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Modern isothermal titration calorimetry instruments give great precision, but for comparable accuracy they require chemical calibration. For the heat factor, one recommended process is HCl into the weak base TRIS. In studying this reaction with a VP-ITC and two Nano-ITCs, we have encountered some problems, most importantly a titrant volume shortfall Δv ≈ 0.3 μL, which we attribute to diffusive loss of HCl in the syringe tip. This interpretation is supported by a mathematical treatment of the diffusion problem. The effect was discovered through a variable-v protocol, which thus should be used to properly allow for it in any reaction that similarly approaches completion. We also find that the effects from carbonate contamination and from OH - from weak base hydrolysis can be more significant that previously thought. To facilitate proper weighting in the least-squares fitting of data, we have estimated data variance functions from replicate data. All three instruments have low-signal precision of σ ≈ 1 μJ; titrant volume uncertainty is a factor of ∼2 larger for the Nano-ITCs than for the VP-ITC. The final heat factors remain uncertain by more than the ∼1 % precision of the instruments and are unduly sensitive to the HCl concentration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

In this study, a novel supramolecular deep eutectic solvent consisting of sulfated-β-CD and citric acid (S-β-CD-CA) is reported for the first time. This innovative system was evaluated as a sole chiral selector in capillary electrophoresis for the enantioseparation of six fluorine-substituted amphetamine analogs, yielding remarkable outcomes. Baseline separations of all amphetamine analogs under study were achieved in less than 21.00 min using the S-β-CD-CA as the chiral selector. It was observed that the addition of 0.050 % v/v S-β-CD-CA into the background electrolyte resulted in the baseline separation of five out of the six fluorine-substituted amphetamine analogs, while in the case of the para-substituted amphetamine analog, 4-fluoramphetamine (4-FA), a higher percentage (0.15 % v/v) was required to achieve baseline enantioseparation. These findings emphasized the potential of this new supramolecular system in providing a class of solvents with promising chiral recognition properties., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Constantina Kapnissi-Christodoulou reports financial support, administrative support, article publishing charges, equipment, drugs, or supplies, and statistical analysis were provided by University of Cyprus., (Copyright © 2024. Published by Elsevier B.V.)

The effect of the combined use of amino acid-based ionic liquids (AAILs) and deep eutectic solvents (DESs) with either cyclodextrin- (CD) or cyclofructan- (CF) based chiral selectors for the chiral separation of amphetamine derivatives was investigated in the present study. A non-significant improvement in enantiomeric separation of target analytes was observed when AAILs were combined with either CF or CD. On the other side, a markedly improved chiral separation of enantiomers was obtained using the dual carboxymethyl-β-cyclodextrin/DES system, highlighting the existence of a synergistic effect. After the addition of 0.5% v/v of choline chloride-ethylene glycol, the resolution of the enantiomers of amphetamine, methamphetamine and 3-fluorethamphetamine, increased from 1.4, 1.1, 1.0 to 1.8, 1.8, and 1.5 min, and the analysis times increased from 19.54, 20.48, 18.71 to 35.71, 35.78 and 32.90 min, respectively. This was not the case for the CF/DES dual system, in which the separation of amphetamines worsened, indicating an antagonistic effect. In conclusion, DESs are a very promising additive in capillary electrophoresis that can improve the separation of chiral molecules in combination with CDs but not CFs., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Constantina Kapnissi-Christodoulou reports financial support was provided by University of Cyprus., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Tomato pomace was slowly pyrolyzed at 350 and 550 °C (under an N 2 flow of 50 L/h) at a rate of 6 °C/min and a residence time of 1:30 h to produce two biochars named B350 and B550, respectively. In addition, the two biochars were chemically activated with ΚΟΗ (at a ratio of 1:10 w/v) at 800 °C to produce two new materials named BA350 and BA550. The four biochars produced were characterized physically and chemically (pH, yield, calorific value). They were also analyzed by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (B.E.T), elemental analysis (EA), and thermogravimetric analysis (TGA). The results showed that as the pyrolysis temperature increased (350 to 550 °C), the specific surface area (SSA) increased. The latter was also significantly increased by the activation process. EA showed a variation in the mineral content of the produced biochars, resulting in a different content of the biochars after activation. The parameters studied showed that biochars from tomato waste could be used as an organic amendment to improve soil fertility in agricultural. In addition, because of their ability to absorb water, they could be used as a water reservoir in soils in arid areas., Competing Interests: Declaration of competing interest The authors have no competing interests to declare that are relevant to the content of this article., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The bamboo family of plants is one of the fastest-growing species in the world. As such, there is an abundance of bamboo residues available for exploitation, especially in southeast Asian, central African and south American regions. The preparation of efficient adsorbents from bamboo residues is an emerging exploitation pathway. Biochars, activated carbons or raw bamboo fibers embedded with nanoparticles, each class of materials has been shown to be highly efficient in adsorption processes. This review aims to summarize recent findings in the application of bamboo-based adsorbents in the removal of organic, inorganic, or gaseous pollutants. Therefore, this review first discusses the preparation methods and surface modification methodologies and their effects on the adsorbent elemental content and other basic properties. The following sections assess the recent progress in the adsorption of heavy metals, organics, and gaseous substances by bamboo-based adsorbents, focusing on the optimum adsorption capacities, adsorption mechanisms and the optimum-fitting kinetic models and isotherms. Finally, research gaps were identified and directions for future research are proposed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

