Synthesis and Characterization of MOF-Derived Structures: Recent Advances and Future Perspectives.

Due to their facile tunability, metal-organic frameworks (MOFs) are employed as precursors and templates to construct advanced functional materials with unique and desired chemical, physical, mechanical, and morphological properties. By tuning MOF precursor composition and manipulating conversion processes, various MOF-derived materials commonly known as MOF derivatives can be constructed. The possibility of controlled and predictable properties makes MOF derivatives a preferred choice for numerous advanced technological applications. The innovative synthetic designs besides the plethora of interdisciplinary characterization approaches applicable to MOF derivatives provide the opportunity to perform a myriad of experiments to explore the performance and offer key insight to develop the next generation of advanced materials. Though there are many published works of literature describing various synthesis and characterization techniques of MOF derivatives, it is still not clear how the synthesis mechanism works and what are the best techniques to characterize these materials to probe their properties accurately. In this review, the recent development in synthesis techniques and mechanisms for a variety of MOF derivates such as MOF-derived metal oxides, porous carbon, composites/hybrids, and sulfides is summarized. Furthermore, the details of characterization techniques and fundamental working principles are summarized to probe the structural, mechanical, physiochemical, electrochemical, and electronic properties of MOF and MOF derivatives. The future trends and some remaining challenges in the synthesis and characterization of MOF derivatives are also discussed.

Head Exposure to Acceleration Database in Sport (HEADSport): a kinematic signal processing method to enable instrumented mouthguard (iMG) field-based inter-study comparisons.

Objective: Instrumented mouthguard (iMG) systems use different signal processing approaches limiting field-based inter-study comparisons, especially when artefacts are present in the signal. The objective of this study was to assess the frequency content and characteristics of head kinematic signals from head impact reconstruction laboratory and field-based environments to develop an artefact attenuation filtering method (HEADSport filter method). Methods: Laboratory impacts (n=72) on a test-dummy headform ranging from 25 to 150 g were conducted and 126 rugby union players were equipped with iMGs for 209 player-matches. Power spectral density (PSD) characteristics of the laboratory impacts and on-field head acceleration events (HAEs) (n=5694) such as the 95th percentile cumulative sum PSD frequency were used to develop the HEADSport method. The HEADSport filter method was compared with two other common filtering approaches (Butterworth-200Hz and CFC180 filter) through signal-to-noise ratio (SNR) and mixed linear effects models for laboratory and on-field events, respectively. Results: The HEADSport filter method produced marginally higher SNR than the Butterworth-200Hz and CFC180 filter and on-field peak linear acceleration (PLA) and peak angular acceleration (PAA) values within the magnitude range tested in the laboratory. Median PLA and PAA (and outlier values) were higher for the CFC180 filter than the Butterworth-200Hz and HEADSport filter method (p<0.01). Conclusion: The HEADSport filter method could enable iMG field-based inter-study comparisons and is openly available at https://github.com/GTBiomech/HEADSport-Filter-Method.

Tailored Microcantilever Optimization for Multifrequency Force Microscopy.

Microcantilevers are at the heart of atomic force microscopy (AFM) and play a significant role in AFM-based techniques. Recent advancements in multifrequency AFM require the simultaneous excitation and detection of multiple eigenfrequencies of microcantilevers to assess more data channels to quantify the material properties. However, to achieve higher spatiotemporal resolution there is a need to optimize the structure of microcantilevers. In this study, the architecture of the cantilever with gold nanoparticles using a dip-coating method is modified, aiming to tune the higher eigenmodes of the microcantilever as integer multiples of its fundamental frequency. Through the theoretical methodology and simulative model, that integer harmonics improve the coupling in multifrequency AFM measurements is demonstrated, leading to enhanced image quality and resolution. Furthermore, via the combined theoretical-experimental approach, the interplay between induced mass and stiffness change of the modified cantilever depending on the attached particle location, size, mass, and geometry is found. To validate the results of this predictive model, tapping-mode AFM is utilized and bimodal Amplitude Modulation AFM techniques to examine and quantify the impact of tuning higher-order eigenmodes on the imaging quality of a polystyrene-polymethylmethacrylate (PS-PMMA) block co-polymer assembly deposited on a glass slide and Highly Ordered Pyrolytic Graphite (HOPG).

