Total Reflection Research Articles

Cigarette paper as evidence: Forensic profiling using ATR-FTIR spectroscopy and machine learning algorithms

This research highlights the underestimated significance of cigarette paper as evidence at crime scenes. The primary objective is to distinguish cigarette paper from similar-looking alternatives, addressing the first research objective. The second objective involves identifying cigarette paper brands using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and machine learning (ML) algorithms. Accurate differentiation of cigarette paper from normal paper is emphasized. ATR-FTIR spectroscopy, coupled with principal component analysis (PCA) for dimensionality reduction, is employed for brand identification. Among fifteen ML algorithms compared, the CatBoost classifier excels for both objectives. This research presents a non-destructive, effective method for studying cigarette paper, contributing valuable insights to crime scene investigations.

High Yield Synthesis of Cellulose Nanocrystals From Avicel by Mechano‐Enzymatic Approach

AbstractCellulose nanocrystals are an important class of bio‐based crystalline nanostructures, finding application in several technological fields, including paper and textile coating, biocomposite engineering, biocatalysts immobilization, etc. This study explores enzymatic hydrolysis of Avicel, using endoglucanase from Aspergillus niger, to find an environmentally friendly method to extract cellulose nanocrystals from cellulose sources. Enzymatic hydrolysis has the advantage of reduced energy consumption and higher environmental friendliness compared to acid hydrolysis. In this work, we report for the first time very high nanocrystals yield by combining mechanical pretreatment of the cellulose starting material with a ball miller and endoglucanase hydrolysis, as a result of an extensive optimization of reaction conditions. In particular, a ball milling pretreatment carried out for 50 minutes at 3 Hz, allowed to isolate enzymatic CNCs with 76 % yield and with crystallinity as high as 75 %. The materials were characterized by X‐Ray diffractometry, attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, dynamic light scattering, zeta potential and field emission scanning electron microscopy (FE‐SEM). Their characteristics were compared with the properties of sulfated CNCs, prepared from Avicel by sulfuric acid hydrolysis. Our results are technologically relevant, as they contribute to the accessibility and sustainability of CNCs for a wide range of applications in various industries.

Steering the Site Distance of Atomic Cu‐Cu Pairs by First‐Shell Halogen Coordination Boosts CO2‐to‐C2 Selectivity

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C‐C coupling to unravel their structure‐performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu‐Cu dual sites with different site distance coordinated by halogen at the first‐shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long‐range Cu‐Cu (Cu‐I‐Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1%, and excellent stability. In addition, the linear relationships that the long‐range Cu‐Cu dual site is accelerated to C2H4 generation and short‐range Cu‐Cu (Cu‐Cl‐Cu) dual site is beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long‐range Cu‐Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C‐C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site‐distance‐dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu‐Cu dual sites.

Steering the Site Distance of Atomic Cu-Cu Pairs by First-Shell Halogen Coordination Boosts CO2-to-C2 Selectivity.

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C-C coupling to unravel their structure-performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu-Cu dual sites with different site distance coordinated by halogen at the first-shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long-range Cu-Cu (Cu-I-Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1%, and excellent stability. In addition, the linear relationships that the long-range Cu-Cu dual site is accelerated to C2H4 generation and short-range Cu-Cu (Cu-Cl-Cu) dual site is beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long-range Cu-Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C-C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site-distance-dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu-Cu dual sites.

Non-invasive diagnostic test for lung cancer using biospectroscopy and variable selection techniques in saliva samples.

Lung cancer is one of the most commonly occurring malignant tumours worldwide. Although some reference methods such as X-ray, computed tomography or bronchoscope are widely used for clinical diagnosis of lung cancer, there is still a need to develop new methods for early detection of lung cancer. Especially needed are approaches that might be non-invasive and fast with high analytical precision and statistically reliable. Herein, we developed a swab "dip" test in saliva whereby swabs were analysed using attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy harnessed to principal component analysis-quadratic discriminant analysis (QDA) and variable selection techniques employing successive projections algorithm (SPA) and genetic algorithm (GA) for feature selection/extraction combined with QDA. A total of 1944 saliva samples (56 designated as lung-cancer positive and 1888 designed as controls) were obtained in a lung cancer-screening programme being undertaken in North-West England. GA-QDA models achieved, for the test set, sensitivity and specificity values of 100.0% and 99.1%, respectively. Three wavenumbers (1422 cm-1, 1546 cm-1 and 1578 cm-1) were identified using the GA-QDA model to distinguish between lung cancer and controls, including ring C-C stretching, CN adenine, Amide II [δ(NH), ν(CN)] and νs(COO-) (polysaccharides, pectin). These findings highlight the potential of using biospectroscopy associated with multivariate classification algorithms to discriminate between benign saliva samples and those with underlying lung cancer.