3,3',3''-(Benzene-1,3,5-triyl)tris(1-phenyl-1H-benzo[e][1,2,4]triazin-4-yl) (1) is a C 3 -symmetrical triradical comprised of three Blatter radical units connected at the 1, 3, 5 positions of a central trimethylenebenzene core. This triradical has an excellent air, moisture, and thermal stability. Single-crystal XRD indicates that triradical 1 adopts a propeller-like geometry with the benzotriazinyl moieties twisted by 174.1(2)° and packs in 1D chains along the c axis to form an extensive network of weak intermolecular interactions. Frozen solution continuous wave (CW) EPR spectra and variable-temperature field-sweep echo-detected (FSED) spectra revealed an intramolecular ferromagnetic exchange within the spin system, supporting a quartet S = 3/2 ground state. DFT calculations further supported these experimental findings., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Since the discovery of the anticancer properties of cis-platin the road for the development of less toxic and more specific metal ion based anticancer drugs has opened. Based on the low toxicity of V IV/V , Mo VI and Zn II metal ions, their binuclear hydroquinonate complexes have been synthesized and their biological activity towards their anticancer properties on various cancerous and non-cancerous cell lines has been evaluated. The new complexes of Zn II with the ligands 2,5-bis((bis(pyridin-2-ylmethyl)amino)methyl)benzene-1,4-diol (H 2 bpymah) and 2,2'-(((2,5-dihydroxy-1,4-phenylene)bis(methylene))bis((carboxymethyl)ammoniumdiyl))diacetate (H 6 bicah) have been synthesized and characterized by X-ray crystallography in solid state and 1 H NMR in aqueous solution. The binuclear nature of the complexes increases their hydrolytic stability in aqueous solutions at pD 7.0, depending on the metal ion. The most hydrolytic stable V V and Zn II hydroquinonate complexes show to activate O 2 towards oxidation of mercaptoethanol in aqueous solutions at physiological pHs. Only the strongest oxidant, the V V complex with bicah 6- , significantly activates the intracellular radical oxygen species (ROS) generation. Apparently, the mercaptoethanol oxidation experiment vs time can be used as a preliminary experiment for the prediction of the in vitro ROS generation activity of the complexes in aqueous solutions., (Copyright © 2022. Published by Elsevier Inc.)

Heavy metals represent a serious issue regarding both environmental and health status. Their monitoring is necessary and it is necessary the development of decentralized approaches that are able to enforce the risk assessment. Electrochemical sensors and biosensors, with the various architectures, represent a solid reality often involved for this type of analytical determination. Although these approaches offer easy-to-use and portable tools, some limitations are often highlighted in presence of multi-targets and/or real matrices. However, chemometrics- and artificial intelligence-based tools, both for designing and for data analyzing, display the capability in producing novel functionality towards the management of complex matrices which often contain more information than those that are visualized with sensor detection. Design of experiment, exploratory, predictive and regression analysis can push the world of electrochemical (bio)sensors beyond the state of the art, because is still too large the number of analytical chemists that do not deal with multivariate thinking. In this paper, the use of multivariate methods applied to electrochemical sensing of heavy metals is showed, and each approach is described in terms of efficacy and outputs., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Uranium (U) pollution in groundwater has become a serious problem worldwide. Even in low concentrations, U has both radiological and toxicological impacts on human health. In this study an integrated hydrogeological approach was applied to conceptualize an aquifer system, and determine the origin of U detected in the aquifer of the eastern Halkidiki region in northern Greece. Data from measurements of groundwater level and hydrochemical and stable isotope analyses of groundwater samples were applied to perform geochemical modeling and multivariate statistical analysis. The modeling and statistical analysis identified three hydrogeochemical groups within the studied hydro-system, and U(VI) as the dominant U species. The first group is linked to the deeper aquifer which is characterized by water-rock interactions with weathering products of granodiorite. In this group the dominant U species is uranyl phosphate and U concentration is 3.7 μg/L. The upper aquifer corresponds to the second hydrogeochemical group where U concentrations are mainly influenced by high concentrations of nitrogen species (NO 3 - ). Factor analysis further discriminated the upper aquifer into a saline coastal zone and an inland zone impacted by agricultural activities. The third hydrogeochemical group presents the highest concentration of U (up to 15 μg/L) in groundwater and corresponds to the internal aquifer system. The U within this system is triggered by the presence of Mn 2 , while the long residence time of the groundwater contributes synergistically to the hydrogeochemical process. Manganese triggers U oxidation in parallel with Fe - precipitation that acts as a regulator of U concentration. Groundwater depletion of the upper aquifers promotes the up-coning of geothermal fluids from fault zones leading to increased concentrations of U in the mid-depth aquifers.2+ , while the long residence time of the groundwater contributes synergistically to the hydrogeochemical process. Manganese triggers U oxidation in parallel with Fe 2+ precipitation that acts as a regulator of U concentration. Groundwater depletion of the upper aquifers promotes the up-coning of geothermal fluids from fault zones leading to increased concentrations of U in the mid-depth aquifers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Cannabis is by far the most widely abused illicit drug globe wide. The analysis of its main psychoactive components in conventional and non-conventional biological matrices has recently gained a great attention in forensic toxicology. Literature states that its abuse causes neurocognitive impairment in the domains of attention and memory, possible macrostructural brain alterations and abnormalities of neural functioning. This suggests the necessity for the development of a sensitive and a reliable analytical method for the detection and quantification of cannabinoids in human biological specimens. In this review, we focus on a number of analytical methods that have, so far, been developed and validated, with particular attention to the new "golden standard" method of forensic analysis, liquid chromatography mass spectrometry or tandem mass spectrometry. In addition, this review provides an overview of the effective and selective methods used for the extraction and isolation of cannabinoids from (i) conventional matrices, such as blood, urine and oral fluid and (ii) alternative biological matrices, such as hair, cerumen and meconium., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

