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Customizable gold nanoparticle platforms are motivating innovations in drug discovery with massive therapeutic potential due to their biocompatibility, stability, and imaging capabilities. Further development requires the understanding of how discrete differences in shape, charge, or surface chemistry affect the drug delivery process of the nanoparticle. The nanoparticle shape can have a significant impact on nanoparticle function as this can, for example, drastically change the surface area available for modifications, such as surface ligand density. In order to investigate the effects of nanoparticle shape on the structure of cell membranes, we directly probed nanoparticle–lipid interactions with an interface sensitive technique termed sum frequency generation (SFG) vibrational spectroscopy. Both gold nanostars and gold nanospheres with positively charged ligands were allowed to interact with a model cell membrane and changes in the membrane structure were directly observed by specific SFG vibrational modes related to molecular bonds within the lipids. The SFG results demonstrate that the +Au nanostars both penetrated and impacted the ordering of the lipids that made up the membrane, while very little structural changes to the model membrane were observed by SFG for the +Au nanospheres interacting with the model membrane. This suggests that the +Au nanostars, compared to the +Au nanospheres, are more disruptive to a cell membrane. Our findings indicate the importance of shape in nanomaterial design and provide strong evidence that shape does play a role in defining nanomaterial-biological interactions.

An online internal standard correction technique for high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was designed using an autosampler system equipped with HPLC to improve the analytical precision. The autosampler was programed to operate in the following sequence: it first takes up a portion of sample solution, rinses the nozzle, sucks air as a spacer, takes an internal standard solution and finally injects all of them into a sampling loop through an injection valve. The repeatability of the sampling (amount 20 μL) was improved from 2.5 to 1.2% using the online internal standard technique. This technique was applied to As speciation in food samples, since food safety monitoring requires high precision and high sample throughput. Rhenium was very suitable as an internal standard element due to its retention time, peak shape and water solubility. This technique effectively improved the analytical precision of the As speciation and got rid of the operation of adding an internal standard solution into samples.

Differential mobility spectrometry (DMS)-based detectors are being widely studied to detect chemical warfare agents, explosives, chemicals, drugs and analyze volatile organic compounds (VOCs). The dispersion plots from DMS devices are complex to effectively analyze through visual inspection. In the current work, we adopted machine learning to differentiate pure chemicals and identify chemicals in a mixture. In particular, we observed the convolutional neural network algorithm exhibits excellent accuracy in differentiating chemicals in their pure forms while also identifying chemicals in a mixture. In addition, we propose and validate the magnitude-squared coherence (msc) between the DMS data of known chemical composition and that of an unknown sample can be sufficient to inspect the chemical composition of the unknown sample. We have shown that the msc-based chemical identification requires the least amount of experimental data as opposed to the machine learning approach.

Since the observation of the first sulfur-containing molecule, carbon monosulfide (CS), in the interstellar medium (ISM) half a century ago, sulfur-bearing species have attracted great attention from the astrochemistry, astrobiology, and planetary geology communities. Nevertheless, it is still not clear in which forms most of the sulfur resides in molecular clouds, an unsolved problem referred to as "sulfur depletion". Reported herein is the formation of thioformic acid (HCOSH)─the simplest thioacid─in interstellar ice analogues containing carbon monoxide (CO) and hydrogen sulfide (H

Subwavelength terahertz (THz) imaging methods are highly desirable for biochemical sensing as well as materials sciences, yet sensitive spectral fingerprinting is still challenging in the frequency domain due to weak light-matter interactions. Here, we demonstrate subwavelength THz resonance imaging (STRING) that overcomes this limitation to achieve ultrasensitive molecular fingerprinting. STRING combines individual ring-shaped coaxial single resonators with near-field spectroscopy, yielding considerable sensitivity gains from both local field enhancement and the near-field effect. As an initial demonstration, we obtained spectral fingerprints from isomers of α-lactose and maltose monohydrates, achieving sensitivity that was enhanced by up to 10 orders of magnitude compared to far-field THz measurements with pelletized samples. Our results show that the STRING platform could enable the development of THz spectroscopy as a practical and sensitive tool for the fingerprinting and spectral imaging of molecules and nanoparticles.

Classical histological methods such as hematoxylin-eosin staining, have been, and in some areas still are, an important benchmark for the evaluation of biological tissues. However, the current method of assessment is primarily a qualitative assessment of the tissue under investigation. The aim of this paper is to contribute to the improvement of classical histological methods, by applying physical techniques that allow objective, quantitative data to be added to qualitative assessments, especially in areas where conflicting results are available. To this end, the effect of hypolipidemic medication on the callus formation process of normal bone and pathological osteoporotic bone was investigated. The study allowed us to associate UV-VIS spectroscopy wave number with specific hematoxylin-eosin staining of different types of bone tissue structures, the evolving structures in the callus formation process. This association allowed the quantitative assessment of the callusing process in ovariectomized (associated with pathological, osteoporotic bone) and non-ovariectomized (associated with normal bone) rats, with three groups - the control group, simvastatin-treated group, and fenofibrate-treated group. The study showed that in the non-ovariectomized groups both treatments delayed callus formation. In the ovariectomized groups, simvastatin delayed and fenofibrate promoted callus formation.

