Photophysical properties of fluorescent imaging biological probes of nucleic acids: SAC-CI and TD-DFT Study

Recently, exciton-controlled hybridization-sensitive fluorescent oligonucleotide (ECHO) probe, which shows strong emission in the near-infrared region via hybridization to the target DNA and/or RNA strand, has been developed. In this work, photophysical properties of the chromophores of these probes and the fluorescent mechanism have been investigated by the SAC-CI and TD-DFT calculations. Three fluorescent cyanine chromophores whose excitation is challenging for TD-DFT methods, have been examined regarding the photo-absorption and emission spectra. The SAC-CI method well reproduces the experimental values with respect to transition energies, while the quantitative prediction by TD-DFT calculations is difficult for these chromophores. Some stable structures of H-aggregate system were computationally located and two of the configurations were examined for the photo-absorption. The present results support for the assumption based on experimental measurement in which strong fluorescence is due to the monomer unit in nearly planar structure and its suppression of probes is to the H-aggregates of two exciton units. Stokes shifts of these three chromophores were qualitatively reproduced by the theoretical calculations, while the energy splitting due to H-aggregate in the hybridized probe was slightly overestimated. © 2018 Wiley Periodicals, Inc.     

Does the gradient-regulated connection improve the description of correlated metal bond properties?

Gradient-regulated connection (GRAC) is a generalized gradient approximation exchange density functional designed by combining the revPBE and PW91 exchange functionals to impose their behaviors in the slowly- and fast-varying density regions, respectively. Such a construction allows one single density functional to accurately estimate both covalent and weak interactions occurring in main-group-based molecular systems. For the first time, the assessment of the performance of the GRAC exchange functional is extended to the modeling of various metal bond energy and structure properties. This assessment shows that when GRAC is coupled with the Perdew, Burke, Ernzerhof (PBE) correlation, the resulting exchange-correlation density functional is an excellent alternative to global hybrids to model bond dissociation energy, atomic electronic excitation energy, and bond length structure properties of single-reference metal bonds. It also shows that coupling with the Tognetti, Cortona, Adamo (TCA) correlation constitutes a robust approach to tackle energy bond properties of organometallic complexes with multi-reference character.     

Multiple Roles of Isocyanides in Palladium‐Catalyzed Imidoylative Couplings: A Mechanistic Study

Kinetic, spectroscopic and computational studies examining a palladium‐catalyzed imidoylative coupling highlight the dual role of isocyanides as both substrates and ligands for this class of transformations. The synthesis of secondary amides from aryl halides and water is presented as a case study. The kinetics of the oxidative addition of ArI with RNC‐ligated Pd⁰ species have been studied and the resulting imidoyl complex [(ArC=NR)Pd(CNR)₂I] (Ar=4‐F‐C₆H₄, R=tBu) has been isolated and characterized by X‐ray diffraction. The unprecedented ability of this RNC‐ligated imidoyl‐Pd complex to undergo reductive elimination at room temperature to give the amide in the presence of water and an F^?/HF buffer is demonstrated. Its behavior in solution has also been characterized, revealing an unexpected strong tendency to give cationic complexes, and notably [(ArC=NR)Pd(CNR)₃]⁺ with excess isocyanide and [(ArC=NR)Pd( )(CNR)]⁺ with bidentate phosphines ( ). These species may be responsible for catalyst deactivation and side‐reactions. Ab initio calculations performed at the DFT level allowed us to rationalize the multiple roles of RNC in the different steps of the catalytic cycle.     

Excited‐State Proton Transfer and Intramolecular Charge Transfer in 1,3‐Diketone Molecules

The photophysical signature of the tautomeric species of the asymmetric (N,N‐dimethylanilino)‐1,3‐diketone molecule are investigated using approaches rooted in density functional theory (DFT) and time‐dependent DFT (TD‐DFT). In particular, since this molecule, in the excited state, can undergo proton transfer reactions coupled to intramolecular charge transfer events, the different radiative and nonradiative channels are investigated by making use of different density‐based indexes. The use of these tools, together with the analysis of both singlet and triplet potential energy surfaces, provide new insights into excited‐state reactivity allowing one to rationalize the experimental findings including different behavior of the molecule as a function of solvent polarity.     