Unraveling Spatiotemporal Transient Dynamics at the Nanoscale via Wavelet Transform-Based Kelvin Probe Force Microscopy.

Mechanistic probing of surface potential changes arising from dynamic charge transport is the key to understanding and engineering increasingly complex nanoscale materials and devices. Spatiotemporal averaging in conventional heterodyne detection-based Kelvin probe force microscopy (KPFM) inherently limits its time resolution, causing an irretrievable loss of transient response and higher-order harmonics. Addressing this, we report a wavelet transform (WT)-based methodology capable of quantifying the sub-ms charge dynamics and probing the elusive transient response. The feedback-free, open-loop wavelet transform KPFM (OL-WT-KPFM) technique harnesses the WT's ability to simultaneously extract spatial and temporal information from the photodetector signal to provide a dynamic mapping of surface potential, capacitance gradient, and dielectric constant at a temporal resolution 3 orders of magnitude higher than the lock-in time constant. We further demonstrate the method's applicability to explore the surface-photovoltage-induced sub-ms hole-diffusion transient in bismuth oxyiodide semiconductor. The OL-WT-KPFM concept is readily applicable to commercial systems and can provide the underlying basis for the real-time analysis of transient electronic and electrochemical properties.

Simultaneous quantification of Young's modulus and dispersion forces with nanoscale spatial resolution.

Many advances in polymers and layered materials rely on a precise understanding of the local interactions between adjacent molecular or atomic layers. Quantifying dispersion forces at the nanoscale is particularly challenging with existing methods often time consuming, destructive, relying on surface averaging or requiring bespoke equipment. Here, we present a non-invasive method able to quantify the local mechanical and dispersion properties of a given sample with nanometer lateral precision. The method, based on atomic force microscopy (AFM), uses the frequency shift of a vibrating AFM cantilever in combination with established contact mechanics models to simultaneously derive the Hamaker constant and the effective Young's modulus at a given sample location. The derived Hamaker constant and Young's modulus represent an average over a small (typically <100) number of molecules or atoms. The oscillation amplitude of the vibrating AFM probe is used to select the length-scale of the features to analyse, with small vibrations able to resolve the contribution of sub-nanometric defects and large ones exploring effectively homogeneous areas. The accuracy of the method is validated on a range of 2D materials in air and water as well as on polymer thin films. We also provide the first experimental measurements of the Hamaker constant of HBN, MoT2, WSe2and polymer films, verifying theoretical predictions and computer simulations. The simplicity and robustness of the method, implemented with a commercial AFM, may support a broad range of technological applications in the growing field of polymers and nanostructured materials where a fine control of the van der Waals interactions is crucial to tune their properties.

Synthesis of water-stable and highly luminescent graphite quantum dots.

Highly stable and environmentally friendly nitrogen-doped graphite quantum dots consisting of ∼12 layers of graphene, average diameter of ∼7.3 nm, prepared by atmospheric pressure microplasma are reported to have blue emission due to surface states created by nitrogen doping (9 atomic%) and reaction with oxygen. The low-temperature synthesis method requires simple precursors in water, with no annealing or filtration, producing crystalline disc-shaped quantum dots with ∼68% photoluminescence emission quantum yield at 420 nm excitation and that have shown stability for more than one month after the synthesis. The nitrogen doping in the quantum dots mainly occurs in graphitic core as substituted type of doping (63-67 atomic%) and the amount of doping is sufficient to create emissive states without impacting the core structure. The optical and chemical properties do not undergo serious retardation even with re-dispersion suggesting easy applicability for cellular imaging or optoelectronics.

Modeling and Analysis of the Capillary Force for Interactions of Different Tip/Substrate in AFM Based on the Energy Method.

