MXene-Enhanced Nanoscale Photoconduction in Perovskite Solar Cells Revealed by Conductive Atomic Force Microscopy.

The use of MXene materials in perovskite solar cells (PSCs) has received significant interest due to their distinct features that result from the termination of functional groups and the oxidation of MXene. Herein, we have used photoconductive atomic force microscopy (pcAFM) to map the local (nanoscale) photovoltaic performances of the Ti3C2Tx MXene nanosheet-integrated TiO2 (MXene@TiO2) electron transport layer-based PSCs to determine the influence of the treatment on the microscopic charge flow inside the devices. At different applied voltages, the morphology and current have been simultaneously measured with nanoscale resolution from the top surfaces of the solar cells without back contacts. The PSCs based on MXene@TiO2 exhibit more enhanced current flow across the grains than the only TiO2-based PSCs. At zero applied bias, the average local photocurrent for MXene-integrated PSCs is several times higher than the reference PSCs and decreases gradually when the positive bias is increased until the open circuit voltage. Considerable differences were also observed in the short circuit current among different locations that appear identical in AFM topography. Our findings reveal the potential of MXene-integrated ETLs to enhance the nanoscale photoconduction and inherent characteristics of the active layers, thereby improving the performance of the polycrystalline photovoltaic devices.

A simple polystyrene microfluidic device for sensitive and accurate SERS-based detection of infection by malaria parasites.

Early and accurate detection of infection by pathogenic microorganisms, such as Plasmodium, the causative agent of malaria, is critical for clinical diagnosis and ultimately determines the patient's outcome. We have combined a polystyrene-based microfluidic device with an immunoassay which utilises Surface-Enhanced Raman Spectroscopy (SERS) to detect malaria. The method can be easily translated to a point-of-care testing format and shows excellent sensitivity and specificity, when compared to the gold standard for laboratorial detection of Plasmodium infections. The device can be fabricated in less than 30 min by direct patterning on shrinkable polystyrene sheets of adaptable three-dimensional microfluidic chips. To validate the microfluidic system, samples of P. falciparum-infected red blood cell cultures were used. The SERS-based immunoassay enabled the detection of 0.0012 ± 0.0001% parasitaemia in a P. falciparum-infected red blood cell culture supernatant, an ∼7-fold higher sensitivity than that attained by most rapid diagnostic tests. Our approach successfully overcomes the main challenges of the current Plasmodium detection methods, including increased reproducibility, sensitivity, and specificity. Furthermore, our system can be easily adapted for detection of other pathogens and has excellent properties for early diagnosis of infectious diseases, a decisive step towards lowering their high burden on healthcare systems worldwide.

Microwave Synthesis of Visible-Light-Activated g-C3N4/TiO2 Photocatalysts.

The preparation of visible-light-driven photocatalysts has become highly appealing for environmental remediation through simple, fast and green chemical methods. The current study reports the synthesis and characterization of graphitic carbon nitride/titanium dioxide (g-C3N4/TiO2) heterostructures through a fast (1 h) and simple microwave-assisted approach. Different g-C3N4 amounts mixed with TiO2 (15, 30 and 45 wt. %) were investigated for the photocatalytic degradation of a recalcitrant azo dye (methyl orange (MO)) under solar simulating light. X-ray diffraction (XRD) revealed the anatase TiO2 phase for the pure material and all heterostructures produced. Scanning electron microscopy (SEM) showed that by increasing the amount of g-C3N4 in the synthesis, large TiO2 aggregates composed of irregularly shaped particles were disintegrated and resulted in smaller ones, composing a film that covered the g-C3N4 nanosheets. Scanning transmission electron microscopy (STEM) analyses confirmed the existence of an effective interface between a g-C3N4 nanosheet and a TiO2 nanocrystal. X-ray photoelectron spectroscopy (XPS) evidenced no chemical alterations to both g-C3N4 and TiO2 at the heterostructure. The visible-light absorption shift was indicated by the red shift in the absorption onset through the ultraviolet-visible (UV-VIS) absorption spectra. The 30 wt. % of g-C3N4/TiO2 heterostructure showed the best photocatalytic performance, with a MO dye degradation of 85% in 4 h, corresponding to an enhanced efficiency of almost 2 and 10 times greater than that of pure TiO2 and g-C3N4 nanosheets, respectively. Superoxide radical species were found to be the most active radical species in the MO photodegradation process. The creation of a type-II heterostructure is highly suggested due to the negligible participation of hydroxyl radical species in the photodegradation process. The superior photocatalytic activity was attributed to the synergy of g-C3N4 and TiO2 materials.

