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Spectrochimica acta
Pergamon
Spectrochimica acta

Pergamon

1386-1425

Spectrochimica acta/Journal Spectrochimica acta
正式出版
收录年代

    Synchrotron Radiation Fourier Transform Infrared (SR-FTIR) spectroscopy in exploring ancient human hair from Roman period Juliopolis: Preservation status and alterations of organic compounds

    Lorentz, K. O.Kamel, G.Lemmers, S. A. M.Miyauchi, Y....
    10页
    查看更多>>摘要:We explore the preservation status and alterations of organic compounds in Roman period human hair strands from a specific individual (M196) excavated at Juliopolis (JP). How do these organic compounds present in this c. 2000-year-old human hair compare to those present in modern hair? Alterations to organic compounds in archaeological human hair are caused by biological degradative processes dependent on multifactorial processes acting on the hair since the deposition of a body in a mortuary context. We investigate the type of organic compounds present using Synchrotron Radiation Fourier Transform Infrared (SR-FTIR). Juliopolis (Iuliopolis) is an ancient multiperiod city, located in the Cayirhan district of Nallihan, northwest of Ankara. The Juliopolis necropolis from which M196 was recovered was in use throughout the Hellenistic, Roman, and Byzantine periods, and yielded over 700 tombs with numerous human remains. One tomb (M196) contained human remains of exceptional preservation status, including substantial amounts of hair. Human hair from archaeological contexts is not only extremely rare, but importantly, has high analytical value, with potential for analysis of diet, geographical origins, ancient DNA, metal exposure, and other aspects of life in a time-resolved manner. These data make significant contributions to the life history of the individual (osteobiography), as well as contribute towards key archaeological questions. As these analyses are in their majority destructive, prior evaluation of the preservation of sufficient amounts of the organic compounds on which many such analyses rely upon is crucial, to avoid unnecessary loss of precious ancient samples. The results of our SR-FTIR analyses at SESAME synchrotron show that keratin in the JP M196 is more degraded in comparison to the modern reference sample. However, the results also point to clear potential for further analyses with techniques relying on organic compound preservation, such as C and N isotopic analyses for diet, and aDNA. (c) 2022 Elsevier B.V. All rights reserved.

    Online rapid total nitrogen detection method based on UV spectrum and spatial interval permutation combination population analysis

    Geng, JingxuanYang, ChunhuaLan, LijuanLi, Yonggang...
    10页
    查看更多>>摘要:Rapidly and accurately detect the total nitrogen (TN) concentration is enormously important for surface water protection considering the critical role it plays in reflecting the eutrophication of surface water. However, traditional TN detection methods have to experience a tedious oxygen digestion process, which tremendously limits the detection speed of TN. To solve this problem, we propose a novel online rapid TN detection method. The transformations of nitrogenous substances during the oxidative digestion process are observed by using ultraviolet (UV) spectroscopy and the concentration of TN can be predicted by only using the variation of spectrum in the early oxygen digestion process. To select the most informative variables hidden in the collected three-dimension spectrum, a new wavelength selection algorithm called spatial interval permutation combination population analysis (siPCPA) is proposed, which considers the spatial-temporal relationships among each variable in the spectrum. By using the real surface water samples collected from Houhu Lake, Changsha, China, the effectiveness of our proposed new detection and selection methods are verified and compared with other state-of-the-art methods. As a result, the practical application experiment shows that our methods can determine the concentration of TN in 5 min with a relative error of less than 5%. (c) 2022 Elsevier B.V. All rights reserved.