The removal of uranium species from aqueous phases using non-hazardous chemicals is still an open challenge, and remediation by adsorption is a prosperous strategy. Among the most crucial concerns regarding the design of an efficient material as adsorbent are, except the cost and the green character, the feasibility to be stable and effective under acidic pH, and to selectively adsorb the desired metal ion (e.g. uranium). Herein, we present a phosphonate functionalized ordered mesoporous silica (OMS-P), prepared by a one-step co-condensation synthesis. The physicochemical features of the material were determined by HR-TEM, XPS, EDX, N 2 sorption, and solid NMR, while the surface zeta potential was also measured. The removal efficiency was evaluated at two different temperatures (20 and 50 °C) in acidic environment to avoid interferences like solid phase formation or carbonate complexation and the adsorption isotherms, including data fitting with Langmuir and Freundlich models and thermodynamic parameters are presented and discussed. The high and homogeneous dispersion of the phosphonate groups within the entire silica's structure led to the greatest reported up-todays capacity (345 mg/g) at pH = 4, which was achieved in less than 10 min. Additionally, OMS-P showed that the co-presence of other polyvalent cation like Eu(III) did not affect the efficiency of adsorption, which occurs via inner-sphere complex formation. The comparison to the non-functionalized silica (OMS) revealed that the key feature towards an efficient, stable, and selective removal of the U(VI) species is the specific surface chemistry rather than the textural and structural features. Based on all the results and spectroscopic validations of surface adsorbed U(VI), the main interactions responsible for the elevated uranium removal were proposed., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The wide use of fossil fuels and their associated environmental concerns, highlighted the importance of affordable and clean energy (goal 7), as adopted by the Sustainable Development Goals of the United Nations for 2030. For years now, the detection of sulfur components in liquid fuels is performed mainly for environmental and health purposes in compliance with the respective legislations. Towards this, the aerobic and anaerobic biodesulfurization (BDS) process, which entails the use of microorganisms to limit the sulfur concentration is followed. To ensure effective BDS, several traditional analytical methods are utilized, although they require bench-top, bulky, costly, and time-consuming instruments along with skilled personnel. The currently employed analytical methods are mostly chromatographic techniques (e.g. liquid and gas) coupled with various detectors. To start with, high-performance liquid chromatography with ultraviolet detector (HPLC-UV), as well as electrospray ionization-LC-mass spectrometry (ESI-LC-MS) were mostly reported. Additionally, many detectors were coupled to gas chromatography (CG) including atomic emission detector (GC-AED), flame ionization detector (GC-FID), flame photometric detector (GC-FPD), sulfur fluorescence detector (GC-SFD), mass selective detector (GC-MS), etc. The solid-phase microextraction (SPME) technique provides extra capabilities when added to the separation techniques. Towards the continuous interest in oil supercomplex synthesis, other atmospheric and surface desorption ionization techniques, as well as the multidimensional 2D chromatographic systems (GC × GC and LC × LC) were also investigated, due to their unsurpassed resolution power. The current review ends with final remarks per applied methodology and the necessity to respect and protect the human environment and life., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, cerumen, a non-conventional biological secretion, was examined as an alternative matrix for forensic analyzis. A fully validated analytical UPLC-MS/MS method was developed for the detection and quantification of the most prevalent psychoactive illicit drug globe wide, Δ 9 -tethrahydrocannabinol, commonly known as THC, and four major cannabinoids found in cannabis Sativa. The method was validated, and standard external calibration curves were established with correlation coefficients > 0.99. A validated experimental procedure, along with a direct extraction of cannabinoids with acidified acetonitrile resulted in a short total analyzis time and a good extraction efficiency for all the analytes under study. LOD and LOQ values were determined to be 0.01-0.08 pg/mg and 0.04-0.23 pg/mg, respectively. To prove applicability of the proposed assay, volunteers were selected, and cerumen samples were examined for cannabis. The analyzis by use of UPLC-MS/MS indicated that all samples were positive, reporting recent cannabis abuse. Surprisingly, both THC and Cannabinol (CBN) were detected, and quantification was possible in 75% of the cases., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Millions of people are using face coverings (including single-use surgical face masks) as a result of the COVID-19 pandemic and a large number of used masks, particularly single-use masks enter uncontrolled the environment since most of the users have little information on how to dispose of them safely. This new important waste is a potential source of microplastics, which is found nowadays in many parks, streets, and coastlines. Discarded masks will be finally drained to the ocean polluting the marine environment and threatening marine life. This short communication examines the role of face masks and subsequently mask-derived microplastics as pollutant carriers in environmental compartments (e.g. hydrosphere, biosphere, etc.) by investigating their sorption characteristics regarding dye molecules. In this context, batch-type equilibrium experiments were performed and the effect of different sorption parameters has been explored (i.e. contact time and temperature). The results show that single-use surgical face masks can act as dye carriers (Methylene Blue, Crystal Violet and Malachite Green) in the aquatic environment. In addition, preliminary experiments on the thermal treatment of face masks and the use of the resulting carbonaceous material as efficient adsorbent have been performed, pointing out a possibility for used mask disinfection and recycling., Competing Interests: The authors declare that there is no conflict of interest regarding the publication of this article., (© 2020 Elsevier B.V. All rights reserved.)