Corrosion Behavior of 3104 Aluminum Cans When Used as Packaging for Chinese Liquor

Aluminum cans are commonly used for packaging soft drinks and low-alcohol beverages due to their good recyclability. To enhance the economic cycle and expand the packaging of liquors, the feasibility of commercial 3104 aluminum cans for packaging Chinese liquor was studied. The aluminum’s migration into alcoholic solutions was studied using inductively coupled plasma emission spectroscopy (ICP-OES). Electrochemical impedance spectroscopy (EIS) was used to study the corrosion process of epoxy coatings on the aluminum cans. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), infrared attenuated total reflection (IR-ATR), and X-ray diffraction (XRD) were used to determine the inner coatings and adhering surfaces of the cans and the corrosion process. The results showed that the maximum aluminum migration in Chinese liquor was 4.3572 mg/kg at 60 °C for 30 days. The epoxy coating was corroded enough to decrease the coating impedance and expose the metal substrate after 25 days. Permeation and aging degradation of coatings are the main factors to consider when packaging liquor.

A novel approach for using submerged structure as wave-trapping zone

Entrapment of waves is a hydrodynamic phenomenon that occurs under certain incident wave circumstances. The present article, based on potential flow theory, deals with the phenomena of waves interacting with a proposed submerged structure. Focus of this study is on the frequencies for which the wave trapping occurs in the region of the proposed structure. The frequencies presented correspond to significantly higher values of velocity potential in the region. We refer this region as a wave-trapping zone. In scattering problem the reflection coefficient is also investigated with respect to submergence depth, water depth, length and rigidity of the structure and other physical parameters. The optimum values of the structural parameters are also proposed for zero transmission and trapping frequencies. The investigation establishes that for a suitable configuration we can achieve a range of frequencies for which such a geometry can be used as breakwater with total reflection and at certain frequencies also for trapping of waves.

Waveguide-based microscope slide for label-free high-resolution imaging

Waveguide-based total internal reflection fluorescence microscopy has been widely adopted due to its excellent signal-to-noise ratio over a large field of view. However, with the increasing demand for label-free imaging, waveguide-based evanescent light scattering microscopy (ESM) has also garnered significant attention. Here, we present a low-cost waveguide-based microscope slide that offers easier integration with conventional optical microscopy. This microscope slide uses an incoherent light source coupled to a lithium tantalate (LT) planar waveguide to generate an evanescent light that illuminates samples located within a few hundred nanometers of the waveguide surface. We perform its application for imaging chromium nanoholes and polystyrene nanospheres, demonstrating its label-free, high-resolution, high-contrast imaging performance. LT waveguide microscope slides provide a simple and effective solution for ESM.

Novel thermally regenerated flexible cellulose-based films

AbstractIn this work, cellulose powder obtained by acid hydrolysis of industrial Eucalyptus kraft pulp was dissolved in NaOH/Urea/H2O system (7/12/81 wt%) in a concentration of 6% (w/v). Cellulose films were prepared by spreading the dissolved cellulose over glass plates, followed by thermal regeneration – a novel approach reported here for the first time. To obtain final flexible films, plasticization was carried out by immersion in aqueous glycerol solutions of various concentrations (10 to 70 wt%) and hot-pressing (at 0.1 MPa and 105 ºC) was used to dry and compress the cellulose films. The resulting films were characterized by Attenuated Total Reflectance Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, contact angle measurements, transparency analysis, and gas permeabilities (oxygen and water vapor). Highly flexible films containing up to 50 wt% of glycerol were successfully obtained, exhibiting no glycerol release upon manual handling. Overall, the produced films demonstrated dense and compact structure, good transparency, flexibility and malleability, and very low oxygen permeability.

Kraft lignin-based polyurethanes: Bulk properties, stability and adhesion to native aluminum surfaces