    Visible-light driven photocatalytic performance of eco-friendly cobalt-doped ZnO nanoarrays: Influence of morphology, cobalt doping, and photocatalytic efficiency

    Zhang, JiyongXu, XinruZhang, WentaoHuang, Yi...
    12页
    查看更多>>摘要:In order to remove the organic pollution from water environment, Co2+-doped ZnO nanoarray photocatalyst was prepared through a hydrothermal process. The influences of Co2+ doping amount and hydrothermal temperature on the nanostructure and photocatalytic performance of Co2+-doped ZnO nanoarray were discussed in detail. The standard ZnO structure and nanoarray morphology of Co2+- doped ZnO samples were achieved and the absorption of visible light was also realized through Co2+ doping. The 2% Co2+-doped ZnO nanoarray prepared at 95 degrees C exhibited excellent photocatalytic activity and could degrade 96% of methylene blue solution within 120 min under visible light. Furthermore, the as prepared 2% Co2+-doped ZnO nanoarray still maintained 91% for removal rate after 3 cycles of photocatalytic degradation, showed good photocatalytic activity and recyclability. All results indicate that ZnO nanoarray with Co2+ doping has a potential application in visible light photocatalysis for environmental protection and pollution control. (c) 2022 Elsevier B.V. All rights reserved.

    NMR and other molecular and elemental spectroscopies for the characterization of samples from an outdoor mural painting by Siqueiros

    Mejia-Gonzalez, AdrianJaidar, YareliZetina, SandraAguilar-Rodriguez, Pablo...
    16页
    查看更多>>摘要:This study presents the use of high resolution Nuclear Magnetic Resonance (NMR) as an outstanding tool for identifying with accuracy the structure of the polymers used as binders and the additives used as plasticizers in samples from a mural painted by David Alfaro Siqueiros between 1964 and 1972, an important period in which his artistic production has not been previously studied. Additionally, the presence of some organic pigments was detected. The mural Trazos de composicion piramidal currently located outside of Siqueiros' studio La Tallera, in Cuernavaca Morelos (Mexico) was an artistic experiment done by Siqueiros to test outdoor painting. Eight micro-samples of paint were thoroughly analyzed by Optical Microscopy (OM), Scanning Electron Microscopy - Energy Dispersive X-Ray Spectroscopy (SEM-EDS), Fiber Optics Reflectance Spectra (FORS), Transmission Fourier Transform Infrared Spectroscopy with Attenuated Total Reflectance mode (FTIR-ATR) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). Through these studies, contrasted with an historical investigation, we demonstrate that the samples present a multi-layered and complex painting system because Siqueiros made at least two versions of the painting. The multi-layered structure and the variable composition of each layer challenged the application of several analytical methodologies traditionally used for cultural heritage materials. In one sample, each layer was separated and they were studied in detail by FTIR-ATR, Py-GC/MS and NMR. This study revealed the presence of two main binders: acrylics in the first layers and nitrocellulose in the last one, also some phthalates and fatty acids were detected as additives. Inorganic pigments and fillers were identified as titanium dioxide and iron red oxide as well as diatoms and carbonates.The main contribution of this study, where NMR spectroscopy was applied for the first time in modern mural painting analysis, is the characterization of the materials used by Siqueiros during the last years of his artistic production.(c) 2022 Elsevier B.V. All rights reserved.

    In-depth probing of thermally-driven phase separation behavior of lamella-forming PS-b-PMMA films by infrared nanoscopy

    Kim, JihoLee, WooseopKim, HyejiRyu, Du Yeol...
    6页
    查看更多>>摘要:A non-invasive, image-based analytic method utilizing scattering-type scanning near-field optical microscopy (s-SNOM) is suggested to evaluate the phase separation behavior of lamella-forming polystyreneb-poly(methyl methacrylate) (PS-b-PMMA) block copolymer films. Taking advantage of the penetrability of the tip-enhanced IR signal into the films, the spatio-spectral maps of each component are constructed. Subsequently, the effect of a sole and combinatorial applications of the self-assembly procedures, such as solvent vapor annealing (SVA) and/or thermal annealing (TA), on the spatial distribution of PS or PMMA components is quantitatively assessed in terms of the areal portions of the PS domain, PMMA domain, and the mixed zone that is adjacent to the domain border. Additionally, by statistically comparing the local concentration profiles, the chemical contrast between the domains turns out to be dependent upon the annealing procedures (namely, SVA and SVA + TA). This technique can pave the way to an uncomplicated but precise investigation of the polymer nanostructure-based thin film devices whose performances are critically governed by the spatial arrangement of the chemical elements. (C) 2022 Elsevier B.V. All rights reserved.

