Nonclassical Growth Mechanism of Double-Walled Metal-Oxide Nanotubes Implying Transient Single-Walled Structures.

The formation of imogolite nanotubes is reported to be a kinetic process involving intermediate roof-tile nanostructures. Here, the structural evolution occurring during the synthesis of aluminogermanate double-walled imogolite nanotubes is in situ monitored, thanks to an instrumented autoclave allowing the control of the temperature, the continuous measurement of pH and pressure, and the regular sampling of gas and solution. Chemical analyses confirm the completion of the precursor's conversion with the release of CO2, ethanol, and dioxane as main side products. The combination of microscopic observations, infrared, and absorption spectroscopies with small and wide-angle X-ray scattering experiments unravel a unique growth mechanism implying transient single-walled nanotubes instead of the self-assembly of stacked proto-imogolite tiles. The growth formation of these transient nanotubes is followed at the molecular level by Quick-X-ray absoprtion specotrscopy experiments. Multivariate data analysis evidences that the near neighboring atomic environment of Ge evolves from monotonous to a more complex one as the reaction progresses. The following transformation into a double-walled nanotube takes place at a nearly constant mean radius, as demonstrated by the simulation of X-ray scattering diagrams. Overall, transient nanotubes appear to serve for the anchoring of a new wall, corresponding to a mechanism radically different from that proposed in the literature.

What Makes On-Chip Microdevices Stand Out in Electrocatalysis?

Clean and sustainable energy conversion and storage through electrochemistry shows great promise as an alternative to traditional fuel or fossil-consumption energy systems. With regards to practical and high-efficient electrochemistry application, the rational design of active sites and the accurate description of mechanism remain a challenge. Toward this end, in this Perspective, a unique on-chip micro/nano device coupling nanofabrication and low-dimensional electrochemical materials is presented, in which material structure analysis, field-effect regulation, in situ monitoring, and simulation modeling are highlighted. The critical mechanisms that influence electrochemical response are discussed, and how on-chip micro/nano device distinguishes itself is emphasized. The key challenges and opportunities of on-chip electrochemical platforms are also provided through the Perspective.

In Situ Monitoring of Competitive Coformer Exchange Reaction by 1H MAS Solid-State NMR.

In a competitive coformer exchange reaction, a recent topic of interest in pharmaceutical research, the coformer in a pharmaceutical cocrystal is exchanged with another coformer that is expected to form a cocrystal that is more stable. There will be a competition between coformers to form the most stable product through the formation of hydrogen bonds. This will cause destabilization of the pharmaceutical products during processing or storage. Therefore, it is important to develop a mechanistic understanding of this transformation by monitoring each and every step of the reaction, employing a technique such as 1H nuclear magnetic resonance (NMR). In this study, an in situ monitoring of a coformer exchange reaction is carried out by 1H magic angle spinning (MAS) solid-state NMR (SSNMR) at a spinning frequency of 60 kHz. The changes in caffeine maleic acid cocrystals on addition of glutaric acid and caffeine glutaric cocrystals on addition of maleic acid were monitored. In all of the reactions, it has been observed that caffeine glutaric acid Form I is formed. When glutaric acid was added to 2:1 caffeine maleic acid, the formation of metastable 1:1 caffeine glutaric acid Form I was observed at the start of the experiment, indicating that the centrifugal pressure is enough for the formation. The difference in the end product of the reactions with a similar reaction pathway of 1:1 and 2:1 reactant stoichiometry indicates that a complete replacement of maleic acid has occurred only in the 1:1 stoichiometry of the reactants. The polymorphic transition of caffeine glutaric acid Form II to Form I at higher temperatures was a crucial reason that triggered the exchange of glutaric acid with maleic acid in the reaction of caffeine glutaric acid and maleic acid. Our results are novel since the new reaction pathways in competitive coformer exchange reactions enabled understanding the remarkable role of stoichiometry, polymorphism, temperature, and centrifugal pressure.

