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AIM: To determine changes in the prevalence of tobacco use among students of nursing and associated factors. BACKGROUND: The prevalence and distribution of smokers among nursing students varies according to the country and period of study. METHOD: Transversal descriptive study by self-answered questionnaire. Eight hundred and fifty four subjects (94.9%) were questioned in the period 2004-2006. FINDINGS: Twenty eight percent of the students declared themselves to be smokers. The habit began before the students started university. The tendency of prevalence by year of survey and by graduation year was downward. The students shown a low nicotine dependency according to Fagerström and little motivation to give up. The average age at the onset of consumption was 14.6 (1.8) years. From the logistical regression analysis, the model best explaining the prevalence of tobacco consumption included the variable of year surveyed and academic background, those coming from the baccalaureate showing a lesser prevalence and tendency to smoke. CONCLUSIONS: Tobacco consumption among students of health sciences was less than in the general population of the same age but high given their future profession. The tendency to smoke is decreasing and most started smoking before joining the university. We recommend an intensification of actions directed at teenagers and the promotion of anti-tobacco campaigns in universities. [ABSTRACT FROM AUTHOR]

In the United States, the rate of incarceration increases on an annual basis. Communities of color – Latinas/os, African Americans and Native Americans, in particular – are the most affected by this alarming expansion of the US prison population. In recent years, Latinas/os have been identified as the fastest rate of imprisonment of all groups in the country. Like African Americans, Latinas/os emerge as trapped by the mass imprisonment phenomenon in the United States. This article examines the trends in incarceration for the US-Latina/o population, as distinguished from recent immigrants from Latin America, and it looks at some of the factors that contribute to the growth of the Latina/o population in state and federal prisons. The racialization of crime; the manner in which criminal justice policy is formulated and justified around the fear of crime; how the courts and the criminal justice system operate; and the role of the media in promoting negative images of Latinas/os are among the areas explored in discerning contributing factors. As with African Americans, common misconceptions linking Latinas/os with criminal behavior must be challenged. In contrast to African Americans, however, Latinas/os are subject to stereotypes that transcend racial myths, with one such stereotype being the false link between immigrants and crime. The fear of crime as a driving force in criminal justice policymaking and persistent negative media images of Latinas/os and immigrants that associate them with crime pose formidable obstacles to the implementation of long-overdue, meaningful, and sensible changes in the prison and criminal justice systems. Ultimately, comprehensive efforts to engage many sectors of society will be necessary to stem the trend toward increased Latina/o incarceration in the United States.Latino Studies (2008) 6, 11–34. doi:10.1057/lst.2008.1 [ABSTRACT FROM AUTHOR]

In shaded environments, minimizing dark respiration during growth could be an important aspect of maintaining a positive whole-plant net carbon balance. Changes with plant size in both biomass distribution to different tissue types and mass-specific respiration rates (Rd) of those tissues would have an impact on whole-plant respiration. In this paper, we evaluated size-related variation in Rd, biomass distribution, and nitrogen (N) and total nonstructural carbohydrate (TNC) concentrations of leaves, stems and roots of three cold-temperate tree species (Abies balsamea (L.) Mill, Acer rubrum L. and Pinus strobus L.) in a forest understory. We sampled individuals varying in age (6 to 24 years old) and in size (from 2 to 500 g dry mass), and growing across a range of irradiances (from 1 to 13% of full sun) in northern Minnesota, USA. Within each species, we found small changes in Rd, N and TNC when comparing plants growing across this range of light availability. Consistent with our hypotheses, as plants grew larger, whole-plant N and TNC concentrations in all species declined as a result of a combination of changes in tissue N and shifts in biomass distribution patterns. However, contrary to our hypotheses, whole-plant and tissue Rd increased with plant size in the three species. [ABSTRACT FROM AUTHOR]

High-valent oxoiron species have been invoked as oxidizing agents in a variety of iron-dependent oxygenases. Taking inspiration from nature, selected nonheme iron complexes have been developed as catalysts to elicit C-H oxidation through the mediation of putative oxoiron(V) species, akin to those proposed for Rieske oxygenases. The addition of carboxylic acids in these iron-catalyzed C-H oxidations has proved highly beneficial in terms of product yields and selectivities, suggesting the direct involvement of iron(V)-oxo-carboxylato species. When the carboxylic acid functionality is present in the alkane substrate, it acts as a directing group, enabling the selective intramolecular γ-C-H hydroxylation that eventually affords γ-lactones. While this mechanistic frame is solidly supported by previous mechanistic studies, direct spectroscopic detection of the key iron(V)-oxo-carboxylato intermediate and its competence for engaging in the selective γ-C-H oxidation leading to lactonization have not been accomplished. In this work, we generate a series of well-defined iron(V)-oxo-carboxylato species ( 2c - 2f ) differing in the nature of the bound carboxylate ligand. Species 2c - 2f are characterized by a set of spectroscopic techniques, including UV-vis spectroscopy, cold-spray ionization mass spectrometry (CSI-MS), and, in selected cases, EPR and Mössbauer spectroscopies. We demonstrate that 2c - 2f undergo site-selective γ-lactonization of the carboxylate ligand in a stereoretentive manner, thus unequivocally identifying metal-oxo-carboxylato species as the powerful yet selective C-H cleaving species in catalytic γ-lactonization reactions of carboxylic acids. Reactivity experiments confirm that the intramolecular formation of γ-lactones is in competition with the intermolecular oxidation of external alkanes and olefins. Finally, mechanistic studies, together with DFT calculations, support a mechanism involving a site-selective C-H cleavage in the γ-position of the carboxylate ligand by the oxo moiety, followed by a fast carboxylate rebound, eventually leading to the selective formation of γ-lactones., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The human phosphatidylinositol 4-phosphate 5-kinase type I α (hPIP5K1α) plays a key role in the development of prostate cancer. In this work, seventeen derivatives of the natural diterpene totarol were prepared by copper(I)-catalysed Huisgen 1,3-dipolar cycloaddition reaction of the correspondingO-propargylated totarol with aryl or alkyl azides and screened for their inhibitory activities toward hPIP5K1α. Five compounds, 3a, 3e, 3f, 3i, and 3r, strongly inhibited the enzyme activity with IC 50 values of 1.44, 0.46, 1.02, 0.79, and 3.65 µM, respectively, with the most potent inhibitor 3e 13-[(1-(3-nitrophenyl)triazol-4yl)methoxy]-totara-8,11,13-triene). These compounds were evaluated on their antiproliferative effects in a panel of prostate cancer cell lines. Compound 3r inhibited the proliferation of LNCaP, PC3 and DU145 cells at 20 µM, strongly, but also has strong cytotoxic effects on all tested cells., 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 Ltd.. All rights reserved.)