    A novel fluorescence method for detection of phosphate anions based on porphyrin metalation

    Zhang, XingpingWang, JiujunYang, HualinJuan, Yewen...
    6页
    查看更多>>摘要:In this work, a novel fluorescence method for the detection of phosphate anions (PO43-) was developed based on porphyrin metalation. Through catalysis by G-quadruplex (G4), Cu2+ could insert into the porphyrins to quench their fluorescence. G4 simultaneously improved the fluorescence of the porphyrins but not that of Cu2+-porphyrin. In the absence of PO43-, the porphyrins were metallized by Cu2+, and no fluorescence was observed. In the presence of PO43-, PO43- could coordinate with Cu2+ to prevent porphyrin metalation. Free porphyrin could bind with G4 to emit strong fluorescence. By comparing four common porphyrins, we found that G4 had the greatest effect on increasing the fluorescence intensity of N-methylmesoporphyrin IX (NMM). Thus, NMM/G4 was chosen for the design of a biosensor. Under optimal experimental conditions, this method showed high sensitivity and satisfactory selectivity for PO43- with a detection limit of 44 nM in a linear range of 0.01-1.0 mu M. The recovery experiments showed recovery rates of 93.75-106.00%, suggesting a great potential for measuring PO43- in real samples. (C) 2022 Elsevier B.V. All rights reserved.

    A multifunctional metal regulator as the potential theranostic agent: Design, synthesis, anti-AD activities and metallic ion sensing properties

    Kou, XiaodiHu, ChengtingShi, XuliYang, Aihong...
    10页
    查看更多>>摘要:Although there is no cure for Alzheimer's disease (AD) due to its complex pathogenesis, early detection and treatment can help delay the development of the disease. So, it is necessary to develop multifunc-tional metal regulators that can integrate the therapeutics and diagnostics effect against AD. In this work, N-(anthracene-9-ylmethylene)benzohydrazide (probe 1), a fluorescent probe with imine and carbonyl as chelating sites was designed and synthesized. Results showed that 1 had good activities related to AD, such as regulation of metal homeostasis, inhibition of beta-amyloid (A beta) aggregation and scavenging of reac-tive oxygen species. The selectivity experiment showed that probe 1 had a good recognition effect on Cu2+. Fluorescence imaging assay also indicated that probe 1 had a good fluorescence imaging effect on Cu2+ in living cells. Furthermore, probe 1 had showed no cytotoxicity and good BBB permeability. These results indicated that probe 1 had potential diagnostic and therapeutic capabilities, and can be used as the multifunctional theranostic agent for AD. (c) 2022 Elsevier B.V. All rights reserved.

    Magnesium sulfate as a potential dye additive for chlorophyll-based organic sensitiser of the dye-sensitised solar cell (DSSC)

    Abdullah, M. H.Daud, K.Khan, A. A.Adilah, M. Y. Syarifah...
    12页
    查看更多>>摘要:In this work, a new chlorophyll dye-sensitiser derived from mitragyna speciosa (MS) leaves, also known as Kratom, was employed for dye-sensitised solar cells (DSSCs). The influence of magnesium sulfate (MgSO4), a low-cost dye additive, and suitable extraction solvents on the performance of DSSCs were examined. Here, the optical properties were investigated using UV-Visible spectroscopy and the functional anchoring group were investigated by FTIR spectroscopy. Meanwhile, the photovoltaic parameters were investigated by I-V measurements. The highest conversion efficiency is obtained when using a dye extracted from methanol solvent in combination with MgSO4 additive, namely methanolic magnesium sulfate (MMSO). This higher power conversion efficiency is mainly attributed to the enhancement of the hydroxyl group in the MMSO dye solutions, which promotes higher dye adsorption and provides an organic dye passivation layer that reduces back-recombination in the cell. Furthermore, MgSO4 aids in the replenishment of magnesium lost in the chlorophyll porphyrin ring during the degradation process. These combined effects have contributed to the overall conversion efficiency of the MMSO cell at 0.26 %, followed by 0.24 % for ethanolic magnesium sulfate (EMSO), respectively. (C) 2022 Elsevier B.V. All rights reserved.

