On the reactions of methyl radicals with nitrilotris(methylenephosphonic-acid) complexes in aqueous solutions

Abstract

The reactions of methyl radicals with M^II-(ntp)(H₂O)₂ complexes were studied. The formation of an unstable intermediate (ntp)(H₂O)M^III-CH₃ is observed. This reaction is an equilibrium process, i.e. the M^III-C bond decomposes via homolysis. The (ntp)(H₂O)M^III-CH₃ complexes isomerize to a more stable form. The results compared to those obtained in analogous reactions of the M^II-(nta)(H₂O)₂ complexes were shown to be similar with one exception – for the nta complexes no isomerization process is observed.     

Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications

Although the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six-coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potential for practical applications based on click chemistry, optical imaging, and surface science.     

CLT for Random Walks of Commuting Endomorphisms on Compact Abelian Groups

Let \(\mathcal S\) be an abelian group of automorphisms of a probability space \((X, {\mathcal A}, \mu )\) with a finite system of generators \((A_1, \ldots , A_d).\) Let \(A^{{\underline{\ell }}}\) denote \(A_1^{\ell _1} \ldots A_d^{\ell _d}\), for \({{\underline{\ell }}}= (\ell _1, \ldots , \ell _d).\) If \((Z_k)\) is a random walk on \({\mathbb {Z}}^d\), one can study the asymptotic distribution of the sums \(\sum _{k=0}^{n-1} \, f \circ A^{\,{Z_k(\omega )}}\) and \(\sum _{{\underline{\ell }}\in {\mathbb {Z}}^d} {\mathbb {P}}(Z_n= {\underline{\ell }}) \, A^{\underline{\ell }}f\), for a function f on X. In particular, given a random walk on commuting matrices in \(SL(\rho , {\mathbb {Z}})\) or in \({\mathcal M}^*(\rho , {\mathbb {Z}})\) acting on the torus \({\mathbb {T}}^\rho \), \(\rho \ge 1\), what is the asymptotic distribution of the associated ergodic sums along the random walk for a smooth function on \({\mathbb {T}}^\rho \) after normalization? In this paper, we prove a central limit theorem when X is a compact abelian connected group G endowed with its Haar measure (e.g., a torus or a connected extension of a torus), \(\mathcal S\) a totally ergodic d-dimensional group of commuting algebraic automorphisms of G and f a regular function on G. The proof is based on the cumulant method and on preliminary results on random walks.     

Cannabis-Derived Compounds Cannabichromene and Δ9-Tetrahydrocannabinol Interact and Exhibit Cytotoxic Activity against Urothelial Cell Carcinoma Correlated with Inhibition of Cell Migration and Cytoskeleton Organization

Cannabis sativa contains more than 500 constituents, yet the anticancer properties of the vast majority of cannabis compounds remains unknown. We aimed to identify cannabis compounds and their combinations presenting cytotoxicity against bladder urothelial carcinoma (UC), the most common urinary system cancer. An XTT assay was used to determine cytotoxic activity of C. sativa extracts on T24 and HBT-9 cell lines. Extract chemical content was identified by high-performance liquid chromatography (HPLC). Fluorescence-activated cell sorting (FACS) was used to determine apoptosis and cell cycle, using stained F-actin and nuclei. Scratch and transwell assays were used to determine cell migration and invasion, respectively. Gene expression was determined by quantitative Polymerase chain reaction (PCR). The most active decarboxylated extract fraction (F7) of high-cannabidiol (CBD) C. sativa was found to contain cannabichromene (CBC) and Δ9-tetrahydrocannabinol (THC). Synergistic interaction was demonstrated between CBC + THC whereas cannabinoid receptor (CB) type 1 and type 2 inverse agonists reduced cytotoxic activity. Treatments with CBC + THC or CBD led to cell cycle arrest and cell apoptosis. CBC + THC or CBD treatments inhibited cell migration and affected F-actin integrity. Identification of active plant ingredients (API) from cannabis that induce apoptosis and affect cell migration in UC cell lines forms a basis for pre-clinical trials for UC treatment.     

Adsorption-Inhibition of Clathrate Hydrates by Self-Assembled Nanostructures

The mechanism by which safranine O (SFO), an ice growth inhibitor, halts the growth of single crystal tetrahydrofuran (THF) clathrate hydrates was explored using microfluidics coupled with cold stages and fluorescence microscopy. THF hydrates grown in SFO solutions exhibited morphology changes and were shaped as truncated octahedrons or hexagons. Fluorescence microscopy and microfluidics demonstrated that SFO binds to the surface of THF hydrates on specific crystal planes. Cryo-TEM experiments of aqueous solutions containing millimolar concentrations of SFO exhibited the formation of bilayered lamellae with an average thickness of 4.2±0.2 nm covering several μm². Altogether, these results indicate that SFO forms supramolecular lamellae in solution, which might bind to the surface of the hydrate and inhibit further growth. As an ice and hydrate inhibitor, SFO may bind to the surface of these crystals via ordered water molecules near its amine and methyl groups, similar to some antifreeze proteins.     

Aggregation Mode,Host-Guest Chemistry in Water,and Extraction Capability of an Uncharged,Water-Soluble,Liquid Pillar[5]arene Derivative

An uncharged, water-soluble per-ethylene-glycol pillar[5]arene derivative ( 1 ) was synthesized and its aggregation mode, host-guest chemistry in water and extraction ability was explored. Compound 1 is a liquid at room temperature; in water, limited self-aggregation occurred at high concentrations as deduced from diffusion NMR and dynamic light scattering. Compound 1 forms pseudo-rotaxane-like 1 : 1 host-guest complexes with 1,ω-di-substituted alkanes with association constants on the order of 10³–10⁴ m ⁻¹. Interestingly, NMR experiments showed that the guest location relative to the host ring system differs among the different complexes. In proof-of-concept experiments, compound 1 was shown to extract structurally related organic compounds from benzene into water with significant selectivity. Compound 1 , which is a liquid at room temperature and has only limited interactions with its side arms, can, in principle, be regarded as a complement to or as a kind of type I porous liquid.     

Characteristics of Second Graders' Mathematical Writing

This study compared the characteristics of second graders' mathematical writing between an intervention and comparison group. Two six‐week Project M2 units were implemented with students in the intervention group. The units position students to communicate in ways similar to mathematicians, including engaging in verbal discourse where they themselves make sense of the mathematics through discussion and debate, writing about their reasoning on an ongoing basis, and utilizing mathematical vocabulary while communicating in any medium. Students in the comparison group learned from the regular school curriculum. Students in both the intervention and comparison groups conveyed high and low levels of content knowledge as indicated in archived data from an open‐response end‐of‐the‐year assessment. A multivariate analysis of variance indicated several differences favoring the intervention group. Both the high‐ and low‐level intervention subgroups outperformed the comparison group in their ability to (a) provide reasoning, (b) attempt to use formal mathematical vocabulary, and (c) correctly use formal mathematical vocabulary in their writing. The low‐level intervention subgroup also outperformed the respective comparison subgroup in their use of (a) complete sentences and (b) linking words. There were no differences between groups in their attempt at writing and attempts at and usage of informal mathematical vocabulary.