The direct disposal of municipal solid waste such as nappies to the environment may create serious pollution problems. Based on the circular economy and waste management concepts, the conversion of nappies and/or their ingredients (such as super absorbent polymer (SAP)) to high added value products is of great importance. In this work, a modified SAP (MSAP) was examined as an adsorbent for treatment of contaminated waters and uranium recovery. Batch experiments and spectroscopic techniques were used to examine the effect of various parameters (pH, contact time, temperature, initial concentration, and ionic strength), and the mechanism of adsorption U(VI) and desorption process. The U(VI) concentration was determined by alpha spectroscopy after addition of 232 U standard tracer solution to account for possible interferences during electrodeposition and alpha particle counting. The maximum adsorption monolayer capacity was found to be 217.4 mg/g at pH 4.0 and at 298 K. The adsorption of U(VI) on MSAP seems to occur mainly via the formation of inner-sphere surface complexes between U(VI) and the carboxylic surface moieties of MSAP. The MSAP could satisfactorily be regenerated with 0.1 M Na 2 CO 3 (>90%) and it also shows a promising applicability to real wastewaters contaminated with U(VI)., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The heavy metal pollution is a worldwide problem and has received a serious concern for the ecosystem and human health. In the last decade, remediation of the agricultural polluted soil has attracted great attention. Phytoremediation is one of the technologies that effectively alleviate heavy metal toxicity, however, this technique is limited to many factors contributing to low plant growth rate and nature of metal toxicities. Arbuscular mycorrhizal fungi (AMF) assisted alleviation of heavy metal phytotoxicity is a cost-effective and environment-friendly strategy. AMF have a symbiotic relationship with the host plant. The bidirectional exchange of resources is a hallmark and also a functional necessity in mycorrhizal symbiosis. During the last few years, a significant progress in both physiological and molecular mechanisms regarding roles of AMF in the alleviation of heavy metals (HMs) toxicities in plants, acquisition of nutrients, and improving plant performance under toxic conditions of HMs has been well studied. This review summarized the current knowledge regarding AMF assisted remediation of heavy metals and some of the strategies used by mycorrhizal fungi to cope with stressful environments. Moreover, this review provides the information of both molecular and physiological responses of mycorrhizal plants as well as AMF to heavy metal stress which could be helpful for exploring new insight into the mechanisms of HMs remediation by utilizing AMF., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Solid phase micro extraction-Gas Chromatography/Mass Spectrometry (SPME-GC/MS) analysis was performed in exhaled breath samples of 48 healthy volunteers: 20 non-smokers, 10 smokers and 18 e-cigarette (EC, vape) users. Each volunteer provided 1 L of exhaled breath in a pre-cleaned Tedlar bag, in which an SPME fiber was exposed to absorb the emitted breath volatile organic compounds (VOCs). The acquired data were processed using multivariate data analysis (MDA) methods in order to identify the characteristic chemicals of the three groups. The results revealed that the breath of non-smokers demonstrated inverse correlation with a variety of molecules related to the breath from smokers including furan, toluene, 2-butanone and other organic substances. Vapers were distinguished from smokers by the chemical speciation of the e-liquids, such as that of esters (e.g. ethyl acetate), terpenes (e.g. α-pinene, β-pinene, d-limonene, p-cymene, etc.) and oxygenated compounds (e.g. 3-hexen-1-ol, benzaldehyde, hexanal, decanal, etc). Two classification models were developed (a) using principal component analysis (PCA) with hierarchical cluster analysis (HCA) and (b) using partial least squares-discriminant analysis (PLS-DA). Both models were validated using 8 new samples (4 vapers and 4 smokers), collected in addition to the 48 samples of the calibration set. The combination of GC/MS breath analysis and MDA contributed successfully in classifying the volunteers into their respective groups and highlighted the relevant characteristic VOCs. The respective dynamic combination (SPME-GC/MS and MDA) provides a means for long term non-invasive monitoring of the population's health status for early detection purposes., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Novel vitamin E chelate derivatives and their V IV/V complexes have been synthesized and characterized, and their anticancer properties have been evaluated. The new complexes have been designed to exhibit enhanced cytotoxicity by combining high lipophilicity with the properties of vanadium to induce the formation of reactive oxygen species (ROS). In particular, the β-tocopherol derivatives with iminodiethanol (β-tocDEA) and dipicolylamine (β-tocDPA) as well their V V and V IV complexes, [V V O(β-tocDEA] and [V IV O(β-tocDPA] have been synthesized and characterized by Nuclear Magnetic Resonance (NMR), Ultra Violet-Visible (UV-Vis) and Electron Paramagnetic Resonance (EPR) spectroscopies. Although the β-tocopherol compounds exhibit antioxidant activity their complexes induce formation of radicals. In addition, two vanadium amphiphilic complexes of 