Despite the great potential of microplasma optical emission spectrometry (OES) for on-site analysis, it remains a challenge to achieve the fast, sensitive, batch, and multielement analysis of trace heavy metals in a complex matrix. Herein, a novel ultrasonic nebulization-accelerated gas-phase enrichment (GPE) following in situ microplasma desorption sampling approach is employed for the determination of trace heavy metals by a miniature dielectric barrier discharge (DBD)-OES device. The volatile heavy metal species obtained by hydride generation (HG) can be quickly separated from the complex matrix under the action of ultrasonic nebulization, adsorbed on the surface of the activated carbon electrode tip for GPE, and then in situ desorbed and excited by DBD microplasma to achieve multielement OES analysis. With an array nebulizer plate, a batch of 10 samples can be handled for GPE in 40 s, and DBD-OES analysis is maintained at a rate of 6 s per sample. Under the optimized conditions, the detection limits for simultaneous determinations of Hg, Cd, Cu, and Sn are 0.005, 0.01, 0.03, and 0.04 μg L

We report on a mid-infrared (mid-IR) photothermal spectrometer for liquid-phase samples for the detection of water in organic solvents, such as ethanol or chloroform, and in complex mixtures, such as jet fuel. The spectrometer is based on a Mach-Zehnder interferometer (MZI) employing a He-Ne laser, a mini-flow cell with two embedded channels placed in the interferometer's arms, and a tunable external cavity quantum cascade laser (EC-QCL) for selective analyte excitation in a collinear arrangement. In this study, the bending vibration of water in the spectral range 1565-1725 cm

We present a primary method for absolute reference material-free measurement of gaseous elemental mercury mass concentration based on laser absorption spectroscopy at wavelengths near 254 nm and anchored to the international system of units. A 76 m-long multipass cell provides a detection limit of 1 ng m

Surgical wound excision is a necessary procedure for burn patients that require the removal of eschar. The extent of excision is currently guided by clinical judgement, with excessinto healthy tissue potentially leading to excessive scar, or inadequate debridement increasing risk of infection. Thus, an objective real-time measure to facilitate accurate excision could support clinical judgement and improve this surgical procedure. This study was designed to investigate the potential use of Rapid evaporative ionisation mass spectrometry (REIMS) as a tool to support data-driven objective tissue excision.Data were acquired using a multi-platform approach that consisted of both Rapid Evaporative Ionisation Mass Spectrometry (REIMS) performed on intact skin, and comprehensive liquid chromatography-mass spectrometry (LC-MS/MS) lipidomics performed on homogenised skin tissue extracts. Data were analysed using principal components analysis (PCA) and multivariate orthogonal projections to latent squares discriminant analysis (OPLS-DA) and logistic regression to determine the predictability of the models.PCA and OPLS-DA models of the REIMS and LC-MS/MS lipidomics data reported separation of excised and healthy tissue. Molecular fingerprints generated from REIMS analysis of healthy skin tissue revealed a high degree of heterogeneity, however, intra-individual variance was smaller than inter-individual variance. Both platforms indicated high levels of skin classification accuracy. In addition, OPLS-DA of the LC-MS/MS lipidomic data revealed significant differences in specific lipid classes between healthy control and excised skin samples; including lower free fatty acids (FFA), monoacylglycerols (MAG), lysophosphatidylglycerol (LPG) and lysophosphatidylethanolamines (LPE) in excised tissue and higher lactosylceramides (LCER) and cholesterol esters (CE) compared to healthy control tissue.Having established the heterogeneity in the biochemical composition of healthy skin using REIMS and LC-MS/MS, our data show that REIMS has the potential to distinguish between excied and healthy skin tissue samples. This pilot study suggests that REIMS may be an effective tool to support accurate tissue excision during burn surgery.

We correlate the strength of interfacial interactions with the adhesive force necessary to separate a polymer from a surface. It is intuitive that interactions would influence adhesion and friction; however, challenges in the direct measurement of the interaction strength at interfaces have obscured the connection between these interactions and such phenomena. We overcome this by using interface-sensitive sum frequency generation spectroscopy to determine the strength of interfacial interactions between polymers and sapphire through a shift in vibrational frequency and compare this with mechanical adhesion tests. Our results indicate that spectroscopic shifts can be used to directly estimate adhesion, especially for polar materials. This work provides a framework to connect molecular interactions to interfacial properties, enabling the design and rapid screening of molecular architectures.

The in vitro antimicrobial activity of Fe(III) and Ga(III) complexes with N'-(2, 3-dihydroxy- phenylmethylidene)-3-pyr- idinecarbohydrazide (H 2 L 1), N'-(2, 4-dihydroxy-phenyl-methylidene)-3- pyridinecarbohydrazide (H 2 L 2), N'-(2, 5-dihy- droxy-phenylmethylidene)-3-pyridinecarbohydrazide (H 2 L 3), N'-(2-hydroxy-3-methoxyphenyl- methylidene)-3-pyri- dine-carbohydrazide (H 2 L 4), N'-(2-hydroxy-4-methoxyphenylmethyl-idene)-3- pyridine-carbohydrazide (H 2 L 5), and N'-(2- hydroxy-5-methoxyphenylmethylidene)-3- pyridinecarbo-hydrazide (H 2 L 6) toward several Gram-positive strains of Staphylococcus aureus, a Gram-negative strain of Escherichia coli, and a yeast Candida albicans were investigated. Fe(III)- complexes do not possess antimicrobial activity against all tested strains at concentrations up to 10 mg mL –1 . Ga(III) com- plexes with dihydroxy derivatives showed selective activity, while the broadest range of antibacterial and antifungal activities was observed for complex with 2- hydroxy-3-methoxy-derivative, ligand H 2 L 5. In addition, the coordination properties of ligands H 2 L 1 –H 2 L 3 in solution were investigated by UV–Vis spectroscopy. The stability constants (logK) for Ga(III)-H 2 L 1:1 complexes in MeOH/H 2 O 1/1 at pH 2.52 were determined, and amounted to 5.8, 5.68, and 4.7, respectively. Detailed characterization of complexes was performed by high-resolution mass spectrometry. The fragmentation pathways for dimer [Fe 2 (L 1) 2 ] 2+ , [Fe(HL) 2 ] + , [Ga(HL 2) 2 ] + and adduct ions are given. The comparison with analogue Ga(III) and Fe(III) com- plexes with compounds H 2 L 4 –H 2 L 6 was made as well.

