Ein Neues,tricyclisches schwefelreiches Phosphan

A New Tricyclic Sulfur-rich Phosphane From the products of the reaction of P₄S₃ with tert-Butyliodide the compound (t-Bu(S)P)₂P₄S₃ was isolated in low yield. The compound is stable and has a structure related to the hydrocarbon brexane. By reaction with triphenylphosphin the compounds (t-BuP)(t-Bu(S)P)P₄S₃ and (t-BuP)₂P₄S₃ were obtained. The ³¹P-nmr spectra of all compounds were solved and used to determine the structure of the molecules. A complete set of ³¹P-nmr data is given.     

Synthesis of PNIPAAm-g-P4VP Microgel as Draw Agent in Forward Osmosis by RAFT Polymerization and Reverse Suspension Polymerization to Improve Water Flux

Microgels have unique and versatile properties allowing their use in forward osmosis areas as a draw agent. In this contribution, poly(4-vinylpyridine) (P4VP) was synthesized via RAFT polymerization and then grafted to a poly(N-Isopropylacrylamide) (PNIPAAm) crosslinking network by reverse suspension polymerization. P4VP was successfully obtained by the quasiliving polymerization with the result of nuclear magnetic resonance and gel permeation chromatography characterization. The particle size and particle size distribution of the PNIPAAm-g-P4VP microgels containing 0, 5, 10, 15 and 20 wt% P4VP were measured by means of a laser particle size analyzer. It was found that all the microgels were of micrometer scale and the particle size was increased with the P4VP load. Inter/intra-molecular-specific interactions, i.e., hydrogen bond interactions were then investigated by Fourier infrared spectroscopy. In addition, the water flux measurements showed that all the PNIPAAm-g-P4VP microgels can draw water more effectively than a blank PNIPAAm microgel. For the copolymer microgel incorporating 20 wt% P4VP, the water flux was measured to be 7.48 L∙m⁻²∙h⁻¹.     

P2X7 Receptors in Astrocytes: A Switch for Ischemic Tolerance

A sub-lethal ischemic episode (preconditioning [PC]) protects neurons against a subsequent lethal ischemic injury. This phenomenon is known as ischemic tolerance. PC itself does not cause brain damage, but affects glial responses, especially astrocytes, and transforms them into an ischemia-resistant phenotype. P2X7 receptors (P2X7Rs) in astrocytes play essential roles in PC. Although P2X7Rs trigger inflammatory and toxic responses, PC-induced P2X7Rs in astrocytes function as a switch to protect the brain against ischemia. In this review, we focus on P2X7Rs and summarize recent developments on how astrocytes control P2X7Rs and what molecular mechanisms they use to induce ischemic tolerance.     

In Silico Analysis of PORD Mutations on the 3D Structure of P450 Oxidoreductase

Cytochrome P450 oxidoreductase (POR) is a membrane-bound flavoprotein that helps in transferring electrons from its NADPH domain to all cytochrome P450 (CYP450) enzymes. Mutations in the POR gene could severely affect the metabolism of steroid hormones and the development of skeletal muscles, a condition known as Cytochrome P450 oxidoreductase deficiency (PORD). PORD is associated with clinical presentations of disorders of sex development, Antley and Bixler’s syndrome (ABS), as well as an abnormal steroid hormone profile. We have performed an in silico analysis of POR 3D X-ray protein crystal structure to study the effects of reported mutations on the POR enzyme structure. A total of 32 missense mutations were identified, from 170 PORD patients, and mapped on the 3D crystal structure of the POR enzyme. In addition, five of the missense mutations (R457H, A287P, D210G, Y181D and Y607C) were further selected for an in-depth in silico analysis to correlate the observed changes in POR protein structure with the clinical phenotypes observed in PORD patients. Overall, missense mutations found in the binding sites of POR cofactors could lead to a severe form of PORD, emphasizing the importance of POR cofactor binding domains in transferring electrons to the CYP450 enzyme family.     

Computational Insight into Biotransformation Profiles of Organophosphorus Flame Retardants to Their Diester Metabolites by Cytochrome P450

Biotransformation of organophosphorus flame retardants (OPFRs) mediated by cytochrome P450 enzymes (CYPs) has a potential correlation with their toxicological effects on humans. In this work, we employed five typical OPFRs including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), and 2-ethylhexyl diphenyl phosphate (EHDPHP), and performed density functional theory (DFT) calculations to clarify the CYP-catalyzed biotransformation of five OPFRs to their diester metabolites. The DFT results show that the reaction mechanism consists of Cα-hydroxylation and O-dealkylation steps, and the biotransformation activities of five OPFRs may follow the order of TCEP ≈ TEP ≈ EHDPHP > TCIPP > TDCIPP. We further performed molecular dynamics (MD) simulations to unravel the binding interactions of five OPFRs in the CYP3A4 isoform. Binding mode analyses demonstrate that CYP3A4-mediated metabolism of TDCIPP, TCIPP, TCEP, and TEP can produce the diester metabolites, while EHDPHP metabolism may generate para-hydroxyEHDPHP as the primary metabolite. Moreover, the EHDPHP and TDCIPP have higher binding potential to CYP3A4 than TCIPP, TCEP, and TEP. This work reports the biotransformation profiles and binding features of five OPFRs in CYP, which can provide meaningful clues for the further studies of the metabolic fates of OPFRs and toxicological effects associated with the relevant metabolites.     

Large-time behavior of perturbed diffusion markov processes with applications to the second eigenvalue problem for fokker-planck operators and simulated annealing

We study the large-time behavior and rate of convergence to the invariant measures of the processes dX (t)=b(X) (t)) dt + (X (t)) dB(t). A crucial constant appears naturally in our study. Heuristically, when the time is of the order exp( – )/² , the transition density has a good lower bound and when the process has run for about exp( – )/², it is very close to the invariant measure. LetL =(²/2) – U · be a second-order differential operator on ^d. Under suitable conditions,L ^z has the discrete spectrum

Exceptional congruences for the coefficients of certain eta-product newforms

Let F(z)=∑_n=1^∞a(n)qⁿ denote the unique weight 16 normalized cuspidal eigenform on . In the early 1970s, Serre and Swinnerton-Dyer conjectured that

     

Stable model categories are categories of modules

A stable model category is a setting for homotopy theory where the suspension functor is invertible. The prototypical examples are the category of spectra in the sense of stable homotopy theory and the category of unbounded chain complexes of modules over a ring. In this paper we develop methods for deciding when two stable model categories represent ‘the same homotopy theory’. We show that stable model categories with a single compact generator are equivalent to modules over a ring spectrum. More generally stable model categories with a set of generators are characterized as modules over a ‘ring spectrum with several objects’, i.e., as spectrum valued diagram categories. We also prove a Morita theorem which shows how equivalences between module categories over ring spectra can be realized by smashing with a pair of bimodules. Finally, we characterize stable model categories which represent the derived category of a ring. This is a slight generalization of Rickard's work on derived equivalent rings. We also include a proof of the model category equivalence of modules over the Eilenberg-Mac Lane spectrum HR and (unbounded) chain complexes of R-modules for a ring R.     

A local trace formula for resonances of perturbed periodic Schrödinger operators

We give a local trace formula for the pair (P₁(h)=P₀+W(hy),P₀), where P₀ is a periodic Schrödinger operator, W is a decreasing perturbation and h is a small positive parameter. We apply this result to establish the existence of ∼h⁻ⁿ resonances near some energy λ of σ(P₀).