Analytical potential of a laser ablation–glow discharge–optical emission spectrometry system for the analysis of conducting and insulating materials

The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionization of the material provided by laser ablation (LA) have been compared to conventional laser induced breakdown spectroscopy (LIBS). In LA–GD both sources can be independently adjusted to optimize the sampling process and then its subsequent excitation. This could involve a number of analytical performance advantages, such as reduced matrix dependence, greater precision and sensitivity than those encountered in LIBS. For such purpose, an ablation chamber design including two electrodes to generate the GD discharge has been built and assayed. A comparison between LIBS and LA–GD–OES has been carried out, both, under reduced argon and helium atmospheres. Different sets of samples (conducting reference materials, glass and fluorine pellets) have been used to evaluate the novel coupled technique. The LA–GD coupled system has shown to provide lower detection limits. In addition, best linear correlations between intensities and concentrations and lower matrix effects have also been found using the coupled system. Moreover, special advantages of the LA–GD–OES have also been demonstrated for the analysis of fluorine.     

Spin-state dynamics of a photochromic iron(II) complex and its immobilization on oxide surfaces via phenol anchors

This work presents a detailed study of the photo-induced spin-state dynamics of the photochromic iron(II) complex 1, where the metal ion is in the field of a tripodal hexa-imine ligand with protolysable phenol groups. The nature of the complex’s ground state has been identified as a spin singlet by ¹H NMR and steady-state UV/vis spectroscopies, and its distorted octahedral structure was analyzed via crystal structure determination. Sub-picosecond and nanosecond time-resolved laser flash photolysis experiments identify the long-lived quintet state of 1 as the selective product of photoexcitation in the UV/vis spectral region. Thermal barriers of spin-state interconversion as a function of solvent and added base are derived from temperature-dependent rates of transient decay. Ground-state recovery is found to be significantly affected by the solvent and is strongly enhanced, in particular, by base-driven solvolysis of the ligand’s phenol groups. Partial spontaneous deprotonation of the phenolic hydroxyl groups of 1 seems to prevail on metal oxide surfaces, i.e. on alumina. Composite materials, like 1 at Al₂O₃, that retain the characteristic spectral features of the parent iron(II) complex can be readily obtained by wet impregnation of hydrous alumina with solutions of 1.     

Role of a high ground-state centrifugal barrier in the breakup of the 31Ne nucleus

An analysis of the breakup of the \begin{document}$ ^{31}{\rm Ne} $\end{document} weakly-bound neutron-halo system on a lead target is presented, considering the \begin{document}$ 2p_{3/2} $\end{document} and \begin{document}$ 1f_{7/2} $\end{document} ground-state configurations. It is shown that a high centrifugal barrier almost wipes out the breakup channel, thus assimilating the breakup of a weakly-bound system to that of a tightly-bound system, and also reduces the range of the monopole nuclear potential. Consequently, a high centrifugal barrier prevents the suppression of the Coulomb-nuclear interference (CNI) peak by weakening couplings to the breakup channel and reducing the range of the monopole nuclear potential, two main factors that would otherwise suppress such a peak. The present study also identifies couplings to the breakup channel and a long-ranged monopole nuclear potential as the main factors that lead to the suppression of the CNI peak. A low centrifugal barrier together with a Coulomb barrier would also effectively prevent the suppression of the CNI peak in proton-halos as reported in the case of the \begin{document}$ ^8{\rm B} $\end{document} proton-halo.     

Enhanced energy transfer from diolefinic laser dyes to meso-tetrakis (4-sulfonatophenyl) porphyrin immobilized on silver nanoparticles: DFT,TD-DFT and spectroscopic studies