Optical methods are appropriate for monitoring of constituents in suspensions and emulsions. A simple multi-wavelength, multi-reflectance spectroscopic technique, called MRS-Technology, is introduced. Two different signals of a sample are measured: the reflectance from a small and from a large measuring volume corresponding to the reduced scattering coefficient [Formula: see text] and to the sum of [Formula: see text] and the absorption coefficient μABS, respectively. Analytical relations between the MRS reflectance and μABS as well as [Formula: see text] are derived. The investigations on MRS method are carried out using milk as an example. For this purpose “virtual” milk samples are defined. μABS and [Formula: see text] are calculated by means of the Mie scattering theory in the ultraviolet–visible–shortwave near-infrared (UV-Vis-SWNIR) spectral range. Using this data analytical reflectances can be calculated based on MRS theory as well as numerical reflectances obtained by Monte Carlo (MC) simulation. Analytical and numerical results are compared and investigated. The spectral behavior of the analytical reflectances is very similar to that of the numerical MC reflectances in the case of medium and low absorptions. By means of simple multilinear regression techniques (MLR), simple correlations between fat and protein volume fractions and reflectances could be generated with acceptable root mean square error (RMSE) values. Each correlation shows that best results will be achieved by using reflectances at sample-specific wavelengths for small and large measuring volumes of a sample indicating the potential of the MRS-Technology.

Different environmental and industrial technologies seek for fast and automatic ammonia detection systems, capable of the selective measurement of the concentration of its isotopes at sub-ppm levels, without any interference with the common contaminants. In this work, we report the quasi-simultaneous measurement ofsup14/supNHsub3/subandsup15/supNHsub3/subconcentrations based on a near-infrared diode laser-based photoacoustic system. Using a widely tunable external cavity diode laser, four nearby wavelengths within the range of 1531.3-1531.8 nm were optimal circumstances for sensitive detection, while avoiding interference with water vapor. Subsequently, a more robust distributed feedback diode laser was employed to tune the laser wavelength on the sub-second timescale by varying its driving current rather than using much slower temperature tuning. The detection limit of our system is 0.15 and 0.73 ppm forsup14/supNHsub3/subandsup15/supNHsub3/sub(with an accuracy below 0.1%), respectively, and the response time is 3.5 s.

The determination of the extinction coefficient of human dental enamel to deliver further optical properties of enamel to improve the understanding of light propagation in teeth and to improve restoration materials.The extinction coefficient was measured within a spectral range of 300-980 nm using a collimated transmission setup. 35 specimens from 16 donors were examined. The donors were categorized by age and the researched specimen were categorized by tooth type, tooth quality and lateral expansion of the enamel to clarify the influence of these parameters.The obtained spectrally resolved extinction coefficient was accurately described by a power law, which agrees with theoretical scattering models. The results were evaluated with regard to the influence of parameters such as subject age, tooth type, enamel sample quality and enamel width. For this purpose, both the average values of multiple measurements of a single sample in a defined spectral range as well as the curve slope of the averaged results versus wavelength were compared.The results provide detailed information about the optical properties of human enamel. The wide spectrum investigated provides important information for the evaluation of the main scatterers and the optical impression under any light condition. However, the deviation of the extinction coefficient varies less between the mean values for the specimens grouped by several parameters than between the specimens themselves within a group. This indicates a unique optical behaviour for every specimen and this requires consideration in the development of artificial materials.

The ongoing integration of quantum chemistry, statistical mechanics, and artificial intelligence is paving the route toward more effective and accurate strategies for the investigation of the spectroscopic properties of medium-to-large size chromo- phores in condensed phases. In this context we are developing a novel workflow aimed at improving the generality, reliability, and ease of use of the available computational tools. In this paper we report our latest developments with specific reference to unsupervised atomistic simulations employing non periodic boundary conditions (NPBC) followed by clustering of the trajectories employing optimized feature spaces. Next accurate variational computations are performed for a representative point of each cluster, whereas intracluster fluctuations are taken into account by a cheap yet reliable perturbative approach. A number of methodological improvements have been introduced including, e.g., more realistic reaction field effects at the outer boundary of the simulation sphere, automatic definition of the feature space by continuous perception of solute−solvent interactions, full account of polarization and charge transfer in the first solvation shell, and inclusion of vibronic contributions. After its validation, this new approach has been applied to the challenging case of solvatochromic effects on the UV−vis spectra of a prototypical nitroxide radical (TEMPO) in different solvents. The reliability, effectiveness, and robustness of the new platform is demonstrated by the remarkable agreement with experiment of the results obtained through an unsupervised approach characterized by a strongly reduced computational cost as compared to that of conventional quantum mechanics and molecular mechanics models without any accuracy reduction.