Rapid and simultaneous determination of curcuminoids and gingerols in food products containing turmeric and ginger using paper spray mass spectrometry

Turmeric and ginger are extensively employed as functional ingredients due to their high content of curcuminoids and gingerols, considered the key bioactive compounds found in these roots. In this study, we present an innovative and fast method for the assay of curcuminoids and gingerols in different foods containing the two spices, with the aim of monitoring the quality of products from a nutraceutical perspective. The proposed approach is based on paper spray tandem mass spectrometry coupled with the use of a labeled internal standard, which has permitted to achieve the best results in terms of specificity and accuracy. All the calculated analytical parameters were satisfactory; accuracy values are around 100% for all spiked samples and the precision data result lower than 15%. The protocol was applied to several real samples, and to demonstrate its robustness and reliability, the results were compared to those arising from the common liquid chromatographic method.     

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.     

NMR,LC-MS Characterization of Rydingia michauxii Extracts,Identification of Natural Products Acting as Modulators of LDLR and PCSK9

Rydingia michauxii (Briq.) Scheen and V.A.Albert (Lamiaceae) is used in Iranian traditional medicine to treat malaria, diabetes, hyperlipidemia, rheumatism and cardiovascular diseases. NMR and LC-DAD-MSⁿ analyses were used to establish extract composition and phenylethanoid, flavonoid glycosides, lignans, labdane diterpenes and iridoids were identified and quantified. The main constituents were isolated, and structures were elucidated based on NMR, polarimetric and MS measurements. A new natural compound, ent-labda-8(17),13-dien-18-glucopyranosyl ester-15,16-olide is described here. The effects of ent-labda-8(17),13-dien-18-oic acid-15,16-olide (1), ent-labda-8(17),13-dien-18-glucopyranosyl es-ter-15,16-olide (2), antirrhinoside (3), echinacoside (4), verbascoside (5), and apigenin 6,8-di-C-glucoside (6), on the low-density lipoprotein receptor (LDLR) and proprotein convertase subtilisin/kexin type 9 (PCSK9), were studied in the human hepatocarcinoma cell line Huh7. Among the six constituents, (3) showed the strongest induction of the LDLR (3.7 ± 2.2 fold vs. control) and PCSK9 (3.2 ± 1.5 fold vs. control) at a concentration of 50 µM. The in vitro observations indicated a potential lipid lowering activity of (3) with a statin-like mechanism of action.     

Chemometric Investigation and Antimicrobial Activity of Salvia rosmarinus Spenn Essential Oils

To ensure the better production and sustainable management of natural resources, a chemometric investigation was conducted to examine the effect of cooperative and harvesting periods on the crop yields and chemical compositions of Salvia rosmarinus Spenn essential oils in the Oriental region of Morocco. The samples were collected from three cooperatives over nine time periods from January 2018 to April 2019. The chemical composition of Salvia rosmarinus Spenn essential oils was analyzed by gas chromatography coupled with mass spectrometry. The data from this study were processed by multivariate analyses, including principal component analysis (PCA) and hierarchical cluster analysis (HCA). The disc diffusion technique and a determination of the minimal inhibitory concentration were performed to study the antibacterial properties of the oils. Statistical analysis showed that the cooperative and harvest period have a significant effect on yields. The highest yield of essential oil was recorded in April 2019 at cooperative C1. The PCA and the HCA results were divided into two groups: Group A for the summer season and group B for the winter season. The samples collected during summer were characterized by a high amount of 1,8-cineole component and a high yield of essential oil, whereas the samples collected during winter were qualified by a high amount of α-pinene component and a low yield of essential oil. The antibacterial activity of Salvia rosmarinus Spenn essential oils showed that Mycobacterium smegmatis ATCC23857 and Bacillus subtilis ATCC 23857 are the most susceptible strains, stopping growth at 1/500 (v/v). The least susceptible strain is Escherichia coli ATCC25922, with an MIC value corresponding to 1/250 (v/v). The findings of this study could have a positive economic impact on the exploitation of rosemary in the Oriental region, especially during the best harvest periods, as they indicate how to obtain the best yields of oils richest in 1,8-cineole and α-pinene chemotypes.     

Optimal rectangular MITC finite elements for Reissner–Mindlin plates

In recent years a family of finite elements named mixed interpolated tensorial components (MITC) has been introduced for the numerical approximation of Reissner–Mindlin plates. The elements have been proved to be locking free. In this article, we consider the MITC rectangular finite elements and show that it is possible to reduce the number of internal degrees of freedom in the approximation of the rotation field without losing order of convergence. Our mathematical analysis is carried out combining some results for the Stokes problem with the special features of the MITC finite elements. © 1997 John Wiley & Sons, Inc. Numer Methods Partial Differential Eq 13: 575–585, 1997