Atomic layer deposition of Al-doped ZnO nanomembrane within situmonitoring.

Due to shortcomings such as poor homogeneity of Al doping, precisely controlling the thickness, inability to conformally deposit on high aspect ratio devices and high pinhole rate, the applications of Al-doped ZnO (AZO) nanomembrane in integrated optoelectronic devices are remarkably influenced. Here, we reportin situmonitoring during the atomic layer deposition (ALD) of AZO nanomembrane by using an integrated spectroscopic ellipsometer. AZO nanomembranes with different compositions were deposited with real-time and precise atomic level monitoring of the deposition process. We specifically investigate the half-reaction and thickness evolution during the ALD processes and the influence of the chamber temperature is also disclosed. Structural characterizations demonstrate that the obtained AZO nanomembranes without any post-treatment are uniform, dense and pinhole-free. The transmittances of the nanomembranes in visible range are >94%, and the optimal conductivity can reach up to 1210 S cm-1. The output of current research may pave the way for AZO nanomembrane to become promising in integrated optoelectronic devices.

Droplet Microfluidic-Based In Situ Analyzer for Monitoring Free Nitrate in Soil.

Monitoring nutrients in the soil can provide valuable information for understanding their spatiotemporal variability and informing precise soil management. Here, we describe an autonomous in situ analyzer for the real-time monitoring of nitrate in soil. The analyzer can sample soil nitrate using either microdialysis or ultrafiltration probes placed within the soil and quantify soil nitrate using droplet microfluidics and colorimetric measurement. Compared with traditional manual sampling and lab analysis, the analyzer features low reagent consumption (96 µL per measurement), low maintenance requirement (monthly), and high measurement frequency (2 or 4 measurements per day), providing nondrifting lab-quality data with errors of less than 10% using a microdialysis probe and 2-3% for ultrafiltration. The analyzer was deployed at both the campus garden and forest for different periods of time, being able to capture changes in free nitrate levels in response to manual perturbation by the addition of nitrate standard solutions and natural perturbation by rainfall events.

Development of an Underwater Adaptive Penetration System for In Situ Monitoring of Marine Engineering Geology.

In recent years, offshore wind farms have frequently encountered engineering geological disasters such as seabed liquefaction and scouring. Consequently, in situ monitoring has become essential for the safe siting, construction, and operation of these installations. Current technologies are hampered by limitations in single-parameter monitoring and insufficient probe-penetration depth, hindering comprehensive multi-parameter dynamic monitoring of seabed sediments. To address these challenges, we propose a foldable multi-sensor probe and establish an underwater adaptive continuous penetration system capable of concurrently measuring seabed elevation changes and sediment pore water pressure profiles. The reliability of the equipment design is confirmed through static analysis of the frame structure and sealed cabin. Furthermore, laboratory tests validate the stability and accuracy of the electrical and mechanical sensor measurements. Preliminary tests conducted in a harbor environment demonstrate the system's effectiveness.

Embeddable Chloride Sensor for Monitoring Chloride Penetration into Cement Mortar.

A composite solid chloride sensor consisting of two single sensors, i.e., Ag/AgCl working electrode and Mn/MnO2 reference electrode, was developed. The Ag/AgCl electrode was prepared by the anodic polarization method, while the Mn/MnO2 reference electrode was prepared using the powder compaction technique. Then, the electrochemical performances such as stability, reproducibility, and sensitivity of the composite and single sensors were investigated in a saturated Ca(OH)2 solution and mortar specimen. A current density of 0.5 mA/cm2 and polarization time of 2.5 h were the optimal preparation parameters of the Ag/AgCl selective electrode. The Ag/AgCl selective electrode showed a linear potential response with the logarithm of chloride ion content in solution and had good stability, reproducibility, and anti-polarization performances. In addition, the Mn/MnO2 electrode exhibited potential stability after being activated in an alkaline solution for 60 days. The composite sensor demonstrated exceptional sensitivity to the Cl- content, boasting a slope of approximately 51.1 mV/decade, and showcased excellent stability in both solution and mortar specimens. In every measurement, the time needed for the potential of a composite sensor to become stable was less than 30 s. The sensor enables non-destructive in situ monitoring of the chloride ion content in cement mortar, thus realizing early warning of deterioration of reinforcement and guaranteeing long service life of the structure.