Evaporation is an interfacial phenomenon in which a water molecule breaks the intermolecular hydrogen (H-) bonds and enters the vapor phase. However, a detailed demonstration of the role of interfacial water structure in the evaporation process is still lacking. Here, we purposefully perturb the H-bonding environment at the air/water interface by introducing kosmotropic (HPO

We report a multicomponent gas sensor based on hollow-core fiber (HCF) photothermal spectroscopy with frequency-division multiplexing (FDM). A single antiresonant HCF (AR-HCF) is used as the gas cell, which supports broadband transmission from near-infrared (NIR) to mid-infrared (MIR), covering the absorption lines of water vapor (H

Biological tissues may be studied using photoacoustic (PA) spectroscopy, which can yield a wealth of physical and chemical data. However, it is really challenging to directly analyse these tissues because of a lot of data. Data mining techniques can get around this issue. In order to diagnose prostate cancer via PA spectrum assessment, this work describes the machine learning (ML) technique implementation, such as supervised classification and unsupervised hierarchical clustering. The collected PA signals were preprocessed using Pwelch method, and the features are extracted using two methods such as hierarchical cluster and correlation assessment. The extracted features are classified using four ML-methods, namely, Support Vector Machine (SVM), Naïve Bayes (NB), decision tree C4.5, and Linear Discriminant Analysis (LDA). Furthermore, as these components alter throughout the progression of prostate cancer, this study focuses on the composition and distribution of collagen, lipids, and haemoglobin. In diseased tissues compared to normal tissues, there is a stronger correlation between the various chemical components ultrasonic power spectra, suggesting that the microstructural dispersion in tumour tissues has been more uniform. The accuracy of several classifiers used in cancer tissue diagnosis was greater than 94% for all four methods, which is effective than that of benchmark medical methods. Thus, the method shows significant promise for the noninvasive, early detection of severe prostate cancer.

International audience; The still unexplained daytime HONO concentration in the Earth’s atmosphere and the impact of water on the HONO chemistry have been a mystery for decades. Several pathways and many modeling methods have failed to reproduce the atmospheric measurements. We reveal in this study the first spectroscopic observation and characterization of the complex of HONO with water observed through its rotational signature. Under the experimental conditions, HONO–water is stable, particularly straightforward to form, and features intense absorption signals. This could explain both the influence of water on the HONO chemistry and the missing HONO sources, as well as the missing contribution of many other molecules of atmospheric relevance that skew the accuracy of field measurements and the full account of partitioning species in the atmosphere.

International audience; Fractional electron capture probability ratios of 125I were measured using metallic magnetic calorimeters (MMCs). Due to the 4π geometry of the source embedded in the absorber, detection efficiency of nearly 99% was observed for K, L, M, and N capture events. The fractional capture probabilities were calculated from peak area ratios.

For the first time, air-assisted cloud point extraction (AACPE) was presented to preconcentrate metal ions. The procedure was conjugated with inductively coupled plasma-optical emission spectroscopy for determination of samarium. In this procedure, samarium ions were complexed with aluminon and extracted into Triton X-114 in the presence of potassium iodide. The mixture was repeatedly sucked and dispersed with a syringe (three times) to create cloud solution. Experimental factors that affect the extraction competence of the AACPE procedure, such as pH, amount of aluminon and Triton X-114, salt addition, number of suction/injection cycles, and centrifugation rate and time, have been investigated and optimized. A linear calibration curve from 0.2 to 200.0 μg L−1 with enrichment factor and detection limit of 102 and 0.06 μg L−1, respectively, was established under the optimum experimental conditions. The approach was used to determine samarium in wastewater and rock samples, with recoveries ranging from 98% to 99%. Graphical abstract

The hydrogen bonding network that surrounds the flavin in Blue Light Utilizing FAD (BLUF) photoreceptors plays a crucial role in sensing and communicating the changes in the electronic structure of the flavin to the protein matrix upon light absorption. The network contains a highly conserved tyrosine that is essential for photoactivation. Using time-resolved infrared spectroscopy (TRIR) and unnatural amino acid (UAA) incorporation, we investigated the photoactivation mechanism and the role of the conserved tyrosine (Y6) in the forward reaction of the photoactivated adenylyl cyclase (AC) from Oscillatoria Acuminata (OaPAC). Our work elucidates the direct connection between the photoactivation process in the BLUF domain and the structural and functional implications on the partner protein for the first time. The TRIR results demonstrate formation of FADH● as an intermediate species on the photoactivation pathway which decays to form the signaling state. Using fluorotyrosine analogs to modulate the physical properties of Y6, the TRIR data reveal that a change in the pKa and/or reduction potential of Y6 has a profound effect on the forward reaction, consistent with a mechanism involving proton transfer or proton-coupled electron transfer from Y6 to the electronically excited FAD. Decreasing the pKa from 9.9 to

Vibrational sum frequency generation (SFG) spectroscopy can specifically probe molecular species non-centrosymmetrically arranged in a centrosymmetric or isotropic medium. This capability has been extensively utilized to detect and study molecular species present at the two-dimensional (2D) interface at which the centrosymmetry or isotropy of bulk phases is naturally broken. The same principle has been demonstrated to be very effective for the selective detection of non-centrosymmetric crystalline nanodomains interspersed in three-dimensional (3D) amorphous phases. However, the full spectral interpretation of SFG features has been difficult due to the complexity associated with the theoretical calculation of SFG responses of such 3D systems. This paper describes a numerical method to predict the relative SFG intensities of non-centrosymmetric nanodomains in 3D systems as functions of their size and concentration as well as their assembly patterns, i.e., the distributions of tilt, azimuth, and rotation angles with respect to the lab coordinate. We applied the developed method to predict changes in the CH and OH stretch modes characteristic to crystalline cellulose microfibrils distributed with various orders, which are relevant to plant cell wall structures. The same algorithm can also be applied to any SFG-active nanodomains interspersed in 3D amorphous matrices.