We synthesized a series of four parent aza-β -ketoiminate organoboron complexes and performed spectroscopic studies using both experimental and computational techniques. We studied how benzannulation influences the vibronic structure of the UV/Vis absorption bands with a focus on the bright lowest-energy π → π* electronic excitation. Theoretical simulations, accounting for inhomogeneous broadening effects using different embedding schemes, allowed gaining in-depth insights into the observed differences in band shapes induced by structural modifications. We observed huge variations in the distributions of vibronic transitions depending on the position of benzannulation. By and large, the harmonic approximation combined with the adiabatic hessian model delivers qualitatively correct band shapes for the one-photon absorption spectra, except in one case. We also assessed the importance of non-Condon effects (accounted for by the linear term in Herzberg-Teller expansion of the dipole moment) for S 0 → S 1 band shapes. It turned out that non-Condon contributions have no effect on the band shape in one-photon absorption spectra. In contrast, these effects significantly change the Franck-Condon band shapes of the two-photon absorption spectra. For one of the studied organoboron complexes we also performed a preliminary exploration of mechanical anharmonicity, resulting in an increase of the intensity of the 0-0 transition, which improves the agreement with the experimental data compared to the harmonic model.

We analyze the varying susceptibilities of different density functional approximations (DFAs) to present spurious oscillations on the profiles of several vibrational properties. Among other problems, these spurious oscillations cause significant errors in harmonic and anharmonic IR and Raman frequencies and intensities. This work hinges on a judicious strategy to dissect the exchange and correlation components of DFAs and pinpoint the origins of these oscillations. We identify spurious oscillations in derivatives of all energy components with respect to nuclear displacements, including those energy terms that do not involve numerical integrations. These indirect spurious oscillations are attributed to suboptimal electron densities resulting from a self-consistent field procedure using a DFA that exhibits direct spurious oscillations. Direct oscillations stem from inaccurate numerical integration of the exchange and correlation energy density functionals. A thorough analysis of direct spurious oscillations reveals that only a handful of exchange and correlation components are insensitive to spurious oscillations, giving rise to three families of functionals, BH&H, LSDA, and BLYP. Among the functionals in these families, we encounter four widespread DFAs: BLYP, B3LYP, LC-BLYP, and CAM-B3LYP. Certain DFAs like PBE appear less sensitive to spurious oscillations due to compensatory cancellations between their energy components. Additionally, we found non-negligible but small oscillations in PBE and TPSS, which could be safely employed provided a sufficiently large integration grid is used in the calculations. These findings hint at the key components of current approximations to be improved and emphasize the necessity to develop accurate DFAs suitable for studying molecular spectroscopies.

In this Communication, we study the effect of spurious oscillations in the profiles of energy derivatives with respect to nuclear coordinates calculated with density functional approximations (DFAs) for formaldehyde, pyridine, and furan in their ground and electronic excited states. These spurious oscillations, which can only be removed using extensive integration grids that increase enormously the CPU cost of DFA calculations, are significant in the case of third- and fourth-order energy derivatives of the ground and excited states computed by M06-2X and ω B97X functionals. The errors in question propagate to anharmonic vibronic spectra computed under the Franck-Condon approximation, i.e. , positions and intensities of vibronic transitions are affected to a large extent (shifts as significant as hundreds of cm -1 were observed). On the other hand, the LC-BLYP and CAM-B3LYP functionals show a much less pronounced effect due to spurious oscillations. Based on the results presented herein, we recommend either LC-BLYP or CAM-B3LYP with integration grids (250, 974) (or larger) for numerically stable simulations of vibronic spectra including anharmonic effects.

Phyllachora maydis is a fungal pathogen causing tar spot of corn (Zea mays L.), a new and emerging, yield-limiting disease in the United States. Since being first reported in Illinois and Indiana in 2015, P. maydis can now be found across much of the corn growing regions of the United States. Knowledge of the epidemiology of P. maydis is limited but could be useful in developing tar spot prediction tools. The research presented here aims to elucidate the environmental conditions necessary for the development of tar spot in the field and the creation of predictive models to anticipate future tar spot epidemics. Extended periods (30-day windowpanes) of moderate mean ambient temperature (18-23 °C) were most significant for explaining the development of tar spot. Shorter periods (14- to 21-day windowpanes) of moisture (relative humidity, dew point, number of hours with predicted leaf wetness) were negatively correlated with tar spot development. These weather variables were used to develop multiple logistic regression models, an ensembled model, and two machine learning models for the prediction of tar spot development. This work has improved the understanding of P. maydis epidemiology and provided the foundation for the development of a predictive tool for anticipating future tar spot epidemics., (© 2023. Springer Nature Limited.)

Tar spot, caused by  Phyllachora maydis , is an emerging disease of corn in the United States. Stromata of  P. maydis  are sometimes surrounded by necrotic lesions known as fisheyes and were previously reported to be caused by the fungus Microdochium   maydis . The association of  M. maydis  with fisheye lesions has not been well documented outside of initial descriptions from the early 1980s. The objective of this work was to assess and identify Microdochium -like fungi associated with necrotic lesions surrounding P. maydis stromata using a culture-based method. In 2018, corn leaf samples with fisheye lesions associated with tar spot stromata were collected from 31 production fields across Mexico, Illinois, and Wisconsin. Cultures of pure isolates collected from Mexico believed to be M. maydis were included in the study. A total of 101 Microdochium / Fusarium -like isolates were obtained from the necrotic lesions, and 91% were identified as  Fusarium  spp., based on initial ITS sequence data. Multi-gene (ITS, TEF1-α, RPB1, and RPB2) phylogenies were constructed for a subset of 55 isolates;  Microdochium ,  Cryptostroma , and  Fusarium  reference sequences were obtained from GenBank. All the necrotic lesion isolates clustered within  Fusarium  lineages and were phylogenetically distinct from the Microdochium  clade. All Fusarium isolates from Mexico belonged to the  F. incarnatum-equiseti  species complex, whereas >85% of the U.S. isolates grouped within the  F. sambucinum  species complex. Our study suggests that initial reports of M. maydis were misidentifications of resident Fusarium spp. [Formula: see text] Copyright © 2023 The Author(s). This is an open access article distributed under the CC BY-NC-ND 4.0 International license., Competing Interests: The author(s) declare no conflict of interest.

Titanium compounds in low oxidation states are highly reducing species and hence powerful tools for the functionalization of small molecules. However, their potential has not yet been fully realized because harnessing these highly reactive complexes for productive reactivity is generally challenging. Advancing this field, herein we provide a detailed route for the formation of titanium(III) orthophenylendiamido (PDA) species using [LiBHEt 3 ] as a reducing agent. Initially, the corresponding lithium PDA compounds [Li 2 ( Ar PDA)(thf) 3 ] (Ar = 2,4,6-trimethylphenyl ( Mes PDA), 2,6-diisopropylphenyl ( i Pr PDA)) are combined with [TiCl 4 (thf) 2 ] to form the heterobimetallic complexes [{TiCl( Ar PDA)}(μ- Ar PDA){Li(thf) n }] ( n = 1, Ar = i Pr 3 and n = 2, Ar = Mes 4 ). Compound 4 evolves to species [Ti( Mes PDA) 2 ] ( 6 ) via thermal treatment. In contrast, the transformation of 3 into [Ti( i Pr PDA) 2 ] ( 5 ) only occurs in the presence of [LiNMe 2 ], through a lithium-assisted process, as revealed by density functional theory (DFT). Finally, the Ti(IV) compounds 3 - 6 react with [LiBHEt 3 ] to give rise to the Ti(III) species [Li(thf) 4 ][Ti( Ar PDA) 2 ] (Ar = i Pr 8 , Mes 9 ). These low-valent compounds in combination with [PPN]Cl (PPN = bis(triphenylphosphine)iminium) are proved to be highly selective catalysts for the copolymerization of CO 2 and cyclohexene epoxide. Reactions occur at 1 bar pressure with activity/selectivity levels similar to Salen-Cr(III) compounds.