Condensation and Protection of DNA by the Myxococcus xanthus Encapsulin: A Novel Function.

Encapsulins are protein nanocages capable of harboring smaller proteins (cargo proteins) within their cavity. The function of the encapsulin systems is related to the encapsulated cargo proteins. The Myxococcus xanthus encapsulin (EncA) naturally encapsulates ferritin-like proteins EncB and EncC as cargo, resulting in a large iron storage nanocompartment, able to accommodate up to 30,000 iron atoms per shell. In the present manuscript we describe the binding and protection of circular double stranded DNA (pUC19) by EncA using electrophoretic mobility shift assays (EMSA), atomic force microscopy (AFM), and DNase protection assays. EncA binds pUC19 with an apparent dissociation constant of 0.3 ± 0.1 µM and a Hill coefficient of 1.4 ± 0.1, while EncC alone showed no interaction with DNA. Accordingly, the EncAC complex displayed a similar DNA binding capacity as the EncA protein. The data suggest that initially, EncA converts the plasmid DNA from a supercoiled to a more relaxed form with a beads-on-a-string morphology. At higher concentrations, EncA self-aggregates, condensing the DNA. This process physically protects DNA from enzymatic digestion by DNase I. The secondary structure and thermal stability of EncA and the EncA-pUC19 complex were evaluated using synchrotron radiation circular dichroism (SRCD) spectroscopy. The overall secondary structure of EncA is maintained upon interaction with pUC19 while the melting temperature of the protein (Tm) slightly increased from 76 ± 1 °C to 79 ± 1 °C. Our work reports, for the first time, the in vitro capacity of an encapsulin shell to interact and protect plasmid DNA similarly to other protein nanocages that may be relevant in vivo.

Interindividual heterogeneity affects the outcome of human cardiac tissue decellularization.

The extracellular matrix (ECM) of engineered human cardiac tissues corresponds to simplistic biomaterials that allow tissue assembly, or animal derived off-the-shelf non-cardiac specific matrices. Decellularized ECM from human cardiac tissue could provide a means to improve the mimicry of engineered human cardiac tissues. Decellularization of cardiac tissue samples using immersion-based methods can produce acceptable cardiac ECM scaffolds; however, these protocols are mostly described for animal tissue preparations. We have tested four methods to decellularize human cardiac tissue and evaluated their efficiency in terms of cell removal and preservation of key ECM components, such as collagens and sulfated glycosaminoglycans. Extended exposure to decellularization agents, namely sodium dodecyl sulfate and Triton-X-100, was needed to significantly remove DNA content by approximately 93% in all human donors. However, the biochemical composition of decellularized tissue is affected, and the preservation of ECM architecture is donor dependent. Our results indicate that standardization of decellularization protocols for human tissue is likely unfeasible, and a compromise between cell removal and ECM preservation must be established in accordance with the scaffold's intended application. Notwithstanding, decellularized human cardiac ECM supported human induced pluripotent-derived cardiomyocyte (hiPSC-CM) attachment and retention for up to 2 weeks of culture, and promoted cell alignment and contraction, providing evidence it could be a valuable tool for cardiac tissue engineering.

Reusable and highly sensitive SERS immunoassay utilizing gold nanostars and a cellulose hydrogel-based platform.