2,2'-((2-hydroxyoctadecyl)azanediyl)bis(ethan-1-ol) (C18DEA) and 1-(bis(pyridin-2-ylmethyl)amino)octadecan-2-ol (C18DPA) known to activate O 2 and produce ROS were synthesized and characterized (C. Drouza, A. Dieronitou, I. Hadjiadamou, M. Stylianou, J. Agric. Food. Chem., vol. 65, 2017, pp. 4942-4951). The four amphiphilic vanadium complexes exhibit enhanced hydrolytic stability. All compounds found to be cytotoxic for cancer cells exhibiting activity similar or higher to cis-platin., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The adsorption of Cu(II) ions by biochar fibres prior and after modification with 2-thiouracil on real and artificial samples has been studied by batch-type adsorption experiments, FTIR and XPS spectroscopy and competition reactions using U(VI) ions as competitor cations. The experimental data of the artificial samples clearly show that the modified material presents extraordinary higher affinity for Cu(II) ions even in the acidic pH range, the spectroscopic data indicate the formation of inner-sphere complexes and the competition reactions significantly higher selectivity of the 2-thiouracil modified biochar fibres for Cu(II). The 2-thiouracil-modified biochar fibres have been successfully applied to acid mine drainage (AMD) samples regarding the selective separation of Cu(II) ions from "real" samples. Regarding the desorption of copper from the biochar surface, although 100% copper recovery was achieved by eluting the metal ion using 1 M HNO3, the deterioration of the modified biochar fibers due to extensive 2-thiouracil release from the biochar surface limits the applicability of the present adsorbent in routine and large-scale applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

D-pinitol (3-O-methyl-D-chiro-inositol) is a well-known bioactive compound with anti-diabetic and anti-oxidant biological functions. A gas chromatography-mass spectrometry (GC-MS) method was developed for its quantitation in carob syrup, flesh and seed samples originated from Cyprus. The analysis was performed after derivatization of carbohydrates and polyols into trimethylsilyl ether derivatives. D-pinitol was determined in 13 carob syrup samples, in concentrations ranging 65.71 ± 4.60 - 77.72 ± 5.44 mg/g (mean: 68.58 ± 4.80 mg/g, n = 13). In two commercial samples, it was determined in relative medium-low concentrations (21.96 ± 1.54 and 44.71 ± 3.13 mg/g), revealing possible adulteration; however, this needs further investigation. Similarly, it was determined in high concentrations in carob flesh samples, in concentrations ranging 53.20 ± 3.72 - 54.58 ± 3.82 mg/g (mean: 53.81 ± 3.76 mg/g, n = 3). On the other hand, seed samples proved very poor in D-pinitol (

Ceratonia siliqua, known as the carob, is considered to be of high nutritional value and of great economic significance due to its unique composition. The beneficial effects of carob against cancer, metabolic syndrome, diabetes, diarrhea, hyperlipidemia and gastro esophageal reflux disease are only a few of its therapeutic actions. Metabolomics-based analysis provides an ultimate tool, for the deciphering of nutritional intervention derived metabolic alterations. In the present study, 16 male Wistar rats were treated with carob powder for a 15-day period. Fecal and urine samples were collected at 5 time points (0, 1, 5, 10 and 15 days). By the applied HILIC-MS/MS method, 63 and 67 hydrophilic metabolites were detected in the fecal and urine samples, respectively, including amino acids, organic acids, sugars, vitamins and other endogenous compounds. A clear group separation based on fecal metabolome was observed after 1 day and 15 days treatment, while only a mild differentiation at day 1 was observed based on urine metabolome. Twenty-one fecal metabolites were responsible for the separation including amino acids and their derivatives, vitamins and organic acids. However, only 7 metabolites were altered in rat urine samples. Metabolic alterations in fecal samples could be attributed to physiological and biochemical adaptations derived from the nutritional intervention. Fecal targeted metabolomics were proven to be suitable for uplifting and highlighting such alterations., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Human smuggling and associated cross-border crimes have evolved as a major challenge for the European Union in recent years. Of particular concern is the increasing trend of smuggling migrants hidden inside shipping containers or trucks. Therefore, there is a growing demand for portable security devices for the non-intrusive and rapid monitoring of containers to detect people hiding inside. In this context, chemical analysis of volatiles organic compounds (VOCs) emitted from the human body is proposed as a locating tool. In the present study, an in-house made ion mobility spectrometer coupled with gas chromatography (GC-IMS) was used to monitor the volatile moieties released from the human body under conditions that mimic entrapment. A total of 17 omnipresent volatile compounds were identified and quantified from 35 ion mobility peaks corresponding to human presence. These are 7 aldehydes (acrolein, 2-methylpropanal, 3-methylbutanal, 2-ethacrolein, n-hexanal, n-heptanal, benzaldehyde), 3 ketones (acetone, 2-pentanone, 4-methyl-2-pentanone), 5 esters (ethyl formate, ethyl propionate, vinyl butyrate, butyl acetate, ethyl isovalerate), one alcohol (2-methyl-1-propanol) and one organic acid (acetic acid). The limits of detection (0.05-7.2 ppb) and relative standard deviations (0.6-11%) should