Photoluminescence and photostability investigations of biocompatible semiconductor nanocrystals coated with glutathione using low laser power

Polybutylcyanoacrylate nanoparticles (PBCA NPs) are candidates for a drug delivery system, which can cross the blood–brain barrier (BBB). Because little is known about their toxicity, we exposed cells to PBCA NPs in vitro and in vivo and monitored their life and death assays. PBCA NPs were fabricated with different surfactants according to the mini-emulsion technique. Viabilities of HeLa and HEK293 cells after NP incubation were quantified by analysing cellular metabolic activity (MTT-test). We then repetitively injected i.v. rhodamine-labelled PBCA NP variations into rats and monitored the survival and morphology of retrogradely labelled neurons by in vivo confocal neuroimaging (ICON) for five weeks. To test for carrier-efficacy and safety, PBCA NPs loaded with Kyotorphin were injected in rats, and a hot plate test was used to quantify analgesic effects. In vitro, we found dose-dependent cell death which was, however, only detectable at very high doses and mainly seen in the cultures incubated with NPs fabricated with the tensids SDS and Tween. However, the in vivo experiments did not show any NP-induced neuronal death, even with particles which were toxic at high dose in vitro, i.e. NPs with Tween and SDS. The increased pain threshold at the hot plate test demonstrated that PBCA NPs are able to cross the BBB and thus comprise a useful tool for drug delivery into the central nervous system (CNS). Our findings showing that different nanoparticle formulations are non-toxic have important implications for the value of NP engineering approaches in medicine.     

The basin boundary of the breakup channel in chaotic rearrangement scattering

Nonlinear Dynamics - We present an example of demonstration for the basin boundaries in classical rearrangement scattering with particular emphasis on the breakup channel. Whereas the basin...     

Generalizing reduction-based algebraic multigrid

Algebraic multigrid (AMG) methods are often robust and effective solvers for solving the large and sparse linear systems that arise from discretized PDEs and other problems, relying on heuristic graph algorithms to achieve their performance. Reduction-based AMG (AMGr) algorithms attempt to formalize these heuristics by providing two-level convergence bounds that depend concretely on properties of the partitioning of the given matrix into its fine- and coarse-grid degrees of freedom. MacLachlan and Saad (SISC 2007) proved that the AMGr method yields provably robust two-level convergence for symmetric and positive-definite matrices that are diagonally dominant, with a convergence factor bounded as a function of a coarsening parameter. However, when applying AMGr algorithms to matrices that are not diagonally dominant, not only do the convergence factor bounds not hold, but measured performance is notably degraded. Here, we present modifications to the classical AMGr algorithm that improve its performance on matrices that are not diagonally dominant, making use of strength of connection, sparse approximate inverse (SPAI) techniques, and interpolation truncation and rescaling, to improve robustness while maintaining control of the algorithmic costs. We present numerical results demonstrating the robustness of this approach for both classical isotropic diffusion problems and for non-diagonally dominant systems coming from anisotropic diffusion.     

Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps: Novel structure and reactivity features of chromium complexed arene diradical species

The reaction of Fischer carbene complexes with conjugated enediynes that feature a pendant alkene group has been examined. The reaction proceeds through carbene–alkyne coupling to generate an enyne–ketene intermediate. This intermediate then undergoes Moore cyclization to generate a chromium complexed arene diradical, which then undergoes cyclization with the pendant alkene group. The radical cyclization prefers the 6-endo mode unless radical-stabilizing groups are present to favor the 5-exo mode. The intermediate diradical species were evaluated computationally in both the singlet and triplet configurations. Arene triplet diradicals feature minimal spin density at oxygen and delocalization to chromium. The 6-endo cyclization product was kinetically and thermodynamically favored.     

Plant-Based Indole Alkaloids: A Comprehensive Overview from a Pharmacological Perspective

Plant-based indole alkaloids are very rich in pharmacological activities, and the indole nucleus is considered to contribute greatly to these activities. This review’s fundamental objective is to summarize the pharmacological potential of indole alkaloids that have been derived from plants and provide a detailed evaluation of their established pharmacological activities, which may contribute to identifying new lead compounds. The study was performed by searching various scientific databases, including Springer, Elsevier, ACS Publications, Taylor and Francis, Thieme, Wiley Online Library, ProQuest, MDPI, and online scientific books. A total of 100 indole compounds were identified and reviewed. The most active compounds possessed a variety of pharmacological activities, including anticancer, antibacterial, antiviral, antimalarial, antifungal, anti-inflammatory, antidepressant, analgesic, hypotensive, anticholinesterase, antiplatelet, antidiarrheal, spasmolytic, antileishmanial, lipid-lowering, antimycobacterial, and antidiabetic activities. Although some compounds have potent activity, some only have mild-to-moderate activity. The pharmacokinetic profiles of some of the identified compounds, such as brucine, mitragynine, 7-hydroxymitragynine, vindoline, and harmane, were also reviewed. Most of these compounds showed promising pharmacological activity. An in-depth pharmacological evaluation of these compounds should be performed to determine whether any of these indoles may serve as new leads.     