The development of robust and sensitive point-of-care testing platforms is necessary to improve patient care and outcomes. Surface-enhanced Raman scattering (SERS)-based immunosensors are especially suited for this purpose. Here, we present a highly sensitive and selective SERS immunoassay, demonstrating for example the detection of horseradish peroxidase (HRP), in a sandwich format. The strength of our biosensor lies in merging: (i) SERS-immunotags based on gold nanostars, allowing exceptional intense SERS from attached Raman probes, covalent attachment of anti-HRP antibodies by a simple chemical method providing exceptional antigen binding activity; (ii) the ease of preparation of the capture platform from a regenerated cellulose-based hydrogel, a transparent material, ideal for microfluidics applications, with low background fluorescence and Raman signal, particularly suited for preserving high activity of the covalently bound anti-HRP antibodies. The sandwich complexes formed were characterised by atomic force microscopy, and by scanning electron microscopy coupled with electron diffraction spectroscopy; and (iii) the robustness of the simple Classical Least Squares method for SERS data analysis, resulting in superior discrimination of SERS signals from the background and much better data fitting, compared to the commonly used peak integral method. Our SERS immunoassay greatly improves the detection limits of traditional enzyme-linked immunosorbent assay approaches, and its performance is better or comparable to those of existing SERS-based immunosensors. Our approach successfully overcomes the main challenges of application at point-of-care, including increasing reproducibility, sensitivity, and specificity, associated with an environmentally friendly and robust design. Also, the proposed design withstands several cycles of regeneration, a feature absent in paper-SERS immunoassays and this opens the way for sensitive multiplexing applications on a microfluidic platform.

Human Extracellular-Matrix Functionalization of 3D hiPSC-Based Cardiac Tissues Improves Cardiomyocyte Maturation.

Human induced pluripotent stem cells (hiPSC) possess significant therapeutic potential due to their high self-renewal capability and potential to differentiate into specialized cells such as cardiomyocytes. However, generated hiPSC-derived cardiomyocytes (hiPSC-CM) are still immature, with phenotypic and functional features resembling the fetal rather than their adult counterparts, which limits their application in cell-based therapies, in vitro cardiac disease modeling, and drug cardiotoxicity screening. Recent discoveries have demonstrated the potential of the extracellular matrix (ECM) as a critical regulator in development, homeostasis, and injury of the cardiac microenvironment. Within this context, this work aimed to assess the impact of human cardiac ECM in the phenotype and maturation features of hiPSC-CM. Human ECM was isolated from myocardium tissue through a physical decellularization approach. The cardiac tissue decellularization process reduced DNA content significantly while maintaining ECM composition in terms of sulfated glycosaminoglycans (s-GAG) and collagen content. These ECM particles were successfully incorporated in three-dimensional (3D) hiPSC-CM aggregates (CM+ECM) with no impact on viability and metabolic activity throughout 20 days in 3D culture conditions. Also, CM+ECM aggregates displayed organized and longer sarcomeres, with improved calcium handling when compared to hiPSC-CM aggregates. This study shows that human cardiac ECM functionalization of hiPSC-based cardiac tissues improves cardiomyocyte maturation. The knowledge generated herein provides essential insights to streamline the application of ECM in the development of hiPSC-based therapies targeting cardiac diseases.

Toward a Microencapsulated 3D hiPSC-Derived in vitro Cardiac Microtissue for Recapitulation of Human Heart Microenvironment Features.