Porphyrin derivatives are known singlet oxygen sensitizers in photodynamic therapy (PDT). Energy transfer from a class of diolefinic laser dyes (DOLDs) as energy donors to the sodium salt of meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS) as the accepter of energy would extend the range of photon harvesting down to the UV-region. Energy transfer was substantially enhanced in the presence of metallic silver nanoparticles (AgNPs), as revealed by steady-state emission spectroscopy, lifetimes, and quantum mechanics. DOLDs under investigation are 2,5-distyrylpyrazine (DSP), 1,4-bis (β-pyridyl-2 vinyl) benzene (P2VB), and 1,4 bis (2-methylstyryl) benzene (MSB) as efficient donors of intense absorption in the UV-region. AgNPs enhance the rate of energy transfer from DOLDs to TPPS via bringing donor and acceptor into close- proximity with a concomitant increase in dipole–dipole interaction between excited state donor and ground-state acceptor. The DOLDs molecular structures were optimized using the DFT/CAM-B3LYP/6-311G++ (d, p) level of theory. The calculated electronic absorption spectra for the studied DOLDs in the gaseous phase and methanol solvent were studied using the time-dependent density functional theory (TD-DFT) at M06-2X/6-311G++ (2d,2p) level. The calculated absorption/emission spectra for DSP laser dye in methanol are obtained at the TD/ M06-2X/6-311G++(2d, 2p) method. Notably, all theoretical results of the molecular structures under study highly agreed with the practical optical results. Energy transfer rate constants (k_ET) amid energy donor/acceptor pairs were determined by Stern-Volmer constants (KSV) and donors' lifetime measurements. The KSV values indicate an enhanced Fluorescence Resonance Energy Transfer (FRET) efficiencies in the presence of negatively charged AgNPs. The critical transfer distances R_o were determined from the spectral overlap between the emission spectrum of donor and absorption spectrum of TTPS. These outcomes propose the application of designed metal-enhanced FRET for energy-transfer-based assays and photodynamic therapy (PDT) applications.     

Facile Fabrication of PBS/CNTs Nanocomposite Foam for Electromagnetic Interference Shielding

In order to reduce the pollutants of environment and electromagnetic waves, environment friendly polymer foams with outstanding electromagnetic interference shielding are imminently required. In this paper, a kind of electromagnetic shielding, biodegradable nanocomposite foam was fabricated by blending poly (butylene succinate) (PBS) with carbon nanotubes (CNTs) followed by foaming with supercritical CO₂. The crystallization temperature and melting temperature of PBS/CNTs nanocomposites with 4 wt % of CNTs increased remarkably by 6 °C and 3.1 °C compared with that of pure PBS and a double crystal melting peak of various PBS samples appeared in DSC curves. Increasing the CNT content from 0 to 4 wt % leads to an increase of approximately 3 orders of magnitude in storage modulus and nearly 9 orders of magnitude in enhancement of electrical properties. Furthermore, CNTs endowed PBS nanocomposite foam with adjustable electromagnetic interference (EMI) shielding property, giving a specific EMI shielding effectiveness of 28.5 dB cm³/g. This study provides a promising methodology for preparing biodegradable, lightweight PBS/CNTs foam with outstanding electromagnetic shielding properties.     

The enormity of the zinc deficiency problem and available solutions; an overview

The societal cost of micronutrient deficiency (MND) or the “hidden hunger” is in millions of dollars/year, reducing the GDP of some countries by as much as 11%. Zn is an important micronutrient for both plants and animals. An estimated 17% of the world population, or around 1.1 billion people, are at the risk of zinc (Zn) deficiency. The deficiency has been related to adverse pregnancy outcomes, stunted growth, premature deaths, immune system dysfunctions, neuro-behavioral disorders, and recently with the failure to recover from COVID-19. These health risks associated with Zn deficiency have compelled FAO and WHO to recommend Zn fortification of diet. Correcting Zn deficiency is a challenge due to several reasons. Close to half of the agricultural soils are Zn deficient, and chemical Zn fertilizers are costly and ineffective. Developing Zn-rich crops through plant breeding and genetic engineering is challenging. Zn-dense diet is costly and cannot be implemented in the low-income region most affected by Zn deficiency. Lack of consensus among regulatory bodies on defining and diagnosing Zn deficiency in plants and Humans. Awareness and other sociocultural issues. Among the most important available solutions are zinc biofortification of the cereal crops, use of zinc biofertilizers, development of Zn-efficient crops with reduced phytate content. The use of Zn supplements, dietary modification, and diversification, especially with fish, are proposed as the most accessible and affordable solutions. Awareness programs in areas suffering the most from Zn deficiency are required. Despite the suggestions from FAO and WHO, global efforts to combat Zn deficiency matching those for combating diseases like HIV are not in place. Coordinated efforts of the international community, especially policy-makers, agricultural scientists, dieticians, physicians, and others, are required to address the issue of hidden hunger.     

