Crystal structures of 3/4-pyridyl-based thiosemicarbazones and related Cu and Ni coordination compounds

In this investigation, the crystal structures of the thio-ligands 3-formylpyridine 4-phenylthiosemicarbazone (C13H12N4S, 1) and 4-benzoylpyridine 4-ethylthiosemicarbazone (C15H16N4S, 2), and of two new coordination compounds, chlorido(3-formylpyridine 4-phenylthiosemicarbazone-κS)bis(triphenylphosphane-κP)copper(I) acetonitrile monosolvate, [CuCl(C13H12N4S)(C18H15P)2]·CH3CN, 3, and bis(3-formylpyridine 4-ethylthiosemicarbazonato-κ2 N 1,S)nickel(II), [Ni(C9H11N4S)2], 4, are reported. In complex 3, the thio-ligand coordinates in a neutral form to the Cu atom through its S-donor atom, and in complex 4, the anionic thio-ligand chelates to the Ni atom through N- and S-donor atoms. The geometry of complex 3 is distorted tetrahedral [bond angles 99.70 (5)–123.23 (5)°], with the P—Cu—P bond angle being the largest, while that of complex 4 is square planar, with trans-S—Ni—S and N—Ni—N bond angles of 180°.

Synthesis, IR spectroscopic and structural studies of erbium and nickel complexes with N,N'-tetraethyl-N''-trifluoroacetylphosphoroustriamide

A synthesis procedure was developed and a new carbacylamidophosphate type ligand N,N'-tetraethyl-N''-trifluoroacetylphosphoroustriamide (CF3C(O)NHP(O)(NC2H5)2, HL) that contains C(O)NP(O) chelating fragment was isolated in the crystalline state. A mononuclear erbium complex [Er(HL)3(NO3)3] and a tetranuclear nickel complex [Ni4L4(OCH3)4(CH3OH)4] were isolated in the crystalline state. The suggestion about the type and coordination mode of the ligand in complexes was made based on IR spectroscopic investigations: deprotonated (acido-) form in bidentate manner in nickel complex and neutral form in monodentate manner in erbium complex. According to X-ray structural studies, different coordination modes of the ligand in complexes were determined: bidentate chelate manner via the oxygen atoms of the phosphoryl and carbonyl groups of the ligand with the formation of six-membered chelate cycles in case of nickel complex and monodentate manner via the oxygen atom of the phosphoryl group of the ligand in case of erbium complex, the coordination polyhedron of which was interpreted as a distorted three-handed trigonal prism.

How Online Education May Disadvantage Students from Some Cultures and What to Do About It in the Theology Classroom

Distance or online learning is not a culturally neutral form of learning, but, like any educational approach, has been and continues to be shaped by significant historical and cultural forces. Not just what is taught, but also the means by which it is taught – the technological medium of online education – is influenced by culture and should be adjusted accordingly. With illustrations and examples pulled from the author’s experience of teaching theology in both Africa and the United States, this essay explores four “dimensions of culture” – collectivist vs. individualist, high vs. low power distance, high- vs. low-context, and oral vs. literate preference – and analyzes how students from more collectivistic, high power distance, high-context, and oral preference societies may be disadvantaged by commonly used and accepted approaches to distance/online learning. It concludes by offering some practical suggestions for adjusting online theological education to be more culturally responsive.

Synthesis of Novel Heteroleptic Oxothiolate Ni(II) Complexes and Evaluation of Their Catalytic Activity for Hydrogen Evolution

Two heteroleptic nickel oxothiolate complexes, namely [Ni(bpy)(mp)] (1) and [Ni(dmbpy)(mp)] (2), where mp = 2-hydroxythiophenol, bpy = 2,2′-bipyridine and dmbpy = 4,4′-dimethyl-2,2′-bipyridine were synthesized and characterized with various physical and spectroscopic methods. Complex 2 was further characterized by single crystal X-ray diffraction data. The complex crystallizes in the monoclinic P 21/c system and in its neutral form. The catalytic properties of both complexes for proton reduction were evaluated with photochemical and electrochemical studies. Two different in their nature photosensitizers, namely fluorescein and CdTe-TGA-coated quantum dots, were tested under various conditions. The role of the electron donating character of the methyl substituents was revealed in the light of the studies. Thus, catalyst 2 performs better than 1, reaching 39.1 TONs vs. 4.63 TONs in 3 h, respectively, in electrochemical experiments. In contrast, complex 1 is more photocatalytically active than 2, achieving a TON of over 6700 in 120 h of irradiation. This observed reverse catalytic activity suggests that HER mechanism follows different pathways in electrocatalysis and photocatalysis.

