Relation between structure and enthalpy for stacking interactions of aromatic molecules

An approximately linear correlation has been found between the enthalpy of complexation and the area of overlap of the chromophores using published structural and thermodynamical data on the self- and hetero-association of aromatic molecules measured under similar solution conditions. This finding is consistent with the assumption that short-range van-der-Waals forces dominate over other contributions to the enthalpy of stacking of aromatic molecules. It provides a ‘model-independent’ approach for a priori estimation of the enthalpy of aromatic–aromatic stacking interactions from knowledge of the structural properties or vice versa.     

UV/Vis absorption spectroelectrochemistry of folic acid

Journal of Solid State Electrochemistry - UV/Vis absorption spectroelectrochemistry is a very promising analytical technique due to the complementary information that is simultaneously obtained...     

DMT1 Inhibitors Kill Cancer Stem Cells by Blocking Lysosomal Iron Translocation

Cancer stem cells (CSC) constitute a cell subpopulation in solid tumors that is responsible for resistance to conventional chemotherapy, metastasis and cancer relapse. The natural product Salinomycin can selectively target this cell niche by directly interacting with lysosomal iron, taking advantage of upregulated iron homeostasis in CSC. Here, inhibitors of the divalent metal transporter 1 (DMT1) have been identified that selectively target CSC by blocking lysosomal iron translocation. This leads to lysosomal iron accumulation, production of reactive oxygen species and cell death with features of ferroptosis. DMT1 inhibitors selectively target CSC in primary cancer cells and circulating tumor cells, demonstrating the physiological relevance of this strategy. Taken together, this opens up opportunities to tackle unmet needs in anti-cancer therapy.     

Optical Spectroscopy as a Method for Skin Cancer Risk Assessment

Skin cancer is the most prevalent cancer, and its assessment remains a challenge for physicians. This study reports the application of an optical sensing method, elastic scattering spectroscopy (ESS), coupled with a classifier that was developed with machine learning, to assist in the discrimination of skin lesions that are concerning for malignancy. The method requires no special skin preparation, is non‐invasive, easy to administer with minimal training, and allows rapid lesion classification. This novel approach was tested for all common forms of skin cancer. ESS spectra from a total of 1307 lesions were analyzed in a multi‐center, non‐randomized clinical trial. The classification algorithm was developed on a 950‐lesion training dataset, and its diagnostic performance was evaluated against a 357‐lesion testing dataset that was independent of the training dataset. The observed sensitivity was 100% (14/14) for melanoma and 94% (105/112) for non‐melanoma skin cancer. The overall observed specificity was 36% (84/231). ESS has potential, as an adjunctive assessment tool, to assist physicians to differentiate between common benign and malignant skin lesions.     

Nonlinear Boundary Value Problems on Sequence Spaces

In this paper we study the solvability of nonlinear, discrete-time boundary value problems for functional equations. Conditions are established for the existence of solutions to problems of the form $$x(k + 1) = f(k, x(k)) + \lambda g(k, x(k)); \quad k = 0, 1, 2, \ldots$$     

Transfection of Mammalian Cells Using Block Copolypeptide Vesicles

An arginine‐leucine block copolypeptide (R₆₀L₂₀) is synthesized, which is capable of forming vesicles with controllable sizes, able to transport hydrophilic cargo across the cell membrane, and exhibit relatively low cytotoxicity. The R₆₀L₂₀ vesicles also possess the ability to deliver DNA into mammalian cells for transfection. Although the transfection efficiency is lower than that of the commercially available transfection agent Lipofectamine 2000, the R₆₀L₂₀ vesicles are able to achieve transfection with significantly lower cytotoxicity and immunogenicity. This behavior is potentially due to its stronger interaction with DNA which subsequently provides better protection against anionic heparin.

     

A mixed chloride/trifluoromethanesulfonate ligand species in a ruthenium(II) complex

The compound [2‐(aminomethyl)pyridine‐κ²N,N′][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11‐η)‐5H‐dibenzo[a,d]cyclohepten‐5‐amine‐κN](triphenylphosphane‐κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91‐solvate, [Ru(CF₃SO₃)_0.09Cl_0.91(C₆H₈N₂)(C₁₅H₁₃N)(C₁₈H₁₅P)]CF₃SO₃·0.91CH₂Cl₂, belongs to a series of Ru^II complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [Ru^II(OTf)(ampy)(η²‐tropNH₂)(PPh₃)]OTf, where OTf is triflate or trifluoromethanesulfonate, ampy is 2‐(aminomethyl)pyridine and tropNH₂ is 5H‐dibenzo[a,d]cyclohepten‐5‐amine.     

Studies of Nucleophilic Substitution Reactions of p‐Nitrophenyl Acetate with Some Dihydroxamate Ions in Cationic Micellar Media

Pseudo‐first‐order rate constants have been determined for the nucleophilic substitution reactions of p‐nitrophenyl acetate with oxalo, malono, and succinodihydroxamate ions (^?ONHC(O)(CH₂)_nC(O)NHO^?) in phosphate buffer (pH=7.9) at 27°C. The rate data of the reaction revealed that the nucleophilic reactivity sequence of these hydroxamate ions is generally ODHA>MDHA>SDHA. The k_obs value increases upon addition of cationic surfactants to the reaction medium which is typical behavior of micelle‐assisted bimolecular reactions. The pseudo‐phase ion exchange model has been successfully applied to determine binding constant.