A recently developed computational scheme is employed to interpret changes in the infrared spectra of halogen-bonded systems in terms of intermolecular interaction energy components (electrostatic, exchange, induction, dispersion) taking pyridine⋯perfluorohaloarene complexes as examples. For all complexes, we find a strong linear correlation between the different terms of the interaction-induced changes of the IR band associated with an intermolecular halogen bond stretching mode and the corresponding terms of the interaction energy, which implies that the interaction components play similar roles in both properties. This is not true for other vibrational modes localized in one of the monomers studied here, for which the corresponding interaction-induced changes in IR bands may present a completely different decomposition than the interaction energy.

We present a straightforward and low-cost computational protocol to estimate the variation of the charge transfer rate constant, kCT, in a molecular donor-acceptor caused by an external electric field. The proposed protocol also allows for determining the strength and direction of the field that maximize the kCT. The application of this external electric field results in up to a >4000-fold increase in the kCT for one of the systems studied. Our method allows the identification of field-induced charge-transfer processes that would not occur without the perturbation caused by an external electric field. In addition, the proposed protocol can be used to predict the effect on the kCT due to the presence of charged functional groups, which may allow for the rational design of more efficient donor-acceptor dyads., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

The popularity of infrared (IR) spectroscopy is due to its high interpretive power. This study presents a new computational tool for analyzing the IR spectra of molecular complexes in terms of intermolecular interaction energy components. In particular, the proposed scheme enables associating the changes in the IR spectra occurring upon complex formation with individual types of intermolecular interactions (electrostatic, exchange, induction, and dispersion), thus providing a completely new insight into the relations between the spectral features and the nature of interactions in molecular complexes. To demonstrate its interpretive power, we analyze, for selected vibrational modes, which interaction types rule the IR intensity changes upon the formation of two different types of complexes, namely π⋯π stacked (benzene⋯1,3,5-trifluorobenzene) and hydrogen-bonded (HCN⋯HNC) systems. The exemplary applications of the new scheme to these two molecular complexes revealed that the interplay of interaction energy components governing their stability might be very different from that behind the IR intensity changes. For example, in the case of the dispersion-bound π⋯π-type complex, dispersion contributions to the interaction induced IR intensity of the selected modes are notably smaller than their first-order (electrostatic and exchange) counterparts.

The results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an efficient first-principle protocol for simulating vibrationally-resolved absorption spectra, including nonempirical estimations of the inhomogeneous broadening. To this end, we analyze three key aspects: (i) a metric-based selection of density functional approximation (DFA) so to benefit from the computational efficiency of time-dependent density function theory (TD-DFT) while safeguarding the accuracy of the vibrationally-resolved spectra, (ii) an assessment of two vibrational structure schemes (vertical gradient and adiabatic Hessian) to compute the Franck-Condon factors, and (iii) the use of machine learning to speed up nonempirical estimations of the inhomogeneous broadening. In more detail, we predict the absorption band shapes for a set of 20 medium-sized fluorescent dyes, focusing on the bright ππ ★ S 0 → S 1 transition and using experimental results as references. We demonstrate that, for the studied 20-dye set which includes structures with large structural variability, the preselection of DFAs based on an easily accessible metric ensures accurate band shapes with respect to the reference approach and that range-separated functionals show the best performance when combined with the vertical gradient model. As far as band widths are concerned, we propose a new machine-learning-based approach for determining the inhomogeneous broadening induced by the solvent microenvironment. This approach is shown to be very robust offering inhomogeneous broadenings with errors as small as 2 cm -1 with respect to genuine electronic-structure calculations, with a total CPU time reduced by 98%.

Key components of organic-based electro-optic devices are challenging to design or optimize because they exhibit nonlinear optical responses, which are difficult to model or rationalize. Computational chemistry furnishes the tools to investigate extensive collections of molecules in the quest for target compounds. Among the electronic structure methods that provide static nonlinear optical properties (SNLOPs), density functional approximations (DFAs) are often preferred because of their low cost/accuracy ratio. However, the accuracy of the SNLOPs critically depends on the amount of exact exchange and electron correlation included in the DFA, precluding the reliable calculation of many molecular systems. In this scenario, wave function methods such as MP2, CCSD, and CCSD(T) constitute a reliable alternative to compute SNLOPs. Unfortunately, the computational cost of these methods significantly restricts the size of molecules to study, a limitation that hampers the identification of molecules with significant nonlinear optical responses. This paper analyzes various flavors and alternatives to MP2, CCSD, and CCSD(T) methods that either drastically reduce the computational cost or improve their performance but were scarcely and unsystematically employed to compute SNLOPs. In particular, we have tested RI-MP2, RIJK-MP2, RIJCOSX-MP2 (with GridX2 and GridX4 setups), LMP2, SCS-MP2, SOS-MP2, DLPNO-MP2, LNO-CCSD, LNO-CCSD(T), DLPNO-CCSD, DLPNO-CCSD(T0), and DLPNO-CCSD(T1). Our results indicate that all these methods can be safely employed to calculate the dipole moment and the polarizability with average relative errors below 5% with respect to CCSD(T). On the other hand, the calculation of higher-order properties represents a challenge for LNO and DLPNO methods, which present severe numerical instabilities in computing the single-point field-dependent energies. RI-MP2, RIJK-MP2, or RIJCOSX-MP2 are cost-effective methods to compute first and second hyperpolarizabilities with a marginal average error with respect to canonical MP2 (up to 5% for β and up to 11% for γ). More accurate hyperpolarizabilities can be obtained with DLPNO-CCSD(T1); however, this method cannot be employed to obtain reliable second hyperpolarizabilities. These results open the way to obtain accurate nonlinear optical properties at a computational cost that can compete with current DFAs.