Atomic force microscopy (AFM) based single-molecule force spectroscopy (SMFS) is a powerful tool to study the mechanical properties of proteins. In these experiments, site-specific immobilization of proteins is critical, as the tether determines the direction and amplitude of forces applied to the protein of interest. However, existing methods are mainly based on thiol chemistry or specific protein tags, which cannot meet the need of many challenging experiments. Here, we developed a histidine-specific phosphorylation strategy to covalently anchor proteins to an AFM cantilever tip or the substrate via their histidine tag or surface-exposed histidine residues. The formed covalent linkage was mechanically stable with rupture forces of over 1.3 nN. This protein immobilization method considerably improved the pickup rate and data quality of SMFS experiments. We further demonstrated the use of this method to explore the pulling-direction-dependent mechanical stability of green fluorescent protein and the unfolding of the membrane protein archaerhodopsin-3.

The effect of LC mobile phase composition and flow rate (2–50 µL/min) on mobility behavior in vacuum differential mobility spectrometry (vDMS) was investigated for electrosprayed isobaric antidepressant drugs (AD); amitriptyline, maprotiline, venlafaxine; and structurally related antidepressants nortriptyline, imipramine, and desipramine. While at 2 µL/min, no difference in compensation voltage was observed with methanol and acetonitrile, at 50 µL/min, acetonitrile used for LC elution of analytes enabled the selectivity of the mobility separation to be improved. An accurate and sensitive method could be developed for the quantification of six AD drugs in human plasma using trap/elute micro-LC setup hyphenated to vDMS with mass spectrometric detection in the selected ion monitoring mode. The assay was found to be linear over three orders of magnitude, and the limit of quantification was of 25 ng/mL for all analytes. The LC-vDMS-SIM/MS method was compared to a LC-MRM/MS method, and in both cases, inter-assay precisions were lower than 12.5 and accuracies were in the range 91.5–110%, but with a four times reduced analysis time (2 min) for the LC-vDMS-SIM/MS method. This work illustrates that with vDMS, the LC mobile phase composition can be used to tune the ion mobility separation and to improve assay selectivity without additional hardware. Graphical abstract

Direct assessment of blood oxygenation in the human placenta can provide information about placental function. However, the monitoring of placental oxygenation involves invasive sampling or imaging techniques that are poorly suited for bedside use. Here we show that placental oxygen haemodynamics can be non-invasively probed, in real time, up to 4.2 cm below the body surface via concurrent frequency-domain diffuse optical spectroscopy and ultrasound imaging. We developed the multimodal instrument to facilitate assessment of anterior placental properties by leveraging image-reconstruction algorithms that integrate ultrasound information about the morphology of tissue layers with optical information on haemodynamics. In a pilot investigation involving pregnancies in the third trimester, we studied women with normal (15) or some type of abnormal (9) placental function. We found no significant differences in baseline haemoglobin properties, but we found statistically significant differences in the placental haemodynamic responses to maternal hyperoxia. The results suggest that non-invasive monitoring of placental oxygenation may aid the early detection of placenta-related adverse pregnancy outcomes and maternal vascular malperfusion.

Water pollution threatens the safety of human production and life. To quickly respond to water pollution, it is important for water management staff to predict water quality changes in advance. Drawing on the temporality of water quality data, the leaky integrator echo state network (ESN) was introduced to construct the water quality prediction models for dissolved oxygen (DO), permanganate index (CODMn), and total phosphorus (TP), respectively. First, the missing values were filled by the linear trend method of adjacent points, and the outliers were detected and corrected by the Z-score method and the linear trend method. Second, the singular spectrum analysis (SSA) was performed to denoise the original monitoring data, such that the predicted data catch up with the real data, and the model accuracy is not affected by the hidden noise in the data. Third, the correlation between water quality indices was measured by the maximum information coefficient (MIC), and the strongly correlated indices were imported to the prediction model. Finally, according to these strong correlation indicators, the water quality prediction models based on multiple features were constructed, respectively, using the offline and online learning algorithms of the ESN. The hyperparameters of the models were optimized through the sequential model-based optimization (SMBO). Experimental results show that the proposed water quality prediction models, namely, SSA-MIC-SMBO-Offline ESN and SSA-MIC-SMBO-Online ESN, predicted DO, CODMn, and TP accurately, providing suitable tools for practical applications.

