金属-介质-金属渔网超表面结构调控的荧光辐射：空间选择性激发和双增强

增强荧光辐射在生物成像、高灵敏探测、集成光源等方面都具有重要的应用价值.金属纳米颗粒的周围或者金属纳米结构的间隙都可以产生强的电磁场,相应的,这些结构附近的局域态密度也被极大地增强.虽然增强荧光辐射已经在多种金属纳米颗粒和颗粒对中被证明,但是利用金属纳米结构对荧光分子的吸收和辐射过程同时进行调制仍然是一个有挑战的问题.本文研究了金属-介质-金属超表面对荧光辐射的调控,其中局域表面等离激元(LSP)和磁等离激元(MPP)分別与于分子的吸收和辐射过程发中耦合相互作用.对于吸收过程,LSP的耦合作用使得可以通过旋转泵浦激光的偏振态来实现荧光分子的空间选择激发.此外,MPP模式的偏振依赖特性使得矩形渔网结构中的荧光分子的辐射波长和偏振态也受到调控.实验观测结果经过了时域有限差分模拟的验证.本文报道的纳米结构在光辐射器件和纳米尺度集成光源等方面都具有潜在的应用价值.     

Monitoring of Pollutants Content in Bottled and Tap Drinking Water in Italy

The concentration levels of thirteen organic pollutants and selected heavy metals were investigated in 40 plastics bottled and tap water samples. Some of the selected contaminants have an ascertained or suspected endocrine disrupting activity, such as Bisphenol A (BPA) and its analogs, and Bis 2-ethylhexyl phthalate (DEHP), which are used by industries as plasticizers. The most frequently detected pollutants were Bisphenol AF (BPAF) (detection frequency (DF) = 67.5%, mean 387.21 ng L⁻¹), DEHP (DF = 62.5%, mean 46.19 µg L⁻¹) and BPA (DF = 60.0%, mean 458.57 ng L⁻¹), with higher concentration levels found in tap waters. Furthermore, a possible level of exposure to thirteen pollutants via drinking water intake was calculated. Our findings show that, even though the occurrence of contaminants and heavy metals in drinking waters does not pose an immediate, acute health risk for the population, their levels should be constantly monitored and “hard-wired” into everyday practice. Indeed, the health impact to the continuous and simultaneous intake of a huge variety of xenobiotics from various sources by humans is complex and still not fully understood.     

Phosphodiester Silybin Dimers Powerful Radical Scavengers: A Antiproliferative Activity on Different Cancer Cell Lines

Silibinin is the main biologically active component of silymarin extract and consists of a mixture 1:1 of two diastereoisomeric flavonolignans, namely silybin A (1a) and silybin B (1b), which we call here silybins. Despite the high interest in the activity of this flavonolignan, there are still few studies that give due attention to the role of its stereochemistry and, there is still today a strong need to investigate in this area. In this regard, here we report a study concerning the radical scavenger ability and the antiproliferative activity on different cell lines, both of silybins and phosphodiester-linked silybin dimers. An efficient synthetic strategy to obtain silybin dimers in an optical pure form (6aa, 6ab and 6bb) starting from a suitable building block of silybin A and silybin B, obtained by us from natural extract silibinin, was proposed. New dimers show strong antioxidant properties, determined through hydroxyl radical (HO^●) scavenging ability, comparable to the value reported for known potent antioxidants such as quercetin. A preliminary screening was performed by treating cells with 10 and 50 μM concentrations for 48 h to identify the most sensitive cell lines. The results show that silibinin compounds were active on Jurkat, A375, WM266, and HeLa, but at the tested concentrations, they did not interfere with the growth of PANC, MCF-7, HDF or U87. In particular, both monomers (1a and 1b) and dimers (6aa, 6ab and 6bb) present selective anti-proliferative activity towards leukemia cells in the mid-micromolar range and are poorly active on normal cells. They exhibit different mechanisms of action in fact all the cells treated with the 1a and 1b go completely into apoptosis, whereas only part of the cells treated with 6aa and 6ab were found to be in apoptosis.     

The Highly Efficient Synthesis of 1,2-Disubstituted Benzimidazoles Using Microwave Irradiation

The benzimidazole ring of the heterocyclic pharmacophores is one of the most widespread and studied systems in nature. The benzimidazole derivative synthesis study is a crucial point for the development of a clinically available benzimidazole-based drug. Here, we report a simple microwave assisted method for the synthesis of 1,2-disubstituted benzimidazoles. The combination of the molar ratio of N-phenyl-o-phenylenediamine:benzaldehyde (1:1) using microwave irradiation and only 1% mol of Er(OTf)₃ provides an efficient and environmental mild access to a diversity of benzimidazoles under solvent-free conditions. The proposed method allows for the obtainment of the desired products in a short time and with very high selectivity.     