Two oxoiron(IV) isomers ( R 2a and R 2b) of general formula [Fe IV (O)( R PyNMe 3 )(CH 3 CN)] 2+ are obtained by reaction of their iron(II) precursor with NBu 4 IO 4 . The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R 2a and R 2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R 2a reacts one order of magnitude faster than R 2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R 2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Baccharis genus Asteraceae is widely used in traditional treatment against fever, headache, hepatobiliary disorders, skin ulcers, diabetes, and rheumatism, as well as an antispasmodic and diuretic. Its phytochemistry mainly shows the presence of flavonoids and terpenoids such as monoterpenes, sesquiterpenes, diterpenes, and triterpenes. Some of them have been evaluated for biological activities presenting allelopathic, antimicrobial, cytotoxic, and anti-inflammatory properties. In this paper, our research group reported the isolation, characterization, and antifungal evaluation of several molecules isolated from the dichloromethane extract from Baccharis prunifolia , Baccharis trinervis , and Baccharis zumbadorensis against the phytopathogen fungus Botrytis cinerea . The isolated compounds have not previously been tested against Botrytis , revealing an important source of antifungals in the genus Baccharis . Six known flavones were isolated from B. prunifolia . The dichloromethane extracts of B. trinervis and B. zumbadorensis were subjected to a bio-guided isolation, obtaining three known flavones, an α-hydroxidihydrochalcone mixture, one labdane, one triterpene, and two norbisabolenes from the most active fractions. The compounds 4'-methoxy-α-hydroxydihydrochalcone ( 7A ), 3β,15-dihydroxylabdan-7-en-17-al ( 8 ), and 13-nor-11,12-dihydroxybisabol-2-enone ( 11 ) are novel. The most active compounds were the Salvigenin ( 5 ) and 1,2-dihydrosenedigital-2-one ( 10 ) with an IC50 of 13.5 and 3.1 μg/mL, respectively.

We have studied the halogen-bonding interactions of a pyridine-functionalized fluoroborate dye with perfluorohaloarenes (C 6 F 6 , C 6 F 5 Cl, C 6 F 5 Br, and C 6 F 5 I) in the two-component-only liquid phase using fluorescence spectroscopy. Based on the results of spectroscopic measurements and electronic-structure calculations, we have confirmed the stability only for the complex between C 6 F 5 I and the emissive dye, and it has been demonstrated that halogen-bonding interactions are accompanied by significant Stokes shifts for the ππ* band. We also provide experimental evidence that for this complex, the emission is quenched due to a simultaneous decrease of radiative and increase of nonradiative decay rate constants upon halogen-bonding interactions.

Reactions that enable selective functionalization of strong aliphatic C-H bonds open new synthetic paths to rapidly increase molecular complexity and expand chemical space. Particularly valuable are reactions where site-selectivity can be directed toward a specific C-H bond by catalyst control. Herein we describe the catalytic site- and stereoselective γ-lactonization of unactivated primary C-H bonds in carboxylic acid substrates. The system relies on a chiral Mn catalyst that activates aqueous hydrogen peroxide to promote intramolecular lactonization under mild conditions, via carboxylate binding to the metal center. The system exhibits high site-selectivity and enables the oxidation of unactivated primary γ-C-H bonds even in the presence of intrinsically weaker and a priori more reactive secondary and tertiary ones at α- and β-carbons. With substrates bearing nonequivalent γ-C-H bonds, the factors governing site-selectivity have been uncovered. Most remarkably, by manipulating the absolute chirality of the catalyst, γ-lactonization at methyl groups in gem -dimethyl structural units of rigid cyclic and bicyclic carboxylic acids can be achieved with unprecedented levels of diastereoselectivity. Such control has been successfully exploited in the late-stage lactonization of natural products such as camphoric, camphanic, ketopinic, and isoketopinic acids. DFT analysis points toward a rebound type mechanism initiated by intramolecular 1,7-HAT from a primary γ-C-H bond of the bound substrate to a highly reactive Mn IV -oxyl intermediate, to deliver a carbon radical that rapidly lactonizes through carboxylate transfer. Intramolecular kinetic deuterium isotope effect and 18 O labeling experiments provide strong support to this mechanistic picture.

Cobalt-catalyzed C-H amination via M-nitrenoid species is spiking the interest of the research community. Understanding this process at a molecular level is a challenging task, and here we report a well-defined macrocyclic system featuring a pseudo- O h aryl-Co III species that reacts with aliphatic azides to effect intramolecular C sp2 -N bond formation. Strikingly, a putative aryl-Co═NR nitrenoid intermediate species is formed and is rapidly trapped by a carboxylate ligand to form a carboxylate masked-nitrene, which functions as a shortcut to stabilize and guide the reaction to productive intramolecular C sp2 -N bond formation. On one hand, several intermediate species featuring the C sp2 -N bond formed have been isolated and structurally characterized, and the essential role of the carboxylate ligand has been proven. Complementarily, a thorough density functional theory study of the C sp2 -N bond formation mechanism explains at the molecular level the key role of the carboxylate-masked nitrene species, which is essential to tame the metastability of the putative aryl-Co III ═NR nitrene species to effectively yield the C sp2 -N products. The solid molecular mechanistic scheme determined for the C sp2 -N bond forming reaction is fully supported by both experimental and computation complementary studies.

We show that properties of molecules with low-frequency modes calculated with density functional approximations (DFAs) suffer from spurious oscillations along the nuclear displacement coordinate due to numerical integration errors. Occasionally, the problem can be alleviated using extensive integration grids that compromise the favorable cost-accuracy ratio of DFAs. Since spurious oscillations are difficult to predict or identify, DFAs are exposed to severe performance errors in IR and Raman intensities and frequencies or vibrational contributions to any molecular property. Using Fourier spectral analysis and digital signal processing techniques, we identify and quantify the error due to these oscillations for 45 widely used DFAs. LC-BLYP and BH&H are revealed as the only functionals showing robustness against the spurious oscillations of various energy, dipole moment, and polarizability derivatives with respect to a nuclear displacement coordinate. Given the ubiquitous nature of molecules with low-frequency modes, we warrant caution in using modern DFAs to simulate vibrational spectroscopies.

From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1. The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites of the substrate yielding the 2-oxoaustroeupatol (2) and 2,19-dioxoaustroeupatol (3). The treatment of 2 with sodium periodate yields a heterocyclic derivative (ε-caprolactone derivate 4) formed by oxidative cleavage and unexpected intramolecular attack of the hydroxymethylene (C-19) oxygen to the ketonic carbon (C-2). A plausible mechanistic pathway for the obtention of compound 4 is proposed., (© 2022. The Author(s).)

Information on the transcriptomic changes that occur within sclerotia of Aspergillus flavus during its sexual cycle is very limited and warrants further research. The findings will broaden our knowledge of the biology of A. flavus and can provide valuable insights in the development or deployment of non-toxigenic strains as biocontrol agents against aflatoxigenic strains. This article presents transcriptomic datasets included in our research article entitled, "Development of sexual structures influences metabolomic and transcriptomic profiles in Aspergillus flavus " [1], which utilized transcriptomics to identify possible genes and gene clusters associated with sexual reproduction and fertilization in A. flavus . RNA was extracted from sclerotia of a high fertility cross (Hi-Fert-Mated), a low fertility cross (Lo-Fert-Mated), and unmated strains (Hi-Fert-Unmated and Lo-Fert-Unmated) of A. flavus collected immediately after crossing and at every two weeks until eight weeks of incubation on mixed cereal agar at 30 °C in continuous darkness ( n  = 4 replicates from each treatment for each time point; 80 total). Raw sequencing reads obtained on an Illumina NovaSeq 6000 were deposited in NCBI's Sequence Read Archive (SRA) repository under BioProject accession number PRJNA789260. Reads were mapped to the A. flavus NRRL 3357 genome (assembly JCVI-afl1-v2.0; GCA_000006275.2) using STAR software. Differential gene expression analyses, functional analyses, and weighted gene co-expression network analysis were performed using DESeq2 R packages. The raw and analyzed data presented in this article could be reused for comparisons with other datasets to obtain transcriptional differences among strains of A. flavus or closely related species. The data can also be used for further investigation of the molecular basis of different processes involved in sexual reproduction and sclerotia fertility in A. flavus ., Competing Interests: 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., (© 2022 The Author(s).)