Lignin as a byproduct from pulp and paper manufacturing has been extensively investigated as raw material for polymer developments. Although, fundamental topics related to the adhesion mechanisms of lignin-based reactive polyurethanes (LPU) still remain unclear. In this work, LPU thin films on native aluminum surface were prepared and characterized. Diluted in THF, employed as the solvent, reactive mixtures of 4,4′-methylene diphenyl isocyanate (4,4′-MDI) and the soluble fraction of three lignins (liquid hydroxypropylated Kraft lignin and two powder Kraft lignins with different pH) were used for LPU thin film deposition via spin coating on aluminum (PVD layer on silicon wafer). The resulting film thickness ranged from 8 nm to several micrometers. The chemical state of the three LPU compositions was assessed in bulk by infrared attenuated total reflectance (IR-ATR) and in the thin films by infrared external reflection absorption spectroscopy (IR-ERAS). Binding energies of 4,4′-methylene diphenyl diisocyanate with aliphatic and aromatic hydroxyl groups were estimated using Density Functional Theory (DFT) simulations. Thus, besides the elucidation of the bulk chemical state of LPUs, the relation to adhesion and stability of LPUs to a native aluminum surface was evaluated. In addition, film topography and homogeneity were monitored by SFM. All lignin types form uniform and homogeneous films. Results revealed a higher consumption of isocyanate groups (NCO) in the formulation with the alkaline Kraft lignin than with the acid one, despite its lower hydroxyl content. A gradient of unreacted NCO was observed in LPU thin films obtained with the powder Kraft lignin types. Residual NCO is also found in thicker films, while the thinnest films did not contain unreacted NCO anymore, indicating the activating effect of the native aluminum surface on LPU formation.

A methodological approach to age estimation of the intra-puparial period of the forensically relevant blow fly Calliphora vicina via Fourier transform infrared spectroscopy.

Estimating the age of immature blow flies is of great importance for forensic entomology. However, no gold-standard technique for an accurate determination of the intra-puparial age has yet been established. Fourier transform infrared (FTIR) spectroscopy is a method to (bio-)chemically characterise material based on the absorbance of electromagnetic energy by functional groups of molecules. In recent years, it also has become a powerful tool in forensic and life sciences, as it is a fast and cost-effective way to characterise all kinds of material and biological traces. This study is the first to collect developmental reference data on the changes in absorption spectra during the intra-puparial period of the forensically important blow fly Calliphora vicina Robineau-Desvoidy (Diptera: Calliphoridae). Calliphora vicina was reared at constant 20°C and 25°C and specimens were killed every other day throughout their intra-puparial development. In order to investigate which part yields the highest detectable differences in absorption spectra throughout the intra-puparial development, each specimen was divided into two different subsamples: the pupal body and the former cuticle of the third instar, that is, the puparium. Absorption spectra were collected with a FTIR spectrometer coupled to an attenuated total reflection (ATR) unit. Classification accuracies of different wavenumber regions with two machine learning models, i.e., random forests (RF) and support vector machines (SVMs), were tested. The best age predictions for both temperature settings and machine learning models were obtained by using the full spectral range from 3700 to 600 cm-1. While SVMs resulted in better accuracies for C. vicina reared at 20°C, RFs performed almost as good as SVMs for data obtained from 25°C. In terms of sample type, the pupal body gave smoother spectra and usually better classification accuracies than the puparia. This study shows that FTIR spectroscopy is a promising technique in forensic entomology to support the estimation of the minimum post-mortem interval (PMImin), by estimating the age of a given insect specimen.

Photonic crystal-connected bidirectional micro-ring resonator array for duplex mode and wavelength channel (de)multiplexing

The progress of on-chip optical communication relies on integrated multi-dimensional mode (de)multiplexers to enhance communication capacity and establish comprehensive networks. However, existing multi-dimensional (de)multiplexers, involving modes and wavelengths, face limitations due to their reliance on single-directional total internal reflection and multi-level mode conversion based on directional coupling principles. These constraints restrict their potential for full-duplex functionality and highly integrated communication. We solve these problems by introducing a photonic-like crystal-connected bidirectional micro-ring resonator array (PBMRA) and apply it to duplex mode-wavelength multiplexing communication. The directional independence of total internal reflection and the cumulative effect of the subwavelength-scale pillar within the single-level photonic crystal enable bidirectional mode and wavelength multiplexed signals to transmit among multi-pair nodes without interference, improving on-chip integration in single-level mode conversion. As a proof of concept, we fabricated a nine-channel bidirectional multi-dimensional (de)multiplexer, featuring three wavelengths and three TE modes, compactly housed within a footprint of 80 μm×80 μm, which efficiently transmits QPSK-OFDM signals at a rate of 216 Gbit/s, achieving a bit error rate lower than 10−4. Leveraging the co-ring transmission characteristic and the orthogonality of the mode-wavelength channel, this (de)multiplexer also enables a doubling of communication capacity using two physical transmission channels.

Cellulose binary coatings with spherical envelope structure via structure rearrangement in ball milling for integrated radiative cooling-electricity generation.