The Design of Experiment as a Tool to Model Plant Trace-Metal Bioindication Abilities

Bioindicator plants are species that have the capacity to linearly uptake some elements (metal and metalloids) from the growing substrate, thus reflecting their concentration in the soil. Many factors can influence the uptake of these elements by plants, among which is the simultaneous presence of several metals, a common situation in contaminated or natural soils. A novel approach that can be used to validate the bioindication ability of a species growing on a polymetallic substrate is the design of experiment (DoE) approach. The aim of the present study was to apply the DoE in full factorial mode to model the Cu, Cd, Pb, Zn, and Cr bioindication capacity of Polygonum aviculare, used as the model plant. The results showed that P. aviculare has the ability to bioindicate Cd and Cr with a linear uptake (from 0.35 to 6.66, and 0.1 to 3.4 mg kg⁻¹, respectively) unaffected by the presence of other metals. Conversely, the uptake of Pb, Cu, and Zn is strongly influenced by the presence of all the studied metals, making their concentration in the plant shoot not proportional to that of the soil. In conclusion, these preliminary results confirmed that the DoE can be used to predict the bioindicator abilities of a plant for several elements at the same time and to evaluate the interactions that can be established between variables in the growing medium and in the plant itself. However, more studies including other plant species are needed to confirm the effectiveness of this method.     

Pro-Apoptotic and Pro-Autophagic Properties of Cardenolides from Aerial Parts of Pergularia tomentosa

Pergularia tomentosa L., a milkweed tropical plant belonging to the family Asclepiadaceae, is a rich source of unusual cardiac glycosides, characterised by transfused A/B rings and a sugar moiety linked by a double link, generating a dioxanoid structure. In the present report, five cardenolides isolated from the aerial parts of the plant (calactin, calotropin, 12β-hydroxycalactin, 12β,6′-dihydroxycalotropin, and 16α-hydroxycalotropin) were investigated for their biological effects on a human hepatocarcinoma cell line. Cell viability was monitored by an MTT assay. The occurrence of apoptosis was evaluated by detecting caspase-3 activation and chromatin fragmentation. The ability of these compounds to induce autophagy was analysed by monitoring two markers of the autophagic process, LC3 and p62. Our results indicated that all cardenolides had cytotoxic effects, with IC₅₀ ranging from 0.127 to 6.285 μM. All compounds were able to induce apoptosis and autophagy, calactin being the most active one. Some of them also caused a reduction in cell migration and a partial block of the cell cycle into the S-phase. The present study suggests that selected cardenolides from aerial parts of P. tomentosa, particularly calactin, possess potentially desirable properties for further investigation as anticancer agents.     

A High Throughput Screening HPLC-FLD Method for Paralytic Shellfish Toxins (PSTs) Enabling Effective Official Control

Paralytic Shellfish Toxins (PSTs) are marine biotoxins, primarily produced by dinoflagellates of the genera Gymnodinium spp., Alexandrium spp. They can accumulate in shellfish and, through the food chain, be assimilated by humans, giving rise to Paralytic Shellfish Poisoning. The maximum permitted level for PSTs in bivalves is 800 μg STX·2HCl eqv/kg (Reg. EC N° 853/2004). Until recently, the reference analytical method was the Mouse Bioassay, but Reg. EU N° 1709/2021 entered into force on 13 October 2021 and identified in the Standard EN14526:2017 or in any other internationally recognized validated method not entailing the use of live animals as official methods. Then the official control laboratories had urgently to fulfill the new requests, face out the Mouse Bioassay and implement instrumental analytical methods. The “EURLMB SOP for the analysis of PSTs by pre-column HPLC-FLD according to OMA AOAC 2005.06” also introduced a simplified semiquantitative approach to discriminate samples above and below the regulatory limit. The aim of the present paper is to present a new presence/absence test with a cut-off at 600 μg STX·2HCl eqv/kg enabling the fast discrimination of samples with very low PSTs levels from those to be submitted to the full quantitative confirmatory EN14526:2017 method. The method was implemented, avoiding the use of a large number of certified reference standards and long quantification procedures, resulting in an efficient, economical screening instrument available for official control laboratories. The protocol was fully validated, obtaining good performances in terms of repeatability (<11%) and recovery (53–106%) and accredited according to ISO/IEC 17025. The method was applied to mollusks collected from March 2021 to February 2022 along the Marche region in the frame of marine toxins official control.     