Sclerotium (female) fertility, the ability of a strain to produce ascocarps, influences internal morphological changes during sexual reproduction in Aspergillus flavus. Although sclerotial morphogenesis has been linked to secondary metabolite (SM) biosynthesis, metabolic and transcriptomic changes within A. flavus sclerotia during sexual development are not known. Successful mating between compatible strains may result in relatively high or low numbers of ascocarps being produced. Sclerotia from a high fertility cross (Hi-Fert-Mated), a low fertility cross (Lo-Fert-Mated), unmated strains (Hi-Fert-Unmated and Lo-Fert-Unmated) were harvested immediately after crosses were made and every two weeks until 8 weeks of incubation, then subjected to targeted metabolomics (n = 106) and transcriptomics analyses (n = 80). Aflatoxin B 1 production varied between Hi-Fert-Mated and Hi-Fert-Unmated sclerotia, while it remained low or was undetected in Lo-Fert-Mated and Lo-Fert-Unmated sclerotia. Profiling of 14 SMs showed elevated production of an aflavazole analog, an aflavinine isomer, and hydroxyaflavinine in Hi-Fert-Mated sclerotia at 4 to 8 weeks. Similarly, genes ayg1, hxtA, MAT1, asd-3, preA and preB, and genes in uncharacterized SM gene clusters 30 and 44 showed increased expression in Hi-Fert-Mated sclerotia at these time points. These results broaden our knowledge of the biochemical and transcriptional processes during sexual development in A. flavus., Competing Interests: Declaration of competing interest None., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Infrared (IR) spectroscopy is commonly used in chemical laboratories to study the geometrical structure of molecules and molecular complexes. The analysis of experimental IR spectra can nowadays be reliably supported by the results of quantum-chemical computations as vibrational frequencies and corresponding vibrational transition intensities are routinely calculated using harmonic approximation by virtually all quantum chemistry packages. In the present study we combine the methodology of computing vibrational spectra using high-level electron correlation treatments with an analytical potential-based approach to take into account spatial confinement effects. Using this approach, we perform a pioneering analysis of the impact of the spatial confinement caused by a cylindrical harmonic oscillator potential on the harmonic vibrational transition intensities and frequencies of two hydrogen-bonded complexes: HCN…HCN and HCN…HNC. The emphasis is put on the largest-intensity bands, which correspond to the stretching vibrations. The obtained results demonstrate that embedding the molecular complexes in an external confining potential causes significant changes of transition intensities and vibrational frequencies., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Chołuj, Luis, Bartkowiak and Zaleśny.)

From aerial parts of Stevia lucida Lagasca was isolated the natural mixture of isomeric eudesmanolides helenin. The identification and quantification of the constituents of helenin (alantolactone 1 and isoalantolactone 2 , ratio 3:7) was performed through the quantitative analysis of its 1D and 2D NMR spectra.

Electrides are very peculiar ionic compounds where electrons occupy the anionic positions. In a crystal lattice, these isolated electrons often form channels or surfaces, furnishing electrides with many traits with promising technological applications. Despite their huge potential, thus far, only a few stable electrides have been produced because of the intricate synthesis they entail. Due to the difficulty in assessing the presence of isolated electrons, the characterization of electrides also poses some serious challenges. In fact, their properties are expected to depend on the arrangement of these electrons in the molecule. Among the criteria that we can use to characterize electrides, the presence of a non-nuclear attractor (NNA) of the electron density is both the rarest and the most salient feature. Therefore, a correct description of the NNA is crucial to determine the properties of electrides. In this paper, we analyze the NNA and the surrounding region of nine molecular electrides to determine the number of isolated electrons held in the electride. We have seen that the correct description of a molecular electride hinges on the electronic structure method employed for the analyses. In particular, one should employ a basis set with sufficient flexibility to describe the region close to the NNA and a density functional approximation that does not suffer from large delocalization errors. Finally, we have classified these nine molecular electrides according to the most likely number of electrons that we can find in the NNA. We believe this classification highlights the strength of the electride character and will prove useful in designing new electrides.

Herein we explore the intrinsic organometallic reactivity of iron embedded in a tetradentate N 3 C macrocyclic ligand scaffold that allows the stabilization of aryl-Fe species, which are key intermediates in Fe-catalyzed cross-coupling and C-H functionalization processes. This study covers C-H activation reactions using Me L H and FeCl 2 , biaryl C-C coupling product formation through reaction with Grignard reagents, and cross-coupling reactions using Me L B r or H L Br in combination with Fe 0 (CO) 5 . Synthesis under light irradiation and moderate heating (50 °C) affords the aryl-Fe II complexes [Fe II (Br)( Me L )(CO)] ( 1 Me ) and [Fe II ( H L )(CO) 2 ]Br ( 1 H ). Exhaustive spectroscopic characterization of these rare low-spin diamagnetic species, including their crystal structures, allowed the investigation of their intrinsic reactivity., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

The shift towards renewable energy is one of the main challenges of this generation. Dye-sensitized solar cells (DSSCs), based on donor-acceptor architectures, can help in this transition as they present excellent photovoltaic efficiencies yet cheap and simple manufacturing. For molecular heterojunction DSSCs, donor-acceptor pairs are linked in a covalent manner, which facilitates their tailoring and rational design. Nevertheless, reliable computational characterization of charge transfer rate constants (kCT) is needed to speed this development process up. In this context, the performance of time-dependent density functional theory for the calculation of kCT values in donor-acceptor fullerene-based dyads has not been benchmarked yet. Herein, we present a detailed analysis on the performance of seven well-known density functional approximations (DFAs) for this type of system, focusing on several parameters such as the reorganization energies (λ), electronic couplings (VDA), and Gibbs energies (ΔG0CT), as well as the final rate constants. The amount of exact exchange at short range (SR) and long range (LR) electron-electron distances (and the transition from the SR to LR) turned out to be key for the success of the prediction. The tuning of these parameters improves significantly the performance of current DFAs.

Real-space analysis tools afford additive and transferable contributions of atoms to molecular properties. In the case of the molecular (hyper)polarizabilities, the atomic contributions that have been derived so far include a charge-transfer term that is origin-dependent. In this letter, we present the first genuinely origin-independent energy-based (OIEB) methodology for the decomposition of the static (hyper)polarizabilities that benefits from real-space molecular energy decomposition schemes, focusing on the static polarizability and showing that extension to static hyperpolarizabilities is straightforward. The numerical realization of the OIEB method shows the expected origin independence, atomic additivity, and transferability of atomic and functional group polarizability tensors. Furthermore, the OIEB atomic (fragment) polarizability tensors are symmetric by definition.