Passive daytime radiative cooling is a zero-energy consumption cooling technology, which can dissipate heat to outer space via infrared radiation. Recently, coupling radiative cooling technology and thermoelectric devices to generate electricity has attracted much attention. However, existing radiative cooling integrated thermoelectric devices still suffer from low-temperature gradient and output voltage. Here, based on the Mie scattering and internal reflection enhancing principle, an impact-inducing geometry reconstruction approach was proposed to fabricate hierarchical nanostructured cellulosic coatings with good daytime cooling performance to achieve stable electricity generation function, which can be realized by using a scalable and facile wet ball milling technology. Guided by the theoretical simulations of the finite difference time domain method (FDTD), the cellulose and TiO2 nanoparticles can assemble into spherical envelope structured coatings drying by the shear, impact, and friction interaction in the ball milling process, dramatically enhancing the Mie scattering and internal reflection of coatings. The cellulosic coatings exhibit sunlight reflectivity of 0.962 and infrared emissivity of 0.94, resulting in a daytime radiative cooling efficiency of 5.9°C under direct sunlight. Energy Plus stimulation demonstrated 35% cooling energy and 468.9 kWh of cooling energy can be saved annually in China. Meanwhile, this cellulosic coating-based thermoelectric device can deliver a high voltage output of 150mV under 1 Sun due to the strong bonding and high-temperature gradient formation (30°C), which is higher than previous reports. This study will facilitate the development of sustainable power generation device for the goal of green future.

A self-adaptive model for sensing total phosphorus in natural water bodies using Fourier transform mid-infrared attenuated total reflectance spectroscopy

As the most economically developed area in China, the environmental water quality of Guangdong-Hong Kong-Macao Greater Bay Area has received extensive attention, and the spatial variations of total phosphorus (TP) in the Greater Bay were significant, conventional laboratory analysis is difficult to meet the requirements of TP monitoring due to time and cost consuming, and Fourier transform infrared attenuated total reflectance spectroscopy (FTIR-ATR) technology, combined with the self-adaptive partial least squares (SA-PLS) model, was used to determine the TP concentration. The results showed that P-O vibrations were observed in the wavenumber range of 1200–900 cm−1, and prediction models were established by using this range. For the conventional partial least squares (PLS) model, the R2, RMSE and RPD were 0.817, 0.022 mg L−1 and 2.335, respectively, while for the SA-PLS model the prediction was improved with the values of 0.965, 0.010 mg L−1, 5.296, respectively, and the SA-PLS mode prediction was satisfied when the TP content in water was more than 0.05 mg L−1. It was found that the TP determination was interfered by sulfate, when the sulfate content was < 100 mg L−1, both SA-PLS and the conventional PLS model could be used for quantitative analysis of TP; when sulfate content was > 100 mg L−1, PLS model could not be used while the SA-PLS model still achieved an excellent prediction. Therefore, FTIR-ATR combined with SA-PLS model can rapidly determine TP in water, providing an alternative strategy for monitoring TP in natural water bodies.

Sludge Biochar Accelerates Transformative Phenolic Compounds Removal from Wastewater via the Coupling Mechanism

In this work, we investigated the mechanism of the oxidation of phenolic compounds (PCs) by graphitic sludge biochar (SDBCs) via a catalytic coupling regime in the presence of potassium persulfate (PDS). In-situ synchrotron attenuated total reflection Fourier transform infrared spectroscopy (in-situ ATR-FITR) combined with Raman spectroscopy directly monitored the formation of SDBC-PDS⁎ complexes, which drove the electron-transfer pathway as evidenced by electrochemical tests and galvanic cell experiments. The coupling of pollutants into oligomers effectively reduced total organic carbon in water with a low PDS usage (PDS consumption to phenol degradation ratio of 2.2). Furthermore, our research showed that the biochar-based nonradical system effectively treats various PCs, with oxidation rates related to their half-wave potential and Hammett constant. Overall, this work explored sludge biochar engineering, PCs transformation and interfacial coupling mechanism, providing a novel approach for the efficient and cost-effective treatment of phenolic wastewater with low chemical input.

EXPRESS: Understanding Advanced Attenuated Total Reflection Correction: The Low Absorbance Assumption.

We present an attenuated total reflection (ATR) correction scheme capable of rectifying ATR spectra while considering the polarization state for arbitrary angles of incidence, provided that this angle exceeds the critical angle for the entire ATR spectrum. Due to its reliance on the weak absorption approximation, it cannot achieve perfect correction of the ATR spectra. However, comprehending its functionality may offer valuable insights into the concept behind the weak absorption approximation. Depending on the specific polarization state of an instrument accessory combination, this correction scheme may outperform the proprietary advanced ATR correction authored by ThermoFisher while being as user-friendly, but in contrast to the latter completely transparent with regard to its functionality.