Cannabis Yield Increased Proportionally With Light Intensity, but Additional Ultraviolet Radiation Did Not Affect Yield or Cannabinoid Content

Cannabis (Cannabis Sativa L.) is now legally produced in many regions worldwide. Cannabis flourishes under high light intensities (LI); making it an expensive commodity to grow in controlled environments, despite its exceptionally high market value. It is commonly believed that cannabis secondary metabolite levels may be enhanced both by increasing LI and by exposing crops to ultraviolet radiation (UV). However, there is sparse scientific evidence to guide cultivators. Therefore, the impact of LI and UV on yield and quality must be elucidated to enable cultivators to optimize their lighting protocols. We explored the effects of LI, ranging from 350 to 1400 μmol m-2 s-1 and supplemental UV spectra on cannabis yield and potency. There were no spectrum effects on inflorescence yield, but harvest index under UVA+UVB was reduced slightly (1.6%) vs. the control. Inflorescence yield increased linearly from 19.4 to 57.4 g/plant and harvest index increased from 0.565 to 0.627, as LI increased from 350 to 1400 μmol m-2 s-1. Although there were no UV spectrum effects on total equivalent Δ9-tetrahydrocannabinol (T-THC) content in leaves, the neutral form, THC, was 30% higher in UVA+UVB vs. control. While there were no LI effects on inflorescence T-THC content, the content of the acid form (THCA) increased by 20% and total terpenes content decreased by 20% as LI increased from 350 to 1400 μmol m-2 s-1. High LI can substantially increase cannabis yield and quality, but we found no commercially-relevant benefits of adding supplemental UV radiation to indoor cannabis production.

Two-Dimensional Conjugated Covalent Organic Framework Films via Oxidative C–C Coupling Reactions at a Liquid–Liquid Interface

The construction of conjugated covalent organic frameworks (COFs) with strong C–C bond linkage remains a big challenge. Herein, we report a new strategy by using an oxidative C–C coupling reaction between electron-rich pyrrole rings at a liquid–liquid interface. Two threefold symmetric monomers containing three terminal pyrrole units were tested, and both gave two-dimensional conjugated COF films with good crystallinity. The bipyrrole units in the as-formed COFs are partially doped, which can be reduced to the neutral form by hydrazine and redoped by I2 vapor. The I2-doped films showed high conductivity (1.35 S/m). Meanwhile, the unpaired electrons exhibited moderate interlayer antiferromagnetic coupling.

Prospects for the use of calcium ammonium nitrate on acidic soils of the Non-Black Earth Area

The results of the effectiveness of the application of calcium ammonium nitrate (CAN) in winter wheat crops of the “Moskovskaya-39” variety on the dark-gray forest, heavy-loamy soil in the Ryazan region is presented. The advantage of CAN-a a universal form of nitrogen fertilizer, which has a neutral reaction and creates optimal conditions for feeding plants with nitrogen in the zone of its application, where the main mass of plant roots is located, is revealed. Along with nitrogen, fertilizer contains calcium and magnesium, which are essential for the formation of winter wheat productivity, the exchange of carbohydrates and proteins. In the field experience with winter wheat on soils not saturated with bases, the results were obtained, indicating the effectiveness of a physiologically neutral form of nitrogen fertilizer, which showed an advantage over physiologically acidic fertilizer - ammonia nitrate. Dynamics of the formation of the productivity of sowing showed that the area of leaves reached the maximum sizes by the flowering phase of 61.6-76.6 cm2/plant, the largest value of the indicator 76.6 cm2/plant was in the variant with the use of CAN feeding at a dose of 54 kg/ha of nitrogen. The use of CAN provided a reliable increase in the harvest of winter wheat grain in comparison with ammonium nitrate. The grain harvest in the experiment was 63.7 - 67.1 cents per hectare, statistically close were the values of yield in variants using CAN in doses of 68 and 54 kg/ha of nitrogen, the increase in the harvest was 3.8-5.3% respectively. The creation of optimal conditions for winter wheat during the growing season was accompanied by an improvement in the quality of the grain, in comparison with the variant with the use of ammonium nitrate.