Rapid and label-free classification of pathogens based on light scattering,reduced power spectral features and support vector machine

The rapid identification of pathogens is crucial in controlling the food quality and safety. The proposed system for the rapid and label-free identification of pathogens is based on the principle of laser scattering from the bacterial microbes. The clinical prototype consists of three parts: the laser beam, photodetectors, and the data acquisition system. The bacterial testing sample was mixed with 10 mL distilled water and placed inside the machine chamber. When the bacterial microbes pass by the laser beam, the scattering of light occurs due to variation in size, shape, and morphology. Due to this reason, different types of pathogens show their unique light scattering patterns. The photo-detectors were arranged at the surroundings of the sample at different angles to collect the scattered light. The photodetectors convert the scattered light intensity into a voltage waveform. The waveform features were acquired by using the power spectral characteristics, and the dimensionality of extracted features was reduced by applying minimal-redundancy-maximal-relevance criterion (mRMR). A support vector machine (SVM) classifier was developed by training the selected power spectral features for the classification of three different bacterial microbes. The resulting average identification accuracies of E. faecalis,E. coli and S. aureus were 99%, 87%, and 94%, respectively. The overall experimental results yield a higher accuracy of 93.6%, indicating that the proposed device has the potential for label-free identification of pathogens with simplicity, rapidity, and cost-effectiveness.     

嘧啶衍生物与人血清白蛋白的相互作用

在模拟生理条件下,运用荧光光谱、激光闪光光解(LFP)和分子对接等技术研究了8种具有抗肿瘤活性的嘧啶衍生物(PDs,其中PDs A 5-FU为成药,PDs B-H为实验室自制)与人血清白蛋白(HSA)的相互作用.利用Stern-Volmer方程和激光闪光光解技术分析了PDs对HSA的荧光猝灭机制,PDs A和B为静态猝灭,PDs G和H为动态猝灭.用双倒数曲线法得出5种PDs与HSA的结合常数Ka和结合位点数n,在测定条件下5种PDs与载体结合位点数均为1,且均以弱结合力结合,通过热力学参数ΔH,ΔS和ΔG推测出PDs B,C和E与HSA之间的作用力为静电作用力和疏水作用力,PDs A和D与HSA之间的作用力是氢键和范德华力,分子对接结果与其一致.根据F9rster非辐射能量转移理论(FRET)分析了HSA和PDs之间的结合距离(r),其结果均小于4 nm,符合能量转移理论.进一步利用同步荧光、三维荧光和圆二色光谱考察了PDs与HSA结合过程中HSA空间构象的变化,结果显示,仅PDs A和C对HSA的芳香族氨基酸周围的疏水性略有增强作用.体外实验结果表明,HSA可以作为优良的载体来运输和储存PDs A~E,这为嘧啶衍生物的后续研究提供了可参考的实验数据.     

Measuring nitrate concentration in wastewaters with high chloride content

The presence of chloride ions in wastewaters in concentrations above 50 mg/L poses interference in several methods used for the measurement of nitrate-nitrogen. The aim of this study was to characterise the reliability and costs of some commonly available methods for the analysis of nitrate concentration in landfill leachate which contains high chloride levels. To investigate the effect of chloride interference, several widely used methods [ion chromatography (IC), continuous flow analysis (CFA), the German standard method (DIN), cuvette test (CUV), standard addition method (SAM) and reflectometric test (REF)] were used to measure the nitrate concentration in synthetic solutions containing varying concentrations of chloride and nitrate-nitrogen. Nitrate recoveries of the various methods were found to decrease in the following rank order: CUV (>95%) > IC (>90%) > CFA (89%) > DIN (88%) > REF (70%) > SAM (<80%). In the second part of the study, the same methods were used to measure nitrate concentrations in samples of biologically nitrified landfill leachate with and without chloride elimination. For leachate samples without chloride elimination, CUV results were well correlated (linear regression) with IC results (slope = 1.02/R² = 0.99) but to lesser extents with results obtained by CFA (0.91/0.86), DIN (0.89/0.97) and REF (0.86/0.77), and not correlated with SAM (0.74/–1.3). The incurred measurement costs per sample (in Euros) for the methods were as follows: CFA (<0.1) < DIN (0.6) < REF (0.7) < SAM (3) < CUV (3.8) < IC (15). Cuvette tests are recommended as the method of choice due to their accuracy and lower cost than IC.