An Activated Structure Transformable Ratiometric Photoacoustic Nanoprobe for Real-Time Dynamic Monitoring of H2S In Vivo.

H2S has emerged as a promising biomarker for many diseases such as colon cancer and metformin-induced hepatotoxicity. Real-time monitoring of H2S levels in vivo is significant for early accurate diagnosis of these diseases. Herein, a new accurate and reliable nanoprobe (Au NRs@Ag) was designed for real-time dynamic ratiometric photoacoustic (PA) imaging of H2S in vivo based on the endogenous H2S-triggered local surface plasmon resonance (LSPR) red-shift. The Au NRs@Ag nanoprobe can be readily converted into Au NRs@Ag2S via the endogenous H2S-activated in situ sulfurative reaction, subsequently leading to a significant red-shift of the LSPR wavelength from 808 to 980 nm and enabling accurate ratiometric PA (PA980/PA808) imaging of H2S. Moreover, dynamic ratiometric PA imaging of metformin-induced hepatotoxicity was also successfully achieved by the designed PA imaging strategy. These findings provide the possibility of designing a new ratiometric PA imaging strategy for dynamic in situ monitoring of H2S-related diseases.

The Role of Crystalline Intermediates in Mechanochemical Cyclorhodation Reactions Elucidated by in-Situ X-ray Powder Diffraction and Computation.

The occurrence of crystalline intermediates in mechanochemical reactions might be more widespread than previously assumed. For example, a recent study involving the acetate-assisted C-H activation of N-Heterocycles with [Cp*RhCl2 ]2 by ball milling revealed the formation of transient cocrystals between the reagents prior to the C-H activation step. However, such crystalline intermediates were only observed through stepwise intervallic ex-situ analysis, and their exact role in the C-H activation process remained unclear. In this study, we monitored the formation of discrete, stoichiometric cocrystals between benzo[h]quinoline and [Cp*RhCl2 ]2 by ball milling using in-situ synchrotron X-ray powder diffraction. This continuous analysis revealed an initial cocrystal that transformed into a second crystalline form. Computational studies showed that differences in noncovalent interactions made the [Cp*RhCl2 ]2 unit in the later-appearing cocrystal more reactive towards NaOAc. This demonstrated the advantage of cocrystal formation before the acetate-assisted metalation-deprotonation step, and how the net cooperative action of weak interactions between the reagents in mechanochemical experiments can lead to stable supramolecular assemblies, which can enhance substrate activation under ball-milling conditions. This could explain the superiority of some mechanochemical reactions, such as acetate-assisted C-H activation, compared to their solution-based counterparts.

Biomass-assisted fabrication of rGO-AuNPs as surface-enhanced Raman scattering substrates for in-situ monitoring methylene blue degradation.

Reduced graphene oxide-gold nanoparticles nanocomposites (rGO-AuNPs) with high surface-enhanced Raman scattering (SERS) activity was created by biomass-assisted green synthesis with Lilium casa blanca petals biomass for the first time, and its application for methylene blue (MB) degradation was explored through in-situ monitoring. Lilium casa blanca petals biomass was used as a reducing agent to reduce GO and chloroauric acid successively when carrying out rGO-AuNPs in-situ synthesis while it also acted as a capping agent. The produced rGO had oxygen-containing functional groups which had an outstanding performance in enhancing the SERS effect. Characterization results confirmed that the AuNPs were grafted onto the rGO sheet, and the mechanism study showed that total flavonoids in Lilium casa blanca petals biomass were the main biological compounds involved in the reduction. rGO-AuNPs had a high Raman enhancement factor (EF) which could reach 3.88 × 107. The synthesized nanocomposite also had a good catalytic activity that could be employed as catalyst in MB degradation, and it could complete degradation within 15min. The reaction rate increased linearly with the amount of rGO-AuNPs, and the degradation could be in-situ monitored both by UV and SERS.