be sufficient for detecting these markers of human presence in field conditions. This study shows that GC-IMS can be used as a portable field detector of hidden or entrapped people., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The antiproliferative activity of the gold complex [Au(tpp)Cl] (1) (tpp=triphenyphosphine) against human breast adenocarcinoma cells (MCF-7) and normal human fetal lung fibroblast cells (MRC-5) was investigated. The compound exhibits stronger activity against MCF-7 cells than cisplatin. The apoptotic pathway, especially though the mitochondrion damage was concluded by cell cycle arrest, flow cytometry using Annexin V-Fluorescein IsoThioCyanate (FITC) and Propidium Iodide (PI) as indicators, assays and permeabilization of the mitochondrial membrane tests. The molecular mechanism of action of 1 was further studied by: (i) its catalytic activity on the oxidation of linoleic acid (an acid that partakes in membrane fluidity) to hyperoxolinoleic acid by oxygen and (ii) its binding affinity towards the calf thymus (CT) DNA. Since the deactivation of cisplatin by glutathione (GSH), is related with the development of cell resistance, the reaction of 1 with GSH was investigated by UV absorption spectroscopy. The absence of micronucleus in cells confirms that the complex has no in vitro toxicity. The in vivo genotoxicity caused by 1 was evaluated by Allium cepa test., (Copyright © 2017 Elsevier Inc. All rights reserved.)

From the ion point-of-view specific ion effects (SIE) arise as an interplay of ionic size and shape and charge distribution. However in aqueous systems SIE invariably involve water, and at surfaces they involve both interacting surface groups and local fields emanating from the surface. In this review we highlight the fundamental importance of ionic size and hydration on SIE, properties which encompass all types of interacting forces and ion-pairing phenomena and make the Hofmeister or lyotropic series of ions pertinent to a broad range of systems and phenomena. On the other hand ionic hydrophobicity and complexation capacity also determine ionic behavior in a variety of contexts. Over the years we have carried out carefully designed experiments on a few selected soft matter model systems, most involving zwitterionic phospholipids, to assess the importance of fundamental ionic and interfacial properties on ion specific effects. By tuning down direct Coulomb interactions, working with different interfacial geometries, and carefully tuning ion-lipid headgroup interactions it is possible to assess the importance of different parameters contributing to ion specific behavior. We argue that the majority of specific ion effects involving relatively simple soft matter systems can be at least qualitatively understood and demystified., (Copyright © 2017. Published by Elsevier B.V.)

Nitrite is a powerful oxidant that affects the activity of peroxidases towards various substrates and leads to heme macrocycle modifications in members of the peroxidase family, such as the horseradish peroxidase (HRP). We have applied resonance Raman spectroscopy to investigate the structural properties of the species formed in the reaction of NO 2 with the ferric form of HRP. Our data demonstrate that the heme nitrovinyl group is partially formed at near neutral pH, without coordination of NO - to the heme Fe. Nitrite coordinates to the heme Fe at acidic pH in the nitro binding mode, characterized by the detection of the ν(Fe-NO 2 - to the heme Fe. Nitrite coordinates to the heme Fe at acidic pH in the nitro binding mode, characterized by the detection of the ν(Fe-NO 2 ) at 563cm -1 , δ(FeNO 2 ) at 822cm -1 and ν sym . The sensitivity of the vibrations of the heme Fe-nitro complex to H/D exchange indicates H-bonding interaction of the heme-bound ligand with the distal environment that determines the NO 2 binding mode. A model describing the different modes of NO -1 . The sensitivity of the vibrations of the heme Fe-nitro complex to H/D exchange indicates H-bonding interaction of the heme-bound ligand with the distal environment that determines the NO 2 - binding mode. A model describing the different modes of NO 2 - binding in HRP is presented., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The coordination of nitrite in myoglobin (Mb) has been characterized by resonance Raman spectroscopy and the frequencies of the nitrite bound to the heme Fe as well to the 2-vinyl have been computed by density functional theory (DFT) calculations. The DFT Natural Bond Orbital (NBO) analysis and the extensive isotope-labeling in the resonance Raman experiments indicate that NO 2 (O1NO2) is bound to the heme Fe via O1. Based on the vibrational characterization of the reversible transition between low and high spin FeONO/2-nitrovinyl species, we suggest that the key step that triggers the spin-change is the increase of the proximal FeN - bond length. The frequencies of the O and N sensitive bands of the FeONO/2-nitrovinyl species remained largely unchanged in the low- to high-spin transition. Therefore the "greening" process in the reaction of ferric Mb with NO His93 bond length. The frequencies of the O and N sensitive bands of the FeONO/2-nitrovinyl species remained largely unchanged in the low- to high-spin transition. Therefore the "greening" process in the reaction of ferric Mb with NO 2 - proceeds through the FeONO/2-nitrovinyl species, which can exist in either the high or low-spin state., (Copyright © 2016 Elsevier Inc. All rights reserved.)