The combination of cardiomyocytes (CM) and non-myocyte cardiac populations, such as endothelial cells (EC), and mesenchymal cells (MC), has been shown to be critical for recapitulation of the human heart tissue for in vitro cell-based modeling. However, most of the current engineered cardiac microtissues still rely on either (i) murine/human limited primary cell sources, (ii) animal-derived and undefined hydrogels/matrices with batch-to-batch variability, or (iii) culture systems with low compliance with pharmacological high-throughput screenings. In this work, we explored a culture platform based on alginate microencapsulation and suspension culture systems to develop three-dimensional (3D) human cardiac microtissues, which entails the co-culture of human induced pluripotent stem cell (hiPSC) cardiac derivatives including aggregates of hiPSC-CM and single cells of hiPSC-derived EC and MC (hiPSC-EC+MC). We demonstrate that the 3D human cardiac microtissues can be cultured for 15 days in dynamic conditions while maintaining the viability and phenotype of all cell populations. Noteworthy, we show that hiPSC-EC+MC survival was promoted by the co-culture with hiPSC-CM as compared to the control single-cell culture. Additionally, the presence of the hiPSC-EC+MC induced changes in the physical properties of the biomaterial, as observed by an increase in the elastic modulus of the cardiac microtissue when compared to the hiPSC-CM control culture. Detailed characterization of the 3D cardiac microtissues revealed that the crosstalk between hiPSC-CM, hiPSC-EC+MC, and extracellular matrix induced the maturation of hiPSC-CM. The cardiac microtissues displayed functional calcium signaling and respond to known cardiotoxins in a dose-dependent manner. This study is a step forward on the development of novel 3D cardiac microtissues that recapitulate features of the human cardiac microenvironment and is compliant with the larger numbers needed in preclinical research for toxicity assessment and disease modeling.

Supramolecular protein polymers using mini-ferritin Dps as the building block.

A missense mutant of a Dps protein (DNA-binding protein from starved cells) from Marinobacter hydrocarbonoclasticus was used as a building block to develop a new supramolecular assembly complex which enhances the iron uptake, a physiological function of this mini-ferritin. The missense mutation was conducted in an exposed and flexible region of the N-terminal, wherein a threonine residue in position 10 was replaced by a cysteine residue (DpsT10C). This step enabled a click chemistry approach to the variant DpsT10C, where a thiol-ene coupling occurs. Two methods and two types of linker were used resulting in two different mini-ferritin supramolecular polymers, which have maintained secondary structure and native iron uptake physiological function. Electrophoretic assays and mass spectrometry were utilized to confirm that both functionalization and coupling reactions occured as predicted. The secondary structure has been investigated by circular dichroism and synchrotron radiation circular dichroism. Size and morphology were obtained by dynamic light scattering, size exclusion chromatography and atomic force microscopy, respectively. The iron uptake of the synthesized protein polymers was confirmed by UV-Vis spectroscopy loading assays.

Antibody modified gold nanoparticles for fast colorimetric screening of rheumatoid arthritis.

Rheumatoid arthritis (RA) is a systemic autoimmune disease characterized by chronic joint inflammation and one of the main causes of chronic disability worldwide with high prevalence in the ageing population. RA is characterized by autoantibody production, synovial inflammation and bone destruction, and the most accepted biomarker is rheumatoid factor (RF) autoantibodies. In this work, we developed a low-cost approach for the detection and quantification of the RF marker. This colorimetric immunosensor is based on gold nanoprobe crosslinking that results in extensive aggregation in the presence of the pentameric IgM RF. Aggregation of the nanoconjugates yields a color change from red to purple that can be easily observed by the naked eye. The interaction between nanoconjugates and the specific target was confirmed via dynamic light scattering (DLS), Raman spectroscopy and atomic force microscopy (AFM) imaging. This conceptual system shows a LOD of 4.15 UA mL-1 IgM RF (clinical threshold is set for 20 IU mL-1). The one-step biosensor strategy herein proposed is much faster than conventional detection techniques, without the need for secondary antibodies, additional complex washing or signal amplification protocols. To the best of our knowledge this is the first report on target induced aggregation of gold nanoprobes for quantitative colorimetric autoantibody detection.

Imaging the Anomalous Charge Distribution Inside CsPbBr3 Perovskite Quantum Dots Sensitized Solar Cells.