This paper presents a simple and robust model to describe the wet adhesion of the AFM tip and substrate joined by a liquid bridge. The effects of contact angles, wetting circle radius, the volume of a liquid bridge, the gap between the AFM tip and substrate, environmental humidity, and tip geometry on the capillary force are studied. To model capillary forces, while a circular approximation for the meniscus of the bridge is assumed, the combination of the capillary adhesion due to the pressure difference across the free surface and the vertical component of the surface tension forces acting tangentially to the interface along the contact line is utilized. Finally, the validity of the proposed theoretical model is verified using numerical analysis and available experimental measurements. The results of this study can provide a basis to model the hydrophobic and hydrophilic tip/surfaces and study their effect on adhesion force between the AFM tip and the substrate.

Addressing the Silent Spread of Monkeypox Disease with Advanced Analytical Tools.

Monkeypox disease is caused by a virus which belongs to the orthopoxvirus genus of the poxviridae family. This disease has recently spread out to several non-endemic countries. While some cases have been linked to travel from endemic regions, more recent infections are thought to have spread in the community without any travel links, raising the risks of a wider outbreak. This state of public health represents a highly unusual event which requires urgent surveillance. In this context, the opportunities and technological challenges of current bio/chemical sensors, nanomaterials, nanomaterial characterization instruments, and artificially intelligent biosystems collectively called "advanced analytical tools" are reviewed here, which will allow early detection, characterization, and inhibition of the monkeypox virus (MPXV) in the community and limit its expansion from endemic to pandemic. A summary of background information is also provided from biological and epidemiological perspective of monkeypox to support the scientific case for its holistic management using advanced analytical tools.

Unraveling the liquid gliding on vibrating solid liquid interfaces with dynamic nanoslip enactment.

Slip length describes the classical no-slip boundary condition violation of Newtonian fluid mechanics, where fluids glide on the solid surfaces. Here, we propose a new analytical model validated by experiments for characterization of the liquid slip using vibrating solid surfaces. Essentially, we use a microfluidic system integrated with quartz crystal microbalance (QCM) to investigate the relationship between the slip and the mechanical response of a vibrating solid for a moving fluid. We discover a liquid slip that emerges especially at high flow rates, which is independent of the surface wetting condition, having significant contributions to the changes in resonant frequency of the vibrating solid and energy dissipation on its surface. Overall, our work will lead to consideration of 'missing slip' in the vibrating solid-liquid systems such as the QCM-based biosensing where traditionally frequency changes are interpreted exclusively with mass change on the sensor surface, irrespective of the flow conditions.

Total electrification of large-scale nanophotonic arrays by frictional charges.

Localized surface plasmon resonance (LSPR) of metallic nanostructures is a unique phenomenon that controls the light in sub-wavelength volumes and enhances the light-matter interactions. Traditionally, the excitation and measurement of LSPR require bulky external light sources, and efforts to scale down to nano-plasmonic devices have predominantly relied on the system's miniaturization and associated accessories. Addressing this, here we show the generation and detection of LSPR wavelength (λLSPR) shifts in large-area nanostructured Au surfaces using frictional charges generated by triboelectric surfaces. We observe a complex interplay of the localized surface plasmons with frictional charges via concurrent spectroscopic and triboelectric measurements undertaken for the detection of bioconjugation in the streptavidin-biotin complex. When subjected to multivariate principal component analysis, a strong correlation between the triboelectric peak-to-peak voltage output response and the λLSPR shift is observed. Furthermore, we reveal a landscape of the interfacial events involved in the electrical generation/detection of the LSPR by using theoretical models and surface characterization. The demonstrated concept of electrification of plasmon resonance thus provides the underlying basis for the subsequent development of self-powered nano-plasmonic sensors and opens new horizons for advanced nanophotonic applications.

Nanoplasmonic biosensor for rapid detection of multiple viral variants in human serum.