C-F bonds are one of the most inert functionalities. Nevertheless, some [Cu 2 O 2 ] 2+ species are able to defluorinate-hydroxylate ortho -fluorophenolates in a chemoselective manner over other ortho -halophenolates. Albeit it is known that such reactivity is promoted by an electrophilic attack of a [Cu 2 O 2 ] 2+ core over the arene ring, the crucial details of the mechanism that explain the chemo- and regioselectivity of the reaction remain unknown, and it has not being determined either if Cu II 2 (η 2 :η 2 -O 2 ) or Cu III 2 (μ-O) 2 species are responsible for the initial attack on the arene. Herein, we present a combined theoretical and experimental mechanistic study to unravel the origin of the chemoselectivity of the ortho-defluorination-hydroxylation of 2-halophenolates by the [Cu 2 (O) 2 (DBED) 2 ] 2+ complex (DBED = N , N '-di- tert -butylethylenediamine). Our results show that the equilibria between (side-on)peroxo ( P ) and bis(μ-oxo) ( O ) isomers plays a key role in the mechanism, with the latter being the reactive species. Furthermore, on the basis of quantum-mechanical calculations, we were able to rationalize the chemoselective preference of the [Cu 2 (O) 2 (DBED) 2 ] 2+ catalyst for the C-F activation over C-Cl and C-H activations.

In the last 30 years, fullerene-based materials have become popular building blocks for devices with a broad range of applications. Among fullerene derivatives, endohedral metallofullerenes (EMFs, M@C x ) have been widely studied owing to their unique properties and reactivity. For real applications, fullerenes and EMFs must be exohedrally functionalized. It has been shown that encapsulated metal cations facilitate the Diels-Alder reaction in fullerenes. Herein, the Bingel-Hirsch (BH) addition of ethyl bromomalonate over a series of ion-encapsulated M@C 60 (M=Ø, Li + , Na + , K + , Mg 2+ , Ca 2+ , and Cl - ; Ø@C 60 stands for C 60 without any endohedral metal) is quantum mechanically explored to analyze the effect of these ions on the BH addition. The results show that the incarcerated ion has a very important effect on the kinetics and thermodynamics of this reaction. Among the systems studied, K + @C 60 is the one that leads to the fastest BH reaction, whereas the slowest reaction is given by Cl - @C 60 ., (© 2020 Wiley‐VCH GmbH.)

Aspergillus flavus contaminates agricultural products worldwide with carcinogenic aflatoxins that pose a serious health risk to humans and animals. The fungus survives adverse environmental conditions through production of sclerotia. When fertilized by a compatible conidium of an opposite mating type, a sclerotium transforms into a stroma within which ascocarps, asci, and ascospores are formed. However, the transition from a sclerotium to a stroma during sexual reproduction in A. flavus is not well understood. Early events during the interaction between sexually compatible strains of A. flavus were visualized using conidia of a green fluorescent protein (GFP)-labeled MAT1-1 strain and sclerotia of an mCherry-labeled MAT1-2 strain. Both conidia and sclerotia of transformed strains germinated to produce hyphae within 24 h of incubation. Hyphal growth of these two strains produced what appeared to be a network of interlocking hyphal strands that were observed at the base of the mCherry-labeled sclerotia (i.e., region in contact with agar surface) after 72 h of incubation. At 5 wk following incubation, intracellular green-fluorescent hyphal strands were observed within the stromatal matrix of the mCherry-labeled strain. Scanning electron microscopy of stromata from a high- and low-fertility cross and unmated sclerotia was used to visualize the formation and development of sexual structures within the stromatal and sclerotial matrices, starting at the time of crossing and thereafter every 2 wk until 8 wk of incubation. Morphological differences between sclerotia and stromata became apparent at 4 wk of incubation. Internal hyphae and croziers were detected inside multiple ascocarps that developed within the stromatal matrix of the high-fertility cross but were not detected in the matrix of the low-fertility cross or the unmated sclerotia. At 6 to 8 wk of incubation, hyphal tips produced numerous asci, each containing one to eight ascospores that emerged out of an ascus following the breakdown of the ascus wall. These observations broaden our knowledge of early events during sexual reproduction and suggest that hyphae from the conidium-producing strain may be involved in the early stages of sexual reproduction in A. flavus . When combined with omics data, these findings could be useful in further exploration of the molecular and biochemical mechanisms underlying sexual reproduction in A. flavus .

The optimization of nonlinear optical properties for "real-life" applications remains a key challenge for both experimental and theoretical approaches. In particular, for two-photon processes, maximizing the two-photon action cross section (TPACS), the figure of merit for two-photon bioimaging spectroscopy, requires simultaneously controlling all its components. In the present Letter, a series of difluoroborates presenting various heterocyclic rings as an electron acceptor have been synthesized and their absorption, fluorescence, photoisomerization, and two-photon absorption features have been analyzed using both experimental and theoretical approaches. Our results demonstrate that the TPACS values can be fine-tuned by changing the position of a single heteroatom, which alters the fluorescence quantum yields without changing the intrinsic two-photon absorption cross section. This approach offers a new strategy for optimizing TPACS.

The methanol extract form the leaves of Phytolacca icosandra L., afforded the unprecedented artificial triterpenoid fatty acid ester 1 derived from the new natural triterpenoid phytolaccagenic acid 3-O-myristate (1a), along with the three known triterpenoids serjanic, acinosolic and phytolaccagenic acid (2 - 4). Their structures were stablished by HR-EI-MS, 1D and 2D NMR techniques. The possible mechanistic formation of 1 is proposed, and the in vitro toxicity of all compounds was assessed using the brine shrimp lethality assay (BSLA).

The calculation of nonlinear optical properties (NLOPs) using density functional theory (DFT) remains a challenge in computational chemistry. Although the existing range-separated functionals display the best performance for the calculation of this type of properties, their errors strongly depend on the family of molecules studied. Herein, we have explored a new strategy to empirically tune the range-separated LC-BLYP method to improve the accuracy of the calculation of the second hyperpolarizabilities (γ), which are poorly described by current density functional approximations. First, we benchmarked nine of the most accurate commonly used range-separated hybrid and optimally tuned functionals (i.e. B3LYP, PBE0, BH&HLYP, M06-2X, MN15, ωB97X-D, CAM-B3LYP, LC-BLYP and OT-LC-BLYP) for the calculation of γ using as a reference the CCSD(T) values of a chemically diverse set of 60 molecules. Among these nine functionals, LC-BLYP gives the lowest average errors. We determined the value of the range-separation parameter ω required to reproduce the CCSD(T) second hyperpolarizabilities with the LC-BLYP functional (ω CC ) for the set of 60 molecules. Our new tuned range-separated functional, Tα-LC-BLYP, uses a quadratic correlation between ω CC and a molecular descriptor in terms of the linear polarizability and the number of electrons in the molecule. The average error of the γ values obtained with Tα-LC-BLYP is reduced by half or more as compared with the most accurate among the nine density functional approximations benchmarked.