Photoacids and photobases constitute a class of molecules that upon absorption of light undergoes a reversible change in acidity, i.e. p

Most of scintillators used for radiation detection exhibit afterglow, which is emission of light with longer decay times than that of main light pulse. High signal from afterglow has usually negative influence on detection parameters, e.g. for energy resolution in spectrometry measurements. The paper deals with long-term afterglow of some types of scintillators, which is more significant in the case of integral measurement when current in the photodetector is measured. The range of studied decay times was in the order of tens of seconds to days. Seven types of scintillators were measured: BGO, CaF2(Eu), CdWO4, CsI(Tl), LiI(Eu), NaI(Tl) and plastic scintillator. Excitation of scintillators was made using a UV lamp. After UV irradiation, a scintillator was inserted to scintillation detection unit and the anode current of photomultiplier tube was measured with a picoammeter. As results, CaF2(Eu) and plastic scintillator have relatively low long-term afterglow signal compared with other measured scintillators.

Sum-frequency generation (SFG) spectroscopy provides a unique optical probe for interfacial molecules with interface-specificity and molecular specificity. SFG measurements can be further carried out at different polarization combinations, but the target of the polarization-dependent SFG is conventionally limited to investigating the molecular orientation. Here, we explore the possibility of polarization-dependent SFG (PD-SFG) measurements with heterodyne detection (HD-PD-SFG). We stress that HD-PD-SFG enables accurate determination of the peak amplitude, a key factor of the PD-SFG data. Subsequently, we outline that HD-PD-SFG can be used not only for estimating the molecular orientation but also for investigating the interfacial dielectric profile and studying the depth profile of molecules. We further illustrate the variety of combined simulation and PD-SFG studies.

Trace inspection is a key technology for collecting crime scenes in the criminal investigation department. A lot of information can be obtained by restoring and analyzing the remaining traces on the scene. However, with the development of digital technology, digital trace inspection has become more and more popular. So, the main research of this article is the design and realization of the trace inspection system based on hyperspectral imaging technology. This article proposes nondestructive testing technology in hyperspectral imaging technology. Combining basic principles of spectroscopy and the image of residual traces such as car tires, shoe soles, and blood stains, it can identify the key traces. Then, based on the image denoising and least squares support vector machine method, this study improves the accuracy and restoration of the image. Therefore, this study designs a test for the trace inspection system for testing hyperspectral imaging technology. The test items include the performance of the trace inspection system, the noise reduction of the trace inspection system, and the ability of the trace inspection system to inspect blood stains. The final collected data are improved to get the trace inspection system based on hyperspectral imaging technology proposed in this study. Compared with the traditional trace inspection system, the experimental results show that the trace inspection system based on hyperspectral imaging technology can improve the accuracy by 5%–28%, compared with the traditional trace inspection system. The image restoration degree of the hyperspectral imaging technology trace inspection system can be improved by 1%–19%, compared with the traditional trace inspection system.

Oxygen-involved electrocatalytic processes, including the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), are central to a series of advanced modern energy and conversion technologies, such as water electrolyzers, fuel cells, and CO

Although gas phase rotational spectroscopy is a mature field for which millions of rotational spectral lines have been measured in hundreds of molecules with sub-MHz accuracy, it remains a challenge to measure these rotational spectra in excited vibrational modes with the same accuracy. Recently, it was demonstrated that virtually any rotational transition in excited vibrational modes of most molecules may be made to lase when pumped by a continuously tunable quantum cascade laser (QCL). Here, we demonstrate how an infrared QCL may be used to enhance absorption strength or induce lasing of terahertz rotational transitions in highly excited vibrational modes in order to measure their frequencies more accurately. To illustrate the concepts, we used a tunable QCL to excite v3 R-branch transitions in N2O and either enhanced absorption or induced lasing on 20 v3 rotational transitions, whose frequencies between 299 and 772 GHz were then measured using either heterodyne or modulation spectroscopy. The spectra were fitted to obtain the rotational constants B3 and D3, which reproduce the measured spectra to within the experimental uncertainty of ± 5 kHz. We then show how this technique may be generalized by estimating the threshold power to make any rotational transition lase in any N2O vibrational mode.

International audience; Statistical test analysis has proven itself to be versatile tool in various scientific and technical fields, following either a frequentist approach based on a $p$-value, or a Bayesian approach evaluating a Bayes factor. In this study, the authors adapted a Bayesian approach to a radiation-detection application in the industrial context of nuclear decommissioning. The detection of a weak uranium signal on concrete, under the constraint of a very low signal-to-noise ratio, represents in particular a major challenge in this application area. For this purpose, we developed an original Bayesian statistical hypothesis test based on a bivariate gamma distribution of Kibble. Said test allows merging the absolute and relative characters of two Bayesian tests developed in the same context, as well as providing better performance tradeoff in both cases of stationary and non-stationary radiological backgrounds. The simulation-based study showed that the proposed Bayesian test should meet the abovementioned expectations, and allow the detection of a relatively low surface activity uranium contamination, while ensuring a competitive tradeoff between statistical sensitivity and specificity.

Spectrometry of leakage photoneutrons (PN) of a Siemens ONCOR medical linear accelerator head by applying recently invented Sohrabi passive multi-directional multi-detector neutron spherical spectrometry system; measurements of scientific interest and of importance for meeting the regulatory and safety standards.The neutron spectrometry system applied consists of 6 polycarbonate/The well-resolved unfolded directional leakage PN spectra obtained at the 3 positions showed a thermal PN peak of lower intensityfollowed by a tail of epithermal PNs before reaching a fast PN higher peak." The mean PN energy are 0.47 ± 0.03 MeV and 0.48 ± 0.02 MeV respectively for the left and right sides of the head and 0.48 ± 0.02 MeV at the isocenter.Due to importance of leakage PN spectra of an accelerator head being of scientific interest and for meeting regulatory and safety standards, well-resolved leakage PN spectra of 3 locations of the medical accelerator head were determined using Sohrabi passive multi-directional neutron spectrometry system. It is a novel learning that the mean PN spectra and mean PN energy of the 3 locations are quite similar within statistical variations.