Longitudinal magnetic resonance imaging of spinal cord injury in mouse: changes in signal patterns associated with the inflammatory response

Contusion-type spinal cord injury (SCI) in mice was followed longitudinally using in vivo magnetic resonance (MR) imaging along with neurobehavioral tests performed on postinjury Days 1, 7, 14 and 28. Magnetic resonance images were acquired from seven injured wild-type mice using a 9.4-T scanner and presented in sagittal and axial views to reflect the current state of the injured cord neuropathology on each day. The data were analyzed individually to gain more insights on the neuroinflammatory response unique to the mouse, to characterize the spatiotemporal evolution of the lesion and to quantify the changes in lesion volume and length with time. The MR intensity patterns on Day 1 showed acute injuries as focal in one group of three mice and as diffuse in the remaining group of four mice. The focal injuries appeared as a region of hypointensity with well-defined boundaries. These injuries first enlarged on Day 7, but then shrunk slightly by Days 14 and 28. In contrast, the diffuse injuries were initially obscure on Day 1, mainly because of loss of contrast between gray and white matters. On Day 7, lesions expanded asymptotically in both rostral and caudal directions with respect to the epicenter, and maintained its size on Days 14 and 28. Previous studies based on postmortem histological analysis have reported lesions behaving more like in the focal group. However, this new injury with diffuse characteristics may have important implications for SCI research carried out with mice. Unique experiments on genetically engineered mice with altered neuroinflammatory response should help clarify the origin of these differences in the lesion formation.     

Synthesis and characterization of ruthenium heterocyclic-thiocarboxylate complexes

The cyclopentadienyl ruthenium complexes CpRuL₂SCO-het (Cp = η⁵-C₅H₅; L₂ = 2PPh₃ (1), dppe (2)) bearing heterocyclic thiocarboxylate ligands have been synthesized from the reaction of CpRuL₂SH with heterocyclic acid chlorides (ClCO-2-C₄H₃S (a); ClCO-2-C₄H₃O (b); ClCO-1-C₄H₈N (c)). Bubbling of CO gas through a THF solution of (1) produced the mixed carbonyl–phosphine complexes CpRu(PPh₃)(CO)SCO-het (3) with high yields. Complexes (1)-(3) were characterized by spectroscopic methods (i.r., ¹H-n.m.r., ³¹P-n.m.r.) and elemental analysis. The molecular structure of CpRu(PPh₃)₂SCO-2-C₄H₃S (1a) verifies that the thiocarboxylate ligands bind via the sulfur atom (Ru–S = 2.406(2) Å).     

Superparamagnetic nanoparticles for effective delivery of malaria DNA vaccine

Low efficiency is often observed in the delivery of DNA vaccines. The use of superparamagnetic nanoparticles (SPIONs) to deliver genes via magnetofection could improve transfection efficiency and target the vector to its desired locality. Here, magnetofection was used to enhance the delivery of a malaria DNA vaccine encoding Plasmodium yoelii merozoite surface protein MSP1(19) (VR1020-PyMSP1(19)) that plays a critical role in Plasmodium immunity. The plasmid DNA (pDNA) containing membrane associated 19-kDa carboxyl-terminal fragment of merozoite surface protein 1 (PyMSP1(19)) was conjugated with superparamagnetic nanoparticles coated with polyethyleneimine (PEI) polymer, with different molar ratio of PEI nitrogen to DNA phosphate. We reported the effects of SPIONs-PEI complexation pH values on the properties of the resulting particles, including their ability to condense DNA and the gene expression in vitro. By initially lowering the pH value of SPIONs-PEI complexes to 2.0, the size of the complexes decreased since PEI contained a large number of amino groups that became increasingly protonated under acidic condition, with the electrostatic repulsion inducing less aggregation. Further reaggregation was prevented when the pHs of the complexes were increased to 4.0 and 7.0, respectively, before DNA addition. SPIONs/PEI complexes at pH 4.0 showed better binding capability with PyMSP1(19) gene-containing pDNA than those at neutral pH, despite the negligible differences in the size and surface charge of the complexes. This study indicated that the ability to protect DNA molecules due to the structure of the polymer at acidic pH could help improve the transfection efficiency. The transfection efficiency of magnetic nanoparticle as carrier for malaria DNA vaccine in vitro into eukaryotic cells, as indicated via PyMSP1(19) expression, was significantly enhanced under the application of external magnetic field, while the cytotoxicity was comparable to the benchmark nonviral reagent (Lipofectamine 2000).     

A DFT study on the mono lithium and sodium salts of N-(2-hydroxyphenyl)salicylaldimine

This computational organic chemistry study presents results based on density functional theory at the B3LYP/6-31G(d) and B3LYP/cc-PVTZ//B3LYP/6-31G(d) levels of theory. Other computational procedures (HF and MP2) are presented for model structures. Three main points were investigated: some of the electronic structure aspects, the relative stability of isomers, and aromaticity. The results suggest that the title salts are the first Schiff base systems in the literature to exist only in the N-H form, which is characterized as the zwitterion form. Also, the estimated delocalization of the π-electron density in the middle ring indicates that these compounds are the first examples of metalla-hetero[10]annulenes. Analysis of the electron density delocalization indicates that the title compounds are better conductors at the molecular level than the parent Schiff base, and therefore, can be considered as new building blocks for organic materials.