Following our study on hydrogen-bonded (HB) complexes [Phys. Chem. Chem. Phys., 2018, 20, 19841], the physical nature of interaction-induced (non)linear optical properties of another important class of molecular complexes, namely halogen-bonded (XB) systems, was analyzed in this study. The excess electronic and nuclear relaxation (hyper)polarizabilities of nine representative XB complexes covering a wide range of halogen-bond strengths were computed. The partitioning of the excess properties into individual interaction-energy components (electrostatic, exchange, induction, dispersion) was performed by using the variational-perturbational energy decomposition scheme at the MP2/aug-cc-pVTZ level of theory and further supported by calculations with the SCS-MP2 method. In the case of the electronic interaction-induced properties, the physical composition of Δαel and Δγel was found to be very similar for the two types of bonding, despite the different nature of the binding. For Δβel, the XB complexes exhibit a more systematic interplay of interaction-energy contributions compared to the HB systems studied in the previous work. Our analysis revealed that the patterns of interaction-energy contributions to the interaction-induced nuclear-relaxation contributions to the linear polarizability and the first hyperpolarizability are very similar. For both properties the exchange repulsion term is canceled out by the electrostatic and delocalization terms. The physical composition of these contributions is analogous to those observed for the HB complexes.

A mechanistic understanding of electro- and photocatalytic CO 2 reduction is crucial to develop strategies to overcome catalytic bottlenecks. In this regard, for a new CO 2 -to-CO reduction cobalt aminopyridine catalyst, a detailed experimental and theoretical mechanistic study is herein presented toward the identification of bottlenecks and potential strategies to alleviate them. The combination of electrochemistry and in situ spectroelectrochemistry together with spectroscopic techniques led us to identify elusive key electrocatalytic intermediates derived from complex [L N4 Co(OTf) 2 ] ( 1 ) (L N4 = 1-[2-pyridylmethyl]-4,7-dimethyl-1,4,7-triazacyclononane) such as a highly reactive cobalt(I) ( 1 (I) ) and a cobalt(I) carbonyl ( 1 (I) -CO ) species. The combination of spectroelectrochemical studies under CO 2 , 13 CO 2 , and CO with DFT disclosed that 1 (I) reacts with CO 2 to form the pivotal 1 (I) -CO intermediate at the 1 (II/I) redox potential. However, at this reduction potential, the formation of 1 (I) -CO restricts the electrocatalysis due to the endergonicity of the CO release step. In agreement with the experimentally observed CO 2 -to-CO electrocatalysis at the Co I/0 redox potential, computational studies suggested that the electrocatalytic cycle involves striking metal carbonyls. In contrast, under photochemical conditions, the catalysis smoothly proceeds at the 1 (II/I) redox potential. Under the latter conditions, it is proposed that the electron transfer to form 1 (I) -CO from 1 (II) -CO is under diffusion control. Then, the CO release from 1 (II) -CO is kinetically favored, facilitating the catalysis. Finally, we have found that visible-light irradiation has a positive impact under electrocatalytic conditions. We envision that light irradiation can serve as an effective strategy to circumvent the CO poisoning and improve the performance of CO 2 reduction molecular catalysts.

CMWs (coal mine wastes) as the waste products of coal exploitation or washing plants are a source of pollution that generates waste management problems, especially those that are very old and without a known owner. CMW chemical composition indicates that it contains SiO 2 -Al 2 O 3 -Fe 2 O 3 in such percentages that it can be used in the production of Portland cement clinker, which can lead to potential savings in clinker production, not only in raw material but also in fuels if the CMW has a minimum calorific value and has not suffered self-combustion. After characterization of different CMWs from mining sites located in the north of Spain, six types of CMW have been selected and different raw meal formulations have been designed by software, maximizing the substitution rate of CMW and ensuring a correct raw meal chemical parameters. Along with a reference raw meal, all CMW clinkers were sintered, ground with gypsum, and tested determining the setting time, compressive strength, and soundness. The results of the physico-mechanical tests show that the mechanical performance of the CMW cements was consistent with the European requirements for a CEM Type I cement. CMW, especially those with a residual energetic content, can be utilized in clinker raw meal due to its availability in large quantities at low cost with the further significant benefits for waste management and environmental practices in mining and in cement production processes.

Biocontrol using non-aflatoxigenic strains of Aspergillus flavus has the greatest potential to mitigate aflatoxin contamination in agricultural produce. However, factors that influence the efficacy of biocontrol agents in reducing aflatoxin accumulation under field conditions are not well-understood. Shifts in the genetic structure of indigenous soil populations of A. flavus following application of biocontrol products Afla-Guard and AF36 were investigated to determine how these changes can influence the efficacy of biocontrol strains in reducing aflatoxin contamination. Soil samples were collected from maize fields in Alabama, Georgia, and North Carolina in 2012 and 2013 to determine changes in the population genetic structure of A. flavus in the soil following application of the biocontrol strains. A. flavus L was the most dominant species of Aspergillus section Flavi with a frequency ranging from 61 to 100%, followed by Aspergillus parasiticus that had a frequency of <35%. The frequency of A. flavus L increased, while that of A. parasiticus decreased after application of biocontrol strains. A total of 112 multilocus haplotypes (MLHs) were inferred from 1,282 isolates of A. flavus L using multilocus sequence typing of the trpC, mfs , and AF17 loci. A. flavus individuals belonging to the Afla-Guard MLH in the IB lineage were the most dominant before and after application of biocontrol strains, while individuals of the AF36 MLH in the IC lineage were either recovered in very low frequencies or not recovered at harvest. There were no significant ( P > 0.05) differences in the frequency of individuals with MAT1-1 and MAT1-2 for clone-corrected MLH data, an indication of a recombining population resulting from sexual reproduction. Population mean mutation rates were not different across temporal and spatial scales indicating that mutation alone is not a driving force in observed multilocus sequence diversity. Clustering based on principal component analysis identified two distinct evolutionary lineages (IB and IC) across all three states. Additionally, patristic distance analysis revealed phylogenetic incongruency among single locus phylogenies which suggests ongoing genetic exchange and recombination. Levels of aflatoxin accumulation were very low except in North Carolina in 2012, where aflatoxin levels were significantly ( P < 0.05) lower in grain from treated compared to untreated plots. Phylogenetic analysis showed that Afla-Guard was more effective than AF36 in shifting the indigenous soil populations of A. flavus toward the non-toxigenic or low aflatoxin producing IB lineage. These results suggest that Afla-Guard, which matches the genetic and ecological structure of indigenous soil populations of A. flavus in Alabama, Georgia, and North Carolina, is likely to be more effective in reducing aflatoxin accumulation and will also persist longer in the soil than AF36 in the southeastern United States.

Nonlinear optical properties (NLOPs) play a major role in photonics, electro-optics and optoelectronics, and other fields of modern optics. The design of new NLO molecules and materials has benefited from the development of computational tools to analyze the relationship between the electronic structure of molecules and their optical response. In this paper, we present a new means to analyze the response property through the partition of NLOPs in terms of orbital contributions (PNOC). This tool can be used to obtain a real-space representation of the NLOPs, providing a powerful visualization aid to connect the magnitude of the optical property with some parts of the molecule. Unlike other methods to analyze NLOPs, the PNOC decomposes the optical property into orbitals of the unperturbed system, furnishing this method with the ability to assess the performance of single- and multi-determinant electronic structure methods. PNOC can be also used to design small basis sets for an accurate description of large systems, saving a substantial amount of computer time for the calculation of optical properties.