In recent years, correlated insulating states, unconventional superconductivity, and topologically non-trivial phases have all been observed in several moiré heterostructures. However, understanding of the physical mechanisms behind these phenomena is hampered by the lack of local electronic structure data. Here, we use scanning tunnelling microscopy and spectroscopy to demonstrate how the interplay between correlation, topology, and local atomic structure determines the behaviour of electron-doped twisted monolayer-bilayer graphene. Through gate- and magnetic field-dependent measurements, we observe local spectroscopic signatures indicating a quantum anomalous Hall insulating state with a total Chern number of $\pm 2$ at a doping level of three electrons per moiré unit cell. We show that the sign of the Chern number and associated magnetism can be electrostatically switched only over a limited range of twist angle and sample hetero-strain values. This results from a competition between the orbital magnetization of filled bulk bands and chiral edge states, which is sensitive to strain-induced distortions in the moiré superlattice., Article 14 pages, 4 figures & Supplementary Information 13 pages, 9 figures

We report on the absolute quantification of nanoparticle interactions with individual human B cells using quadrupole-based inductively coupled plasma mass spectrometry (ICP-MS). This method enables the quantification of nanoparticle-cell interactions at single nanoparticle and single cell levels. We demonstrated the efficient and accurate detection of individually suspended B cells and found a ~100-fold higher association of colloidally stable positively charged nanoparticles with single B cells than neutrally charged nanoparticles. We confirmed that these nanoparticles were internalized by individual B cells and determined that the internalization occurred via energy-dependent pathways consistent with endocytosis. Using dual analyte ICP-MS, we determined that >80% of single B cells were positive for nanoparticles. Our study demonstrated an ICP-MS workflow for the absolute quantification of nanoparticle-cell interactions with single cell and single nanoparticle resolution. This unique workflow could inform the rational design of various nanomaterials for controlling cellular interactions, including immune cell-nanoparticle interactions.

Protein adsorption to solid carbohydrate interfaces is critical to many biological processes, particularly in biomass deconstruction. To engineer more-efficient enzymes for biomass deconstruction into sugars, it is necessary to characterize the complex protein–carbohydrate interfacial interactions. A carbohydrate-binding module (CBM) is often associated with microbial surface-tethered cellulosomes or secreted cellulase enzymes to enhance substrate accessibility. However, it is not well known how CBMs recognize, bind, and dissociate from polysaccharides to facilitate efficient cellulolytic activity, due to the lack of mechanistic understanding and a suitable toolkit to study CBM–substrate interactions. Our work outlines a general approach to study the unbinding behavior of CBMs from polysaccharide surfaces using a highly multiplexed single-molecule force spectroscopy assay. Here, we apply acoustic force spectroscopy (AFS) to probe a Clostridium thermocellum cellulosomal scaffoldin protein (CBM3a) and measure its dissociation from nanocellulose surfaces at physiologically relevant, low force loading rates. An automated microfluidic setup and method for uniform deposition of insoluble polysaccharides on the AFS chip surfaces are demonstrated. The rupture forces of wild-type CBM3a, and its Y67A mutant, unbinding from nanocellulose surfaces suggests distinct multimodal CBM binding conformations, with structural mechanisms further explored using molecular dynamics simulations. Applying classical dynamic force spectroscopy theory, the single-molecule unbinding rate at zero force is extrapolated and found to agree with bulk equilibrium unbinding rates estimated independently using quartz crystal microbalance with dissipation monitoring. However, our results also highlight critical limitations of applying classical theory to explain the highly multivalent binding interactions for cellulose–CBM bond rupture forces exceeding 15 pN.

Stimuli-responsive structural proteins are emerging as promising biocompatible materials for a wide range of biological and nonbiological applications. To understand the physical properties of structural proteins and to replicate their performance in biosynthetic systems, there is a need to understand the molecular mechanisms and relationships that regulate their structure, dynamics, and properties. Here, we study the dynamics of a recombinant squid-inspired protein from

Multicomponent lipid bilayers are used as models for searching the origin of spatial heterogeneities in biomembranes called lipid rafts, implying the coexistence of domains of different phases and compositions within the lipid bilayer. The spatial organization of multicomponent lipid bilayers on a scale of a hundred nanometers remains unknown. Brillouin spectroscopy providing information about the acoustic phonons with the wavelength of several hundred nanometers has an unexplored potential for this problem. Here, we applied Brillouin spectroscopy for three binary bilayers composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC), and cholesterol. The Brillouin experiment for the oriented planar multibilayers was realized for two scattering geometries involving phonons for the lateral and normal directions of the propagation. The DPPC–DOPC mixtures known for the coexistence of the solid-ordered and liquid-disordered phases had bimodal Brillouin peaks, revealing the phase domains with sizes more than a hundred nanometers. Analysis of the Brillouin data for the binary mixtures concluded that the lateral phonons are preferable for testing the lateral homogeneity of the bilayers, while the phonons spreading across the bilayers are sensitive to the layered packing at the mesoscopic scale.