This review highlights recent advances and applications in open-tubular capillary electrochromatography (OT-CEC) for enantioseparations during the last decade. Although extensive research has been conducted in the area of separations by use of CEC, and a big number of reviews have been published, there is not a review on exclusively the use of chiral stationary phases (CSPs) in OT-CEC for enantioseparations. Therefore, in this review, the design and synthesis of different CSPs are presented, and their potential applications in OT-CEC for enantioseparations are discussed. The different approaches to CSP development include chiral nanomaterials, porous layers, molecular imprinting, sol-gel technique, polyelectrolyte multilayer coating, polymeric coating and others., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Antimony(III) halide complexes of the formulae {[SbBr(Me2DTC)2]n} (1), {[SbI(Me2DTC)2]n} (2) and {[(Me2DTC)2Sb(μ2-I)Sb(Me2DTC)2](+).I3(-)} (3) (Me2DTC = dimethyldithiocarbomate) were synthesized from SbX3, (X = Br or I) and tetramethylthiuram monosulfide (Me4tms) or tetramethylthiuram disulfide (Me4tds). The complexes were characterized by melting point (m.p.), elemental analysis (e.a.), Fourier-transform Infra-Red (FT-IR), Fourier-transform Raman (FT-Raman), Nuclear Magnetic Resonance ((1)H,(13)C-NMR) spectroscopy and Thermogravimetric-Differential Thermal Analysis (TG-DTA). Crystal structures of complexes 1-3 were determined with single crystal X-ray diffraction analysis. Complexes 1 and 2 are polymers with distorted square pyramidal (SP) geometry in each monomeric unit, whereas complex 3 is ionic, containing an iodonium linkage Sb-I(+)-Sb and an I3(-) counter anion; to the best of our knowledge, this is the first ionic antimony(III) iodide complex. The in vitro cytotoxic activity of 1-3 against human adenocarcinoma cells: breast (MCF-7) and cervix (HeLa) cells and non-cancerous cells: MRC-5 (normal human fetal lung fibroblast cells) was evaluated with trypan blue (TB) and sulforhodamine B (SRB) assays. Among antimony(III) compounds with sulfur containing ligand, those of dithiocarbamates exhibit significant cytotoxic activity. Hirshfeld surface volumes were analyzed to clarify the nature of the intermolecular interactions by the 2D fingerprint plot. Molecules with lower H-all atoms inter-molecular interactions exhibit the higher activity against MCF-7 cells. The in vivo genotoxicity of 1-3 was evaluated by the mean of Allium cepa test. Alterations in the mitotic index values due to the chromosomal aberrations were observed in the case of complexes 2 and 3. Since, no such alteration is caused by 1, it makes this compound candidate for further study as potential drug.