As viruses constantly change due to mutation, variants are expected to emerge demanding development of sensors capable of detecting multiple variants using one single sensor platform. Herein, we report the integration of a synthetic binder against SARS-CoV-2 with a nanoplasmonic-based sensing technology, which enables the successful detection of spike proteins of Alpha, Beta and Gamma variants of SARS CoV-2. The recognition event is achieved by specific nanostructured molecularly imprinted polymers (nanoMIPs), developed against a region of the receptor binding domain (RBD) of the SARS CoV-2 spike protein. The transduction is based on the principle of localized surface plasmon resonance (LSPR) associated with silver nanostructures. The nanoMIPs-functionalised LSPR sensor allows for the detection of all 3 protein variants with a limit of detection of 9.71 fM, 7.32 fM and 8.81 pM using wavelength shifts respectively for Alpha, Beta and Gamma spike protein variants. This can be achieved within 30 min from the sample collection, both from blood and using nasal swab, thus making this sensor suitable for rapid detection of COVID-19. Additionally, the turnaround time for sensor development and validation can be completed in less than 8 weeks, making it suitable for addressing future pandemic needs without the requirement for biological binding agents, which is one of the bottlenecks to the supply chain in diagnostic devices.

Clinical evaluation of SARS-CoV-2 lung HRCT and RT-PCR Techniques: Towards risk factor based diagnosis of infectious diseases.

This study uses image analysis techniques for comparative analysis of the lung HRCT features and RT-PCR of 325 suspected patients to COVID-19 pneumonia. Our findings propose more caution in the interpretation of RT-PCR data, promoting, instead, also the quantification of age and sex-based risk factors using HRCT images. Statistical analysis of our methodology reveals a direct relation between intensity, skewness and kurtosis of the radiological features and the gender of patients. Moreover, we investigate the effect of the age of patients on the appearance of COVID-19 pneumonia in the HRCT images. We have also applied our methodology to investigate the effect of time on the severity of COVID-19 pneumonia within the lungs. Subsequently, we find a strong relationship between image analysis and the informed medical diagnosis asserted by the radiologists. Additionally, our results also indicate increase in the severity of lung infection in the first and second week after the onset of the SARS-CoV-2 symptoms. Thereafter, a gradual decrease in the lung damage is observed during the third week. The proposed image analysis methodology can be used as a simple complementary tool for infectious disease diagnostics as demonstrated in this study with an example of SARS-CoV-2 to provide better understanding of the disease for drug and vaccine development.

Opportunities and Challenges for Biosensors and Nanoscale Analytical Tools for Pandemics: COVID-19.

Biosensors and nanoscale analytical tools have shown huge growth in literature in the past 20 years, with a large number of reports on the topic of 'ultrasensitive', 'cost-effective', and 'early detection' tools with a potential of 'mass-production' cited on the web of science. Yet none of these tools are commercially available in the market or practically viable for mass production and use in pandemic diseases such as coronavirus disease 2019 (COVID-19). In this context, we review the technological challenges and opportunities of current bio/chemical sensors and analytical tools by critically analyzing the bottlenecks which have hindered the implementation of advanced sensing technologies in pandemic diseases. We also describe in brief COVID-19 by comparing it with other pandemic strains such as that of severe acute respiratory syndrome (SARS) and Middle East respiratory syndrome (MERS) for the identification of features that enable biosensing. Moreover, we discuss visualization and characterization tools that can potentially be used not only for sensing applications but also to assist in speeding up the drug discovery and vaccine development process. Furthermore, we discuss the emerging monitoring mechanism, namely wastewater-based epidemiology, for early warning of the outbreak, focusing on sensors for rapid and on-site analysis of SARS-CoV2 in sewage. To conclude, we provide holistic insights into challenges associated with the quick translation of sensing technologies, policies, ethical issues, technology adoption, and an overall outlook of the role of the sensing technologies in pandemics.

Dynamic modeling and sensitivity analysis of dAFM in the transient and steady state motions.

In this paper, based on the slow time varying function theory, dynamical equations for the amplitude and phase of the dynamic atomic force microscope are derived. Then, the sensitivity of the amplitude and phase to the dissipative and conservative parts of interaction force is investigated. The most advantage of this dynamical model is the ability to simulate and analysis the dynamics behavior of amplitude and phase of the AFM tip motion not only in the steady state but also in the transient regime. Using numerical analysis the transient and steady state behavior of amplitude and phase is studied and the sensitivity of amplitude and phase to the interaction force is analyzed.