Comet assay in Aegla platensis (Decapoda: Anomura) using a non-lethal hemolymph field sampling for in situ monitoring of freshwater genotoxicity.

This study aimed to apply the comet assay on Aegla platensis crabs as a suitable non-destructive approach for in situ monitoring of freshwater genotoxicity. Animals were captured during four sampling periods in a stream under minor anthropogenic impacts in Southern Brazil. Crabs were captured with a hand net, then the hemolymph samples were collected, and the animals were released into the stream after a 20-min recovery time. Hemolymph samples were transported to the laboratory and used to perform the alkaline comet assay. Results showed an intermediate level in the DNA damage index (range 107.3-165.0 arbitrary unit). No significant differences were observed among the different sampling periods. Hemolymph was successfully used as a non-lethal source of biological samples, and the comet assay using A. platensis proved to be a feasible approach for genotoxicity studies.

A Cell State Monitoring System with Integrated In Situ Imaging and pH Detection.

Cell models are one of the most widely used basic models in biological research, and a variety of in vitro cell culture techniques and models have been developed recently to simulate the physiological microenvironment in vivo. However, regardless of the technique or model, cell culture is the most fundamental but crucial component. As a result, we have developed a cell culture monitoring system to assess the functional status of cells within a biochip. This article focuses on a mini-microscope made from a readily available camera for in situ continuous observation of cell growth within a biochip and a pH sensor based on optoelectronic sensing for measuring pH. With the aid of this monitoring system, scientists can keep an eye on cell growth in real time and learn how the pH of the culture medium affects it. This study offers a new approach for tracking cells on biochips and serves as a valuable resource for enhancing cell culture conditions.

Powder Bed Monitoring Using Semantic Image Segmentation to Detect Failures during 3D Metal Printing.

Monitoring the metal Additive Manufacturing (AM) process is an important task within the scope of quality assurance. This article presents a method to gain insights into process quality by comparing the actual and target layers. Images of the powder bed were captured and segmented using an Xception-style neural network to predict the powder and part areas. The segmentation result of every layer is compared to the reference layer regarding the area, centroids, and normalized area difference of each part. To evaluate the method, a print job with three parts was chosen where one of them broke off and another one had thermal deformations. The calculated metrics are useful for detecting if a part is damaged or for identifying thermal distortions. The method introduced by this work can be used to monitor the metal AM process for quality assurance. Due to the limited camera resolutions and inconsistent lighting conditions, the approach has some limitations, which are discussed at the end.

Wafer Type Ion Energy Monitoring Sensor for Plasma Diagnosis.

We propose a wafer-type ion energy monitoring sensor (IEMS) that can measure the spatially resolved distribution of ion energy over the 150 mm plasma chamber for the in situ monitoring of the semiconductor fabrication process. The IEMS can directly be applied to the semiconductor chip production equipment without further modification of the automated wafer handling system. Thus, it can be adopted as an in situ data acquisition platform for plasma characterization inside the process chamber. To achieve ion energy measurement on the wafer-type sensor, the injected ion flux energy from the plasma sheath was converted into the induced currents on each electrode over the wafer-type sensor, and the generated currents from the ion injection were compared along the position of electrodes. The IEMS operates without problems in the plasma environment and has the same trends as the result predicted through the equation.

Monitoring of Single-Track Melting States Based on Photodiode Signal during Laser Powder Bed Fusion.