Highly luminescent CsPbBr3 perovskite quantum dots (QDs) have gained huge attention in research due to their various applications in optoelectronics, including as a light absorber in photovoltaic solar cells. To improve the performances of such devices, it requires a deeper knowledge on the charge transport dynamics inside the solar cell, which are related to its power-conversion efficiency. Here, we report the successful fabrication of an all-inorganic CsPbBr3 perovskite QD sensitized solar cell and the imaging of anomalous electrical potential distribution across the layers of the cell under different illuminations using Kelvin probe force microscopy. Carrier generation, separation, and transport capacity inside the cells are dependent on the light illumination. Large differences in surface potential between electron and hole transport layers with unbalanced carrier separation at the junction have been observed under white light (full solar spectrum) illumination. However, under monochromatic light (single wavelength of solar spectrum) illumination, poor charge transport occurred across the junction as a consequence of less difference in surface potential between the active layers. The outcome of this study provides a clear idea on the carrier dynamic processes inside the cells and corresponding surface potential across the layers under the illumination of different wavelengths of light to understand the functioning of the solar cells and ultimately for the improvement of their photovoltaic performances.

Quantitative real-time monitoring of RCA amplification of cancer biomarkers mediated by a flexible ion sensitive platform.

Ion sensitive field-effect transistors (ISFET) are the basis of radical new sensing approaches. Reliable molecular characterization of specific detection of DNA and/or RNA is vital for disease diagnostics and to follow up alterations in gene expression profiles. Devices and strategies for biomolecular recognition and detection should be developed into reliable and inexpensive platforms. Here, we describe the development of a flexible thin-film sensor for label free gene expression analysis. A charge modulated ISFET based sensor was integrated with real-time DNA/RNA isothermal nucleic acid amplification: Loop-mediated isothermal amplification (LAMP) and Rolling Circle Amplification (RCA) techniques for c-MYC and BCR-ABL1 genes, allowing for the real-time quantification of template. Also, RCA allowed the direct quantification of RNA targets at room temperature, eliminating the requirement for external temperature controllers and overall complexity of the molecular diagnostic approach. This integration between the biological and the sensor/electronic approaches enabled the development of an inexpensive and direct gene expression-profiling platform.

Oxide-Based Solar Cell: Impact of Layer Thicknesses on the Device Performance.

A ZnO/Cu2O-based combinatorial heterojunction device library was successfully fabricated by a simple spray pyrolysis technique using ITO-coated glass as the substrate. The combinatorial approach was introduced to analyze the impact of the ZnO and Cu2O layer thicknesses on the performance of the solar cells. The thickness of the ZnO layer was varied from ∼50 to 320 nm, and the Cu2O layer was deposited orthogonal to the ZnO thickness gradient. In the case of Cu2O, the thickness varied from ∼200 to 800 nm. The photovoltaic performance of the cells is strongly dependent on the absorber layer thickness for a particular window layer thickness and reaches a maximum short-circuit current density of 3.9 mA/cm2 when the absorber layer thickness just crosses ∼700 nm. Reducing the thicknesses of the active layers leads to a sharp decrease in the device performance. It is shown that the entire built-in bias of the heterojunction is created in the absorber layer due to low carrier density. The poor performance of the devices having lower thicknesses is attributed to different interfacial phenomena such as optical losses due to the thin Cu2O layer, back-contact recombination of the carriers due to the low layer thickness because a minimum heterojunction thickness is required for the formation of the full built-in bias that slows down the recombination of the carriers, and other factors.

Observation of Space Charge Dynamics Inside an All Oxide Based Solar Cell.