This work reports on an extensive assessment of the performance of a wide palette of density functional approximations in predicting the (high-order) electric properties of hydrogen-bonded complexes. To this end, we compute the electronic and vibrational contributions to the electric polarizability and the first and second hyperpolarizabilities, using the CCSD(T)/aug-cc-pVTZ level of theory as reference. For all the studied properties, the average absolute errors below 20% can only be obtained using the CAM-B3LYP functional, while LC-BLYP and MN15 are shown to be only slightly less accurate (average absolute errors not exceeding 30%). Among Minnesota density functionals, i.e., M06, M06-2X, and MN15, we only recommend the latter one, which quite accurately predicts the electronic and vibrational (hyper)polarizabilities. We also analyze the optimal tuning of the range-separation parameter μ for the LC-BLYP functional, finding that this approach does not bring any systematic improvement in the predictions of electronic and vibrational (hyper)polarizabilities and the accuracy of computed properties is largely system-dependent. Finally, we report huge errors in predicting the vibrational second hyperpolarizability by ωB97X, M06, and M06-2X functionals. Based on the explicit evaluation of anharmonic terms contributing to the second hyperpolarizability, this failure is traced down to a poor determination of third- and fourth-order energy derivatives with respect to normal modes. These results reveal serious flaws of some density functional approximations and suggest caution in selecting the appropriate functional to calculate not only electronic and vibrational (hyper)polarizabilities but also other molecular properties that contain vibrational anharmonic contributions.

The nature of the oxidizing species in water oxidation reactions with chemical oxidants catalyzed by α-[Fe(OTf) 2 (mcp)] (1α; mcp = N, N'-dimethyl- N, N'-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine, OTf = trifluoromethanesulfonate anion) and β-[Fe(OTf) 2 (mcp)] (1β) has been investigated. Mössbauer spectroscopy provides definitive evidence that 1α and 1β generate oxoiron(IV) species as the resting state. Decomposition paths of the catalysts have been investigated by identifying and quantifying ligand fragments that form upon degradation. This analysis correlates the water oxidation activity of 1α and 1β with stability against oxidative damage of the ligand via aliphatic C-H oxidation. The site of degradation and the relative stability against oxidative degradation are shown to be dependent on the topology of the catalyst. Furthermore, the mechanisms of catalyst degradation have been rationalized by computational analyses, which also explain why the topology of the catalyst enforces different oxidation-sensitive sites. This information has served in creating catalysts where sensitive C-H bonds have been replaced by C-D bonds. The deuterated analogues D 4 -α-[Fe(OTf) 2 (mcp)] (D 4 -1α), D 4 -β-[Fe(OTf) 2 (mcp)] (D 4 -1β), and D 6 -β-[Fe(OTf) 2 (mcp)] (D 6 -1β) were prepared, and their catalytic activity has been studied. D 4 -1α proves to be an extraordinarily active and efficient catalyst (up to 91% of O 2 yield); it exhibits initial reaction rates identical with those of its protio analogue, but it is substantially more robust toward oxidative degradation and yields more than 3400 TON ( n(O 2 )/ n(Fe)). Altogether this evidences that the water oxidation catalytic activity is performed by a well-defined coordination complex and not by iron oxides formed after oxidative degradation of the ligands.

The IUPAC has recently clarified the term oxidation state (OS), and provided algorithms for its determination based on the ionic approximation (IA) of the bonds supported by atomic electronegativities (EN). Unfortunately, there are a number of exceptions and ambiguities in IUPAC's algorithms when it comes to practical applications. Our comprehensive study reveals the critical role of the chemical environment on establishing the OS, which cannot always be properly predicted using fix atomic EN values. By identifying what we define here as subsystems of enhanced stability within the molecular system, the OS can be safely assigned in many cases without invoking exceptions. New insights about the effect of local aromaticity upon OS are revealed. Moreover, we prove that there are intrinsic limitations of the IA that cannot be overcome. In this context, the effective oxidation state (EOS) analysis arises as a robust and general scheme to derive an OS without any external guidance., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Understanding the effects of different fundamental intermolecular interactions on nonlinear optical properties is crucial for proposing efficient strategies to obtain new materials with tailored properties. In this study, we computed the electronic and vibrational (hyper)polarizabilities of ten hydrogen-bonded molecular complexes employing the MP2, CCSD and CCSD(T) methods combined with the aug-cc-pVTZ basis set. The vibrational contributions to hyperpolarizabilities included nuclear-relaxation anharmonic corrections. The effect of intermolecular interactions was analyzed in terms of excess properties, which are defined as the difference between a property of the complex and the net properties of the noninteracting subsystems. Considering systems covering a wide range of hydrogen bond strengths, the electronic and vibrational excess (hyper)polarizabilities were decomposed into different interaction energy contributions (electrostatic, exchange, induction and dispersion). This systematic study, the very first of this kind, revealed that the physical origins of the electronic and vibrational excess properties are completely different. In the case of vibrational contributions, the decomposition pattern is very similar for the polarizability and first and second hyperpolarizabilities. The exchange contributions to excess vibrational properties are the largest and they have an opposite sign to the electrostatic, induction and dispersion terms. On the other hand, no general patterns can be established for the electronic excess properties.

Electrides are ionic substances containing isolated electrons. These confined electrons are topologically characterised by a quasi-atom, that is, a non-nuclear attractor (NNA) of the electron density. The electronic structure of the octahedral 4 A 1g Li 6 + and 5 A 1g Be 6 species shows that these species have a large number of NNAs. These NNAs have highly delocalised electron densities and, as a result, the chemical bonding pattern of these systems is reminiscent of that in solid metals, in which metal cations are surrounded by a "sea" of delocalised valence electrons. We propose the term metal cluster electrides to refer to this new class of compounds. In this study, we establish a computational protocol to identify, characterize, and design metal cluster electrides and we elucidate the intricate bonding patterns of this particular type of species., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The cytochromes P450 are drug metabolizing enzymes in the body that typically react with substrates through a monoxygenation reaction. During the catalytic cycle two reduction and protonation steps generate a high-valent iron (IV)-oxo heme cation radical species called Compound I. However, with sufficient reduction equivalents present, the catalytic cycle should be able to continue to the reduced species of Compound I, called Compound II, rather than a reaction of Compound I with substrate. In particular, since electron transfer is usually on faster timescales than atom transfer, we considered this process feasible and decided to investigate the reaction computationally. In this work we present a computational study using density functional theory methods on active site model complexes alongside quantum mechanics/molecular mechanics calculations on full enzyme structures of cytochrome P450 enzymes. Specifically, we focus on the relative reactivity of Compound I and II with a model substrate for O⁻H bond activation. We show that generally the barrier heights for hydrogen atom abstraction are higher in energy for Compound II than Compound I for O⁻H bond activation. Nevertheless, for the activation of such bonds, Compound II should still be an active oxidant under enzymatic conditions. As such, our computational modelling predicts that under high-reduction environments the cytochromes P450 can react with substrates via Compound II but the rates will be much slower.