Formation of interstellar cyanoacetamide: a rotational and computational study

Context. Cyanoacetamide is a –CN bearing molecule that is also an amide derivative target molecule in the interstellar medium. Aims. The aim of our investigation is to analyze the feasibility of a plausible formation process of protonated cyanoacetamide under interstellar conditions and to provide direct experimental frequencies of the ground vibrational state of the neutral form in the microwave region in order to enable its eventual identification in the interstellar medium. Methods. We used high-level theoretical computations to study the formation process of protonated cyanoacetamide. Furthermore, we employed a high-resolution laser-ablation molecular beam Fourier transform spectroscopic technique to measure the frequencies of the neutral form. Results. We report the first rotational characterization of cyanoacetamide, and a precise set of the relevant rotational spectroscopic constants have been determined as a first step to identifying the molecule in the interstellar medium. We fully explored the potential energy surface to study a gas-phase reaction on the formation process of protonated cyanoacetamide. We found that an exothermic process with no net activation barrier is initiated by the high-energy isomer of protonated hydroxylamine, which leads to protonated cyanoacetamide.

The Sword in the Soul

This chapter focuses on how youth diagnosed with Asperger’s syndrome and related autism spectrum conditions make sense of their own condition and its contradictions. Drawing on clinical ethnography in spaces where youth on the spectrum engage in shared creative practices, the chapter argues that medicalized discourses of autism as either a pathogen-like disease or a value-neutral form of neurogenetic hardwiring are insufficient to conceptualize the experiences of these youth. Autism, as they describe it, feels both intimate and alien, brings both cherished strength and terrifying vulnerability, and constitutes their sense of identity while also profoundly disrupting it. But the dominant ways of talking about autism, grounded in medical understandings of the self as sharply bounded and continuous, separate these aspects of lived experience from each other, casting them as radically incompatible. Instead, these youth playfully reinvent their autobiographies through an alternative shared mythology of mutant antiheroes with permeable selves, drawn from fantasy media, video games, comic books and other speculative fiction. In doing so, they generate new ways of coming to terms with the complexities of their condition.

The Neutrally Charged Diarylurea Compound PQ401 Kills Antibiotic-Resistant and Antibiotic-Tolerant Staphylococcus aureus

ABSTRACT Resistance or tolerance to traditional antibiotics is a challenging issue in antimicrobial chemotherapy. Moreover, traditional bactericidal antibiotics kill only actively growing bacterial cells, whereas nongrowing metabolically inactive cells are tolerant to and therefore “persist” in the presence of legacy antibiotics. Here, we report that the diarylurea derivative PQ401, previously characterized as an inhibitor of the insulin-like growth factor I receptor, kills both antibiotic-resistant and nongrowing antibiotic-tolerant methicillin-resistant Staphylococcus aureus (MRSA) by lipid bilayer disruption. PQ401 showed several beneficial properties as an antimicrobial lead compound, including rapid killing kinetics, low probability for resistance development, high selectivity to bacterial membranes compared to mammalian membranes, and synergism with gentamicin. In contrast to well-studied membrane-disrupting cationic antimicrobial low-molecular-weight compounds and peptides, molecular dynamic simulations supported by efficacy data demonstrate that the neutral form of PQ401 penetrates and subsequently embeds into bacterial lipid bilayers more effectively than the cationic form. Lastly, PQ401 showed efficacy in both the Caenorhabditis elegans and Galleria mellonella models of MRSA infection. These data suggest that PQ401 may be a lead candidate for repurposing as a membrane-active antimicrobial and has potential for further development as a human antibacterial therapeutic for difficult-to-treat infections caused by both drug-resistant and -tolerant S. aureus. IMPORTANCE Membrane-damaging antimicrobial agents have great potential to treat multidrug-resistant or multidrug-tolerant bacteria against which conventional antibiotics are not effective. However, their therapeutic applications are often hampered due to their low selectivity to bacterial over mammalian membranes or their potential for cross-resistance to a broad spectrum of cationic membrane-active antimicrobial agents. We discovered that the diarylurea derivative compound PQ401 has antimicrobial potency against multidrug-resistant and multidrug-tolerant Staphylococcus aureus. PQ401 selectively disrupts bacterial membrane lipid bilayers in comparison to mammalian membranes. Unlike cationic membrane-active antimicrobials, the neutral form of PQ401 rather than its cationic form exhibits maximum membrane activity. Overall, our results demonstrate that PQ401 could be a promising lead compound that overcomes the current limitations of membrane selectivity and cross-resistance. Also, this work provides deeper insight into the design and development of new noncharged membrane-targeting therapeutics to combat hard-to-cure bacterial infections.