The charge transfer dynamics at interfaces are fundamental to know the mechanism of photovoltaic processes. The internal potential in solar cell devices depends on the basic processes of photovoltaic effect such as charge carrier generation, separation, transport, recombination, etc. Here we report the direct observation of the surface potential depth profile over the cross-section of the ZnO nanorods/Cu2O based solar cell for two different layer thicknesses at different wavelengths of light using Kelvin probe force microscopy. The topography and phase images across the cross-section of the solar cell are also observed, where the interfaces are well-defined on the nanoscale. The potential profiling results demonstrate that under white light illumination, the photoinduced electrons in Cu2O inject into ZnO due to the interfacial electric field, which results in the large difference in surface potential between two active layers. However, under a single wavelength illumination, the charge carrier generation, separation, and transport processes between two active layers are limited, which affect the surface potential images and corresponding potential depth profile. Because of changes in the active layer thicknesses, small variations have been observed in the charge carrier transport mechanism inside the device. These results provide the clear idea about the charge carrier distribution inside the solar cell in different conditions and show the perfect illumination condition for large carrier transport in a high performance solar cell.

Stress Induced Mechano-electrical Writing-Reading of Polymer Film Powered by Contact Electrification Mechanism.

Mechano-electrical writing and reading in polyaniline (PANI) thin film are demonstrated via metal-polymer contact electrification mechanism (CEM). An innovative conception for a non-destructive self-powered writable-readable data sheet is presented which can pave the way towards new type of stress induced current harvesting devices. A localized forced deformation of the interface has been enacted by pressing the atomic force microscopic probe against the polymer surface, allowing charge transfer between materials interfaces. The process yields a well-defined charge pattern by transmuting mechanical stress in to readable information. The average of output current increment has been influenced from 0.5 nA to 15 nA for the applied force of 2 nN to 14 nN instead of electrical bias. These results underscore the importance of stress-induced current harvesting mechanism and could be scaled up for charge patterning of polymer surface to writable-readable data sheet. Time evolutional current distribution (TECD) study of the stress-induced patterned PANI surface shows the response of readability of the recorded data with time.

Microwave Synthesized ZnO Nanorod Arrays for UV Sensors: A Seed Layer Annealing Temperature Study.

The present work reports the influence of zinc oxide (ZnO) seed layer annealing temperature on structural, optical and electrical properties of ZnO nanorod arrays, synthesized by hydrothermal method assisted by microwave radiation, to be used as UV sensors. The ZnO seed layer was produced using the spin-coating method and several annealing temperatures, ranging from 100 to 500 °C, have been tested. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and spectrophotometry measurements have been used to investigate the structure, morphology, and optical properties variations of the produced ZnO nanorod arrays regarding the seed layer annealing temperatures employed. After the growth of ZnO nanorod arrays, the whole structure was tested as UV sensors, showing an increase in the sensitivity with the increase of seed layer annealing temperature. The UV sensor response of ZnO nanorod arrays produced with the seed layer annealed temperature of 500 °C was 50 times superior to the ones produced with a seed layer annealed at 100 °C.

Solvothermal synthesis of gallium-indium-zinc-oxide nanoparticles for electrolyte-gated transistors.

Solution-processed field-effect transistors are strategic building blocks when considering low-cost sustainable flexible electronics. Nevertheless, some challenges (e.g., processing temperature, reliability, reproducibility in large areas, and cost effectiveness) are requirements that must be surpassed in order to achieve high-performance transistors. The present work reports electrolyte-gated transistors using as channel layer gallium-indium-zinc-oxide nanoparticles produced by solvothermal synthesis combined with a solid-state electrolyte based on aqueous dispersions of vinyl acetate stabilized with cellulose derivatives, acrylic acid ester in styrene and lithium perchlorate. The devices fabricated using this approach display a ION/IOFF up to 1 × 10(6), threshold voltage (VTh) of 0.3-1.9 V, and mobility up to 1 cm(2)/(V s), as a function of gallium-indium-zinc-oxide ink formulation and two different annealing temperatures. These results validates the usage of electrolyte-gated transistors as a viable and promising alternative for nanoparticle based semiconductor devices as the electrolyte improves the interface and promotes a more efficient step coverage of the channel layer, reducing the operating voltage when compared with conventional dielectrics gating. Moreover, it is shown that by controlling the applied gate potential, the operation mechanism of the electrolyte-gated transistors can be modified from electric double layer to electrochemical doping.