    A near-infrared dicyanoisophorone-based fluorescent probe for discriminating HSA from BSA

    Liu, BinZeng, ConghuiZheng, DannaZhao, Xiongfei...
    8页
    查看更多>>摘要:Despite the rapid development of fluorescent probe techniques for the detection of human serum albumin (HSA), a probe that discriminates between HSA and bovine serum albumin (BSA) is still a challenging task, since their similar chemical structures. As a continuation of our work, herein, a dicyanoisophoronebased fluorescent probe DCO2 is systematically studied for discrimination of HSA from BSA. The photo physical and sensing performances of DCO2, including basic spectroscopic properties, sensing sensitivity, and selectivity, exhibits that DCO2 could selectively bind with HSA and display remarkable fluorescence enhancement (-254-fold) at 685 nm. The gap of the fluorescent response of DCO2 between HSA and BSA is an obvious increase from 21% to 73% compared to the previous probe DCO1. The sensing mechanism was elucidated by Job's plot, displacement experiment, and molecular docking, suggesting that the specific response to HSA originated from the rigid donor structure and steric hindrance. DCO2 could be buried in the DS1 pocket of HSA, and only partly wedged into the DS1 pocket of BSA with exposing twisted N,Ndiethylamino group outside. Application studies indicated that DCO2 has well detective behavior for HSA in the biological fluids. This work could provide a new approach to design HSA-specific near-infrared fluorescence probes.(c) 2022 Published by Elsevier B.V.

    Rapid quantification of alkaloids, sugar and yield of tobacco (Nicotiana tabacum L.) varieties by using Vis-NIR-SWIR spectroradiometry

    Reis, Amanda SilveiraFurlanetto, Renato HerrigYanes Bernardo Junior, Luiz Antoniode Oliveira, Karym Mayara...
    12页
    查看更多>>摘要:Tobacco genetic improvement programs, as well as the tobacco industry, require techniques that allow the estimation of its attributes in a fast and cheap way. The use of remote sensing through visible, near infrared and short-wave spectroscopy (Vis-NIR-SWIR) has been studied aiming to meet such demand. Thus, the aim of this work was to evaluate the use of Vis-NIR-SWIR spectroradiometer as a rapid tool to estimate alkaloids, sugars and yield of tobacco varieties. For that purpose, a study was carried out in a greenhouse with plants grown in pots (18 dm-3) containing nutrient solutions. The experimental design was completely randomized, with 30 treatments (tobacco varieties) and 10 repetitions. Tobacco leaf reflectance was collected at 13, 34 and 68 days after transplantation (DAT) with a plant-probe device connected to the spectroradiometer by an optical fiber. Subsequently, leaf analysis of alkaloids, sugars and yield were performed, and such attributes were estimated by using the Partial Least Squares Regression (PLSR), combined with the following pre-processing (PP) techniques: multiplicative scatter correction (MSC), Savitzky-Golay (SG) and standard normal variate (SNV). The results showed presence of typical inflections of chemical and structural components of the plants, which allowed obtaining PLSR models with R2p and RPDp superior to 0.71 and 2.27, respectively, for all PP techniques and attributes evaluated. The most important wavelengths were well distributed within the three operating ranges of the spectroradiometer (Vis-NIR-SWIR). Thus, the methodology proposed by this research was able to simultaneously determine all the three attributes (alkaloids, sugars and yield) with excellent predictive capacity. This is a promising result for genetic improvement and processing of tobacco (as well as other crops), since it is necessary to evaluate a large number of samples within a short period and at a low cost. (c) 2022 Elsevier B.V. All rights reserved.