of LCE actuators with complex 3D structures in a robust way. Though exciting progress has been made, how to achieve a proper balance between processability and actuation durability/stability remains a big challenge. Here, we report a strategy to mitigate the conflict between processability and actuation stability by reducing the catalyst content in an epoxy/acid LCE vitrimer system. With a relatively low catalyst content (0.25 mol% to carboxyl group), monodomain LCEs with large actuation strain (â¼95%) and excellent actuation stability (the actuation strain is completely maintained after 100 heating-cooling cycles and more than 90% of the initial strain is retained even after 500 cycles) could be easily prepared. Moreover, the monodomain LCEs can still be readily realigned or directly reconfigured into complex reversible 3D actuators.
Capillary column packed with silica colloidal crystals (SCC) exhibits great efficiency in liquid chromatography because of its highly-ordered structure and extremely narrow channels (about hundred nanometer in diameter) between the particles. However, problems arise due to the extremely high back-pressure created with its dense packings. It is also a challenge to prepare a stable SCC column with an appropriate length for chromatographic separation on a commercial instrument. We have synthesized monodispersed, sub-micron SiO2 particles bonded with C18 functionality and fabricated SCC capillary columns up to 100 mm in length. The packing materials in the column displayed Bragg diffraction with blueish color under irradiation with white light, indicating the formation of SCC. The column performance was evaluated using pressurized capillary electrochromatography (pCEC) and column efficiencies of more than a hundred thousand plates per column (plate height < 1 µm) were achieved using peptide as a sample. The run-to-run reproducibility expressed with RSD in terms of retention time and peak area for aromatic compounds were less than 0.076% and 1.96%, respectively. These results demonstrate that the combination of pCEC and SCC columns may provide an innovative analytical technique with extraordinary efficiency, resolution and speed for the separation of complex samples.
Capillary Electrochromatography/methods , Silicon Dioxide/chemistry , Chromatography, Liquid/methods , Colloids/chemistry , Crystallization , Electroosmosis , Hydrocarbons, Aromatic/isolation & purification , Peptides/isolation & purification , Porosity , Pressure , Reproducibility of Results
[This corrects the article DOI: 10.1039/C7SC02967E.].