Metal–Organic Framework Supported Low‐Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

AbstractIt is still a great challenge to achieve high selectivity of ethanol in CO2 electroreduction reactions (CO2RR) because of the similar reduction potentials and lower energy barrier of possible other C2+ products. Here, we report a MOF‐based supported low‐nuclearity cluster catalysts (LNCCs), synthesized by electrochemical reduction of three‐dimensional (3D) microporous Cu‐based MOF, that achieves a single‐product Faradaic efficiency (FE) of 82.5 % at −1.0 V (versus the reversible hydrogen electrode) corresponding to the effective current density is 8.66 mA cm−2. By investigating the relationship between the species of reduction products and the types of catalytic sites, it is confirmed that the multi‐site synergism of Cu LNCCs can increase the C−C coupling effect, and thus achieve high FE of CO2–to–ethanol. In addition, density functional theory (DFT) calculation and operando attenuated total reflectance surface‐enhanced infrared absorption spectroscopy further confirmed the reaction path and mechanism of CO2–to–EtOH.

Investigating the mechanism of SiO2/4H-SiC interface traps passivation by boron incorporation through FT-IR analysis of near-interface SiO2

This study investigates the effect of boron-incorporation (B-incorp) on SiO2 properties near the SiO2/4H-SiC interface by Fourier transforms infrared spectroscopy with attenuated total reflection mode. We focus on the range of Si–O–Si asymmetric stretching vibrations, whereas B-incorp samples exhibited a different peak shift trend compared to the thermal oxidized samples. The observed peak shift, corroborated by the calculated spectral simulation, suggests a reduction in oxygen deficiency near the interface for B-incorp samples. This suggests a potential link between B-incorp and the passivation of traps near the interface, possibly through its influence on SiO2 stoichiometry.

Discrimination of some expired and unexpired drugs under different conditions using Fourier Transform infrared-Attenuated Total Reflectance

Repackaging of expired medicines has become common in developed countries and can cause serious health problems. Therefore, the identification of these products is of considerable importance. This study investigated the applicability of an analytical method based on Fourier Transform Infrared spectroscopy combined with chemometrics for separating two types of expired and non-expired tablets. The study focuses on vildagliptin, collagen, and vitamin tablets and represents a preliminary study for different types of tablets. Instrumental conditions were determined by central composite design. As a result of the the variance analysis, it was found that the pressure parameter was significant, while the number of scans and resolution were insignificant. The optimum instrumental conditions were determined as attenuated total reflection module pressure 57, scan number 20, and spectral resolution 4 cm−1. Derivatizing spectra were used to find major peaks that make a significant difference. As a result of principal component analysis, PC1 in the 92-96.9% and PC2 in the range of 6.6-3% range explained the total variance. In the results obtained, significant discrimination and clustering between the species were seen, and for all three species, expired and non-expired drug samples with different storage conditions could be separated. Fourier Transform Infrared spectroscopy can be helpful in screening for counterfeit drugs as it is easy to use and requires little sample preparation. It is also thought that this approach may be helpful for the initial evaluation of repackaged tablets.

Control of visible-range transmission and reflection haze by varying pattern size, shape and depth in flexible metasurfaces

Cost-effective soft imprint lithography technique is used to prepare flexible thin polymeric surfaces containing a periodic arrangement of nanodimples and nanobumps of sub-micron size. Using a single master mold of self-assembled colloidal crystal, metasurfaces with different depths and heights of patterns with a fixed pitch are possible, which makes the process inexpensive and simple. These metasurfaces are studied for their diffuse and total transmission and reflection spectra in the visible range. The transmission haze and reflection haze are calculated from the measurements. The surface containing nanobumps of lesser pattern height result in higher values of reflection and transmission haze than from surfaces containing nanodimples of much higher depth for the same pitch. The haze is more dependent on the pattern depth or height and less dependent on the pitch of the pattern. Far-field transmission profiles measured in the same wavelength range from the patterned surfaces show that the scattering increases with the increase of the ratio of pattern depth/height to pitch, similar to the haze measurements conducted with a closed integrating sphere. These profiles show that the angular spread of scattered light in transmission is within 10°, explaining the reason for the relatively low transmission haze in all the patterned surfaces. Simulation results confirm that the nanobump pattern gives higher transmission haze compared to nanodimple pattern. By controlling the ratio of pattern depth/height to pitch of the features on these surfaces, both an increase in optical haze and a balance between total reflection intensity and total transmission intensity can be achieved.Graphical