[FeFe] hydrogenases are highly active catalysts for hydrogen conversion. Their active site has two components: a [4Fe-4S] electron relay covalently attached to the H

Three polymorphs of salicylideneaniline (SA) were prepared, and their photochromic behavior was examined using a recently developed single-crystal microscopic UV-vis spectroscopy approach. This system enabled us to acquire absorption data during the bleaching process as a function of temperature and visible light intensity. First, we demonstrated that, in contrast to the generally accepted assumption, the bleaching curves were notably influenced by the degree of photosaturation at the initial stage. By modifying our kinetic model to include the term representing the initial degree of photosaturation, we successfully obtained the kinetic parameters intrinsic to each crystal structure. Second, we further analyzed the kinetic parameters to show that the bleaching process was accelerated by visible light irradiation to a significantly higher degree than by thermal relaxation. The two bleaching-prompting effects were quantitatively compared between two photochromic polymorphs, α

The accuracy and precision of laser-induced breakdown spectroscopy (LIBS) quantitative analysis are significantly limited by the spectral noise. Normalization and ensemble averaging of multiple spectra were often used to preprocess spectra. However, these methods cannot completely remove the spectral noise. Data uncertainty due to the irremovable spectral noise will affect LIBS quantitative analysis. Therefore, this paper proposes a method using data uncertainty to improve the performance of LIBS quantitative analysis. The proposed method uses several spectra to characterize each sample to preserve some data uncertainty in the calibration data matrix. Thus, the data uncertainty is used to optimize the calibration model for improving the toleration to the spectral signal variation. As a result, the optimized calibration model had better accuracy and robustness than the calibration model trained by conventional method. The best root mean square error of prediction (RMSEP) of the ash content of coal was 1.152% for the optimized calibration model, while that for the conventional calibration model was 1.718%. The optimized calibration model also showed a lower relative standard deviation (RSD) value of repeated predictions. Moreover, the calibration model for predicting the ash content in biomass was also optimized by the proposed method. The optimized calibration model outperformed the conventional calibration model again, which demonstrated the extensive applicability of the proposed method.

We demonstrate the sensitivity enhancement in inductively coupled plasma mass spectrometry (ICP-MS) by combining ultrasonic nebulization via the nitrogen mixed gas effect. We showed the effect of nitrogen gas concentration (0-5%) in the nebulizer gas on the signal sensitivity for 63 elements using commercially available (concentric and ultrasonic) nebulizers. In addition, the limit of detection (ng L

Lipid nanoparticles (LNPs) are the most widely investigated delivery systems for nucleic acid-based therapeutics and vaccines. Loading efficiency of nucleic acids may vary with formulation conditions, and it is considered one of the critical quality attributes of LNP products. Current analytical methods for quantification of cargo loading in LNPs often require external standard preparations and preseparation of unloaded nucleic acids from LNPs; therefore, they are subject to tedious and lengthy procedures, LNP stability, and unpredictable recovery rates of the separated analytes. Here, we developed a modeling approach, which was based on locally weighted regression (LWR) of ultraviolet (UV) spectra of unpurified samples, to quantify the loading of nucleic acid cargos in LNPs

Vibronic coupling, the interplay of electronic and nuclear vibrational motion, is considered a critical mechanism in photoinduced reactions such as energy transfer, charge transfer, and singlet fission. However, our understanding of how particular vibronic couplings impact excited-state dynamics is lacking due to the limited number of experimental studies of model molecular systems. Herein, we use two-dimensional electronic spectroscopy (2DES) to launch and interrogate a range of vibronic coherences in two distinct types of perylenediimide slip stacks─along the short and long molecular axes, which form either an excimer or a mixed state between the Frenkel exciton (FE) and charge transfer states. We explore the functionality of these vibronic coherences using quantum beatmaps, which display the Fourier amplitude signal oscillations as a function of pump and probe frequencies, along with knowledge of the characteristic signatures of the FE, ionic, and excimer species. We find that a low-frequency vibrational mode of the short-axis slip stack appears concomitantly with the formation of the excimer state, survives 2-fold longer than in the FE state in the reference monomer, and shows a phase shift compared to other modes. For the long-axis slip stacks, a pair of low-frequency modes coupled to a high-frequency coordinate of the FE state were found to play a critical role in mixed-state generation. Our findings thus experimentally reveal the complex and varying roles of vibronic couplings in tightly packed multimers undergoing a range of photoinduced processes.

The introduction of "deep learning" algorithms for feature identification in digital imaging has paved the way for artificial intelligence applications that up to a decade ago were considered technologically impossible to achieve, from the development of driverless vehicles to the fully automated diagnostics of cancer and other diseases from histological images. The success of deep learning applications has, in turn, attracted the attention of several researchers for the possible use of these methods in chemometrics, applied to the analysis of complex phenomena as, for example, the optical emission of laser-induced plasmas. In this paper, we will discuss the advantages and disadvantages of convolutional neural networks, one of the most diffused deep learning techniques, in laser-induced breakdown spectroscopy (LIBS) applications (classification and quantitative analysis), to understand the real potential of "deep LIBS" in practical everyday use. In particular, the comparison with the results obtained using "shallow" artificial neural networks will be presented and discussed, taking as a case study the analysis of six bronze samples of known composition. (Figure presented.).