The already known Ag(I)-Sb(III) compound of the formula {Ag(Ph3Sb)3(NO3)} (1) and two novel mixed metal Ag(I)-Sb(III) metallotherapeutics of the formulae {Ag(Ph3Sb)3(SalH)}(2) and {Ag(Ph3Sb)3(Asp)}(3) (SalH2=salicylic acid, AspH=aspirin or 2-acetylsalicylic acid and Ph3Sb=triphenyl antimony(III)) have been synthesised and characterised by m.p., vibrational spectroscopy (mid-FT-IR), (13)C-,(1)H-NMR, UV-visible (UV-vis) spectroscopic techniques, high resolution mass spectroscopy (HRMS) and X-ray crystallography. Compounds 1,-3 were treated with the surfactant cetyltrimethylammonium bromide (CTAB) in order to enhance their solubility and as a consequence their bioactivity. The resulting micelles a-c were characterised with X-ray powder diffraction (XRPD) analysis, X-ray fluorescence (XRF) spectroscopy, Energy-dispersive X-ray spectroscopy (EDX), conductivity, Thermal gravimetry-differential thermal analysis (TG-DTA), and atomic absorption. Compounds 1-3 and the relevant micelles a-c were evaluated for their in vitro cytotoxic activity against human cancer cell lines: MCF-7 (breast, estrogen receptor (ER) positive), MDA-MB-231 (breast, ER negative) and MRC-5 (normal human fetal lung fibroblast cells) with sulforhodamine B (SRB) colorimetric assay. The results show significant increase in the activity of micelles compared to that of the initial compounds. Moreover, micelles exhibited lower activity against normal cells than tumor cells. The binding affinity of a-c towards the calf thymus (CT)-DNA, lipoxygenase (LOX) and glutathione (GSH) was studied by the fluorescent emission light and UV-vis spectroscopy., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Field experiments were devised to mimic the entrapment conditions under the rubble of collapsed buildings aiming to investigate the evolution of volatile organic compounds (VOCs) during the early dead body decomposition stage. Three pig carcasses were placed inside concrete tunnels of a search and rescue (SAR) operational field terrain for simulating the entrapment environment after a building collapse. The experimental campaign employed both laboratory and on-site analytical methods running in parallel. The current work focuses only on the results of the laboratory method using thermal desorption coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (TD-GC×GC-TOF MS). The flow-modulated TD-GC×GC-TOF MS provided enhanced separation of the VOC profile and served as a reference method for the evaluation of the on-site analytical methods in the current experimental campaign. Bespoke software was used to deconvolve the VOC profile to extract as much information as possible into peak lists. In total, 288 unique VOCs were identified (i.e., not found in blank samples). The majority were aliphatics (172), aromatics (25) and nitrogen compounds (19), followed by ketones (17), esters (13), alcohols (12), aldehydes (11), sulfur (9), miscellaneous (8) and acid compounds (2). The TD-GC×GC-TOF MS proved to be a sensitive and powerful system for resolving the chemical puzzle of above-ground "scent of death"., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A simple donor atom additivity relationship has been used to calculate the donor atom electrochemical contribution (DEC) of the Oac (acetylacetonate-enolic oxygen), OPh (phenolic oxygen), SPh (mercaptophenol sulfur), Nam (deprotonate amide nitrogen), Nim (imine nitrogen) and Npy (pyridine nitrogen) to the redox processes of the square pyramidal vanadyl complexes. The study focuses on the amidate vanadyl complexes because of (a) their biological interest and (b) the existence of data from plethora complexes studied in great details. The electrochemical contributions for the vanadyl oxidation and reduction processes increase following the same order, OPh~Oac(enolic)

This report provides an overview of the application of chiral ionic liquids (CILs) in separation technology, and particularly in capillary electrophoresis and both gas and liquid chromatography. There is a large number of CILs that have been synthesized and designed as chiral agents. However, only a few have successfully been applied in separation technology. Even though this application of CILs is still in its early stages, the scientific interest is increasing dramatically. This article is focused on the use of CILs as chiral selectors, background electrolyte additives, chiral ligands and chiral stationary phases in electrophoretic and chromatographic techniques. Different examples of CILs, which contain either a chiral cation, a chiral anion or both, are presented in this review article, and their major advantages along with their potential applications in chiral electrophoretic and chromatographic recognition are discussed., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Disposed olive cake generates hydrophilic components that can be mobilized in the aquatic environment. This paper deals with the characterization of such components, isolated by alkaline extraction. It is shown that these substances possess properties very much resembling humic acid, including a substantial inventory of proton exchanging groups. Extraction and purification of the hydrophilic components from the disposed olive cake was performed by the standard approach for isolation of humic acids from solid sources, i.e. alternating alkaline dissolution and acid flocculation, leaving the purified extract in the protonated form. The purified sample was characterized by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Fourier Transform Infra Red Spectroscopy (FTIR), UV-vis, Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Asymmetrical Flow Field-Flow Fractionation (AFFFF). The complex formation properties were investigated by potentiometry using Cu(II) ion selective electrode under atmospheric conditions at I=0.1M NaClO(4) (aqueous solution) and pH 6. The formation constant for the CuHA complex is found to be logbeta=5.3+/-0.4 which is close to the corresponding value (logbeta=5.2+/-0.4) obtained from similar investigations with the commercially available Aldrich humic acid (this study) and corresponding published values for various humic acids. Both, structural properties and complex formation data show that the olive cake extract has considerable similarities with humic acids from different sources, pointing towards potential similarities in environmental behavior and impact.

The understanding of the dynamics and conformational control involved in the interplay between structure and function of nitric oxide reductase (Nor) and heme-copper oxidoreductases in their function to convert nitric oxide (NO) to nitrous oxide (N2O) is of fundamental importance in bioenergetics. We have applied resonance Raman spectroscopy to investigate the NO ligation/deligation reactions and the extent of communication between the metal centers at the heme a3-CuB site of heme-copper oxidases and of the heme Fe-non-heme Fe in Nor. The present study provides information of the electronic and vibrational structure of intermediates, and thus, it forms the basis for an atomic-level description of the key steps in the N-N bond formation and the N-O bond cleavage mechanism. The present experiments provide evidence as to the validity of the proposed hypothesis of the common evolutionary origin of aerobic respiration and bacterial denitrification.