Single track is the basis for the melt pool modeling and physics work in laser powder bed fusion (LPBF). The melting state of a single track is closely related to defects such as porosity, lack of fusion, and balling, which have a significant impact on the mechanical properties of an LPBF-created part. To ensure the reliability of part quality and repeatability, process monitoring and feedback control are emerging to improve the melting states, which is becoming a hot topic in both the industrial and academic communities. In this research, a simple and low-cost off-axial photodiode signal monitoring system was established to monitor the melting pools of single tracks. Nine groups of single-track experiments with different process parameter combinations were carried out four times and then thirty-six LPBF tracks were obtained. The melting states were classified into three classes according to the morphologies of the tracks. A convolutional neural network (CNN) model was developed to extract the characteristics and identify the melting states. The raw one-dimensional photodiode signal data were converted into two-dimensional grayscale images. The average identification accuracy reached 95.81% and the computation time was 15 ms for each sample, which was promising for engineering applications. Compared with some classic deep learning models, the proposed CNN could distinguish the melting states with higher classification accuracy and efficiency. This work contributes to real-time multiple-sensor monitoring and feedback control.

NIR-II Ratiometric Lanthanide-Dye Hybrid Nanoprobes Doped Bioscaffolds for In Situ Bone Repair Monitoring.

In situ monitoring of tissue regeneration progression is of primary importance to basic medical research and clinical transformation. Despite significant progress in the field of tissue engineering and regenerative medicine, few technologies have been established to in situ inspect the regenerative process. Here, we present an integrated second near-infrared (NIR-II, 1000-1700 nm) window in vivo imaging strategy based on 3D-printed bioactive glass scaffolds doped with NIR-II ratiometric lanthanide-dye hybrid nanoprobes, allowing for in situ monitoring of the early inflammation, angiogenesis, and implant degradation during mouse skull repair. The functional bioactive glass scaffolds contribute to more effective bone regeneration because of their excellent angiogenic and osteogenic activities. The reliability of ratiometric fluorescence imaging, coupled with low autofluoresence in the NIR-II window, facilitates the accuracy of in vivo inflammation detection and high-resolution visualization of neovascularization and implant degradation in deep tissue.

Field investigation on the change process of microbial community structure in large-deep reservoir during the initial impoundment.

During the initial impoundment of large-deep reservoir, the aquatic environment changed dramatically in various aspects such as water level, hydrological regime, and pollutants, which could alter microorganisms' community structure, break the balance of the aquatic ecosystem and even endanger the aquatic ecosystem. However, the interaction of microbial communities and water environment during the initial impoundment process of a large-deep reservoir remained unclear. To this end, in-situ monitoring and sampling analysis on water quality and microbial communities during the initial impoundment process of a typical large-deep reservoir named Baihetan were conducted so as to explore the response of microbial community structure to the changes of water environmental factors during the initial impoundment of large deep reservoir and reveal the key driving factors affecting microbial community structure. The spatio-temporal variation in water quality was analyzed, and the microbial community structure in the reservoir was investigated based on high-throughput sequencing. The results showed that the COD of each section increased slightly, and the water quality after impoundment was slightly poorer than that before the impoundment. Water temperature and pH were proved to be the key factors affecting the structure of bacterial and eukaryotic communities respectively during the initial impoundment. The research results revealed the role of microorganisms and their interaction with biogeochemical processes in the large-deep reservoir ecosystem, which was crucial for later operation and management of the reservoir and the protection of the reservoir water environment.

Modelling the dispersion of particulate matter (PM10) via wind erosion from opencast mining-Moldova Noua tailings ponds, Romania.