How Water Interacts with the NOH Group: The Rotational Spectrum of the 1:1 N,N-diethylhydroxylamine·Water Complex

The rotational spectrum of the 1:1 N,N-diethylhydroxylamine-water complex has been investigated using pulsed jet Fourier transform microwave spectroscopy in the 6.5–18.5 GHz frequency region. The most stable conformer has been detected as well as the 13C monosubstituted isotopologues in natural abundance and the 18O enriched water species, allowing to determine the nitrogen nuclear quadrupole coupling constants and the molecular structure in the vibrational ground state. The molecule has a Cs symmetry and the water lies in the bc symmetry plane forming two hydrogen bonds with the NOH frame with length: dHOH·NOH = 1.974 Å and dH2O·HON = 2.096 Å. From symmetry-adapted perturbation theory calculations coupled to atoms in molecule approach, the corresponding interaction energy values are estimated to be 24 and 13 kJ·mol−1, respectively. The great strength of the intermolecular interaction involving the nitrogen atom is in agreement with the high reactivity of hydroxylamine compounds at the nitrogen site.     

Quantitative Determination of Polyphenols and Flavonoids in Cistus × incanus on the Basis of IR,NIR and Raman Spectra

Cistus is a plant that has been used in natural medicine for hundreds of years; it works primarily as an antioxidant and cleansing agent. Cistus × incanus leaves or herb can be an attractive source of polyphenols and flavonoids. The official protocols of active compound analysis relies on the extraction of compounds of interest from plant matter, which makes their determination long and costly. An analysis of plant material in its native state can be performed using vibrational spectroscopy. This paper presents a comparison of Raman spectroscopy, attenuated total reflection in mid-infrared and diffuse reflectance technique in the near-infrared region for the simultaneous quantification of total polyphenols (TPC) and flavonoids (TF) content, as well as the determination of FRAP antioxidant activity of C. incanus material. Utilizing vibrational spectra and using partial least squares algorithm, TPC and TF were quantified with the RSEP_VAL errors in the 2.7–5.4% range, while FRAP antioxidant activity for validation sets was determined with relative errors ranged from 5.2 to 9.3%. For the analyzed parameters, the lowest errors of predictions were computed for models constructed using Raman data. The developed models allow for fast and precise quantification of the studied active compounds in C. incanus material without any chemical sample treatment.     

Facile Access to Hetero-poly-functional Arenes and meta-Substituted Arenes via Two-Step Dimetalation and Mg/Halogen-Exchange Protocol

The Grignard reagent, iPrMgCl and its lithium chloride-enhanced ‘turbo’ derivative iPrMgCl⋅LiCl have been employed to investigate the single iodo/magnesium exchange reactions of the trisubstituted arenes, 2,5-diiodo-N,N-diisopropylbenzamide 1 , 1,4-diiodo-2-methoxybenzene 2 , and 1,4-diiodo-2-(trifluoromethyl)benzene 3 . These three arenes themselves were initially prepared by a double ortho-, meta′-deprotonation of N,N-diisopropylbenzamide, anisole and (trifluoromethyl)benzene, respectively, using the sodium magnesiate reagent [Na₄Mg₂(TMP)₆(nBu)₂] (where TMP is 2,2,6,6-tetramethylpiperidide), and subsequent electrophilic quenching with iodine/THF solution. Thus, by following a combined deprotonation and magnesium/halogen exchange strategy, the simple monosubstituted arenes can be converted to trisubstituted diiodoarenes, which can ultimately be transformed into the corresponding mono-magnesiated arenes, in THF at −40 °C, within seconds in good yields. The other functional group (OMe, NiPr₂ or CF₃ respectively) present on the di-iodoarenes helps direct the exchange reaction to the ortho position, whereas subsequent addition of different electrophiles permits the preparation of hetero-poly-functional-arenes, with three different substituents in their structure. Intriguingly, if water is used as the electrophile, a new and facile route to prepare meta-substituted arenes, which cannot be easily obtained by conventional processes, is forthcoming. In contrast to directed ortho-metalation (DoM) chemistry, this reaction sequence can be thought of as InDirect meta-Metalation (IDmM). The scope of the chemistry has been tested further by exposing the initial unreacted iodo-functionality at the meta-position to a second Mg/I-exchange reaction and subsequent functionalization.