Historically, Romania is known as a mining site of mineral substances, including gold, silver, copper, lead, zin, uranium, manganese, salt, and coal, whereby their long periods of exploitation and extraction affected human health and the environment in various ways. In Moldova Noua southwest region of Romania, we investigated the environmental impacts of mining activities on air quality over 2021. We quantified PM10 emission rates through in situ monitoring, dispersion modelling, and horizontal and vertical fluxes. Statistical metrics, including the fraction within factor 2 (FAC2), mean bias (MB), mean gross error (MGE), normalized mean bias (NMB), normalized mean gross error (NMGE), coefficient of efficiency (COE), index of agreements (IOAs), and Taylor diagram signifying standards deviation (SD), root mean squared error (RMSE), and correlation coefficient (R), were used to evaluate the reliability of modelling results against observation. Results conclude that PM10 dispersion agrees with MB, MGE, NMB, NMGE, COE, IOA, and Taylor diagram and moderately with FAC2 metrics. PM10 hotspot was investigated in the vicinity of the tailings ponds of 115.5 µg m-3 annual mean, 563.7 µg m-3 daily mean, 63.3 µg m-2 s-1 annual horizontal flux, and 3.0 µg m-2 s-1 annual vertical flux. PM10 dispersion was identified to expand to Moldova Noua City and nearby country Serbia. Findings concluded that a windy air mass accumulation across the overburdened dumps and ponds causes the increase of PM10 in the air, resulting in the region's pollution. Therefore, results recommend adopting a strategic mitigation measure for residents, policymakers, stakeholders, and urban planners.

Low- versus Mid-frequency Raman Spectroscopy for in Situ Analysis of Crystallization in Slurries.

Slurry studies are useful for exhaustive polymorph and solid-state stability screening of drug compounds. Raman spectroscopy is convenient for monitoring crystallization in such slurries, as the measurements can be performed in situ even in aqueous environments. While the mid-frequency region (400-4000 cm-1) is dominated by intramolecular vibrations and has traditionally been used for such studies, the low-frequency spectral region (<200 cm-1) probes solid-state related lattice vibrations and is potentially more valuable for understanding subtle and/or complex crystallization behavior. The aim of the study was to investigate low-frequency Raman spectroscopy for in situ monitoring of crystallization of an amorphous pharmaceutical in slurries for the first time and directly compare the results with those simultaneously obtained with mid-frequency Raman spectroscopy. Amorphous indomethacin (IND) slurries were prepared at pH 1.2 and continuously monitored in situ at 5 and 25 °C with both low- and mid-frequency Raman spectroscopy. At 25 °C, both spectral regions profiled amorphous IND in slurries as converting directly from the amorphous form toward the α crystalline form. In contrast, at 5 °C, principal component analysis revealed a divergence in the detected conversion profiles: the mid-frequency Raman suggested a direct conversion to the α crystalline form, but the low-frequency region showed additional transition points. These were attributed to the appearance of minor amounts of the ε-form. The additional solid-state sensitivity of the low-frequency region was attributed to the better signal-to-noise ratio and more consistent spectra in this region. Finally, the low-frequency Raman spectrum of the ε-form of IND is reported for the first time.

In situmonitoring the productivity of ultra-small gold nanoparticles generated by pulsed-laser ablation of a high-speed rotating gold target in pure water.

We investigate the productivity of ultra-small gold nanoparticles generated by pulsed-laser ablation in liquid of a high-speed rotating gold target as functions of laser ablation time and rotation speed of the target in the range 90-3000 rpm. These experiments were performed byin situmonitoring the extinction spectra of the gold colloidal suspension. The time evolution of the gold volume fraction in the colloidal suspension of the target was determined by modeling the extinction spectra using the shape distribution effective medium theory. The time dependence of the ablation rate, deduced from that of the volume fraction, shows an initial exponential decay followed by a steady-state value at longer ablation time. The influence of the laser-induced roughening of the target surface on the time evolution of the ablation rate is clearly demonstrated. The experimental results also reveal the dependence of the time evolution of the ablation rate of the target on its rotation speed. The effect of the liquid flow on the ablation rate of the target is analyzed and discussed.