Diastereospecific intramolecular Ullmann couplings: unique chiral auxiliary for the preparation of 3,3'-disubstituted MeO-BIPHEP derivatives

[reaction: see text] A chiral auxiliary is described that provides only one diastereomer during intramolecular Ullmann couplings. Treatment of five Ullmann coupling precursors with Cu powder in DMF at 115 degrees C provides 2,2',3,3',6,6'-hexasubstituted 1,1'-biphenyls as single diastereomers in yields ranging from 66% to 91%.     

Predicting mathematical aptitude for higher education

This present study seeks to predict mathematical aptitude for higher education by examining the relationship between mathematics results from the Caribbean Examinations Council (CXC) general proficiency examination and the results from the General Certificate of Education (GCE) advanced level examination. This present study arose from a more extensive study that used a random sample of 177 high school students in the age cohort 17?19+ from a 7-year state-run, co-educational institution with a broad-based curriculum and a wide catchment area of student intake in The Republic of Trinidad and Tobago, West Indies. Semi-structured interviews and student academic records from the school comprised the survey instruments used for the study. Student grades were quantified using numerical scales. Findings suggest that the comprehension profile (Profile 2) of the CXC general proficiency level mathematics serves as a good predictor of mathematical aptitude for GCE advanced level mathematics. Implications for predicting mathematical aptitude for higher education and related issues are discussed.     

Variable Resolution Bivariate Plots

Abstract

Scatterplots are the method of choice for displaying the distribution of points in two dimensions. They are used to discover patterns such as holes, outliers, modes, and association between the two variables. A common problem is overstriking—the overlap on the plotting surface of glyphs representing individual observations. Overstriking can create a misleading impression of the data distribution. The variable resolution bivariate plots (Varebi plots) proposed in this article deal with the problem of overstriking by mixing display of a density estimate and display of individual observations. The idea is to determine the display format by analyzing the actual amount of overstriking on the screen. Thus, the display format will depend on the sample size, the distribution of the observations, the size and shape of individual icons, and the size of the window. It may change automatically when the window is resized. Varebi plots reveal detail wherever possible, and show the overall trend when displaying detail is not feasible.     

On the Spectra of Striped Sign Patterns

Sign patterns consisting of some positive and some negative columns, with at least one of each kind, are shown to allow any self-conjugate spectrum, and thus to allow any inertia. In the case of the n × n sign pattern with all columns positive, given any self-conjugate multiset consisting of n m 1 complex numbers supplemented by a sufficiently large positive number, it is shown how to construct a positive normal matrix whose spectrum is this multiset. Thus, the positive sign pattern allows any inertia with at least one positive eigenvalue.     

The siRNAsome: A Cation‐Free and Versatile Nanostructure for siRNA and Drug Co‐delivery

Nanoparticles show great potential for drug delivery. However, suitable nanostructures capable of loading a range of drugs together with the co‐delivery of siRNAs, which avoid the problem of cation‐associated cytotoxicity, are lacking. Herein, we report an small interfering RNA (siRNA)‐based vesicle (siRNAsome), which consists of a hydrophilic siRNA shell, a thermal‐ and intracellular‐reduction‐sensitive hydrophobic median layer, and an empty aqueous interior that meets this need. The siRNAsome can serve as a versatile nanostructure to load drug agents with divergent chemical properties, therapeutic proteins as well as co‐delivering immobilized siRNAs without transfection agents. Importantly, the inherent thermal/reduction‐responsiveness enables controlled drug loading and release. When siRNAsomes are loaded with the hydrophilic drug doxorubicin hydrochloride and anti‐P‐glycoprotein siRNA, synergistic therapeutic activity is achieved in multidrug resistant cancer cells and a tumor model.     

Finger Growth and Selection in a Poisson Field

Journal of Statistical Physics - Solutions are found for the growth of infinitesimally thin, two-dimensional fingers governed by Poisson’s equation in a long strip. The analytical results...     

PAd2‐DalPhos Enables the Nickel‐Catalyzed C−N Cross‐Coupling of Primary Heteroarylamines and (Hetero)aryl Chlorides

Base‐metal catalysts capable of enabling the assembly of heteroatom‐dense molecules by cross‐coupling of primary heteroarylamines and (hetero)aryl chlorides, while sought‐after given the ubiquity of unsymmetrical di(hetero)arylamino fragments in pharmacophores, are unknown. Herein, we disclose the new “double cage” bisphosphine PAd2‐DalPhos ( L2 ). The derived air‐stable Ni^II pre‐catalyst C2 functions well at low loadings in challenging test C?N cross‐couplings with established substrates, and facilitates the first Ni‐catalyzed C?N cross‐couplings of primary five‐ or six‐membered ring heteroarylamines and activated (hetero)aryl chlorides, with synthetically useful scope that is competitive with Pd catalysis.     

Novel tricyclic diamines 2. Synthesis of 1,7-diazaisoadamantane, 1,5-diazaisoadamantane and 1,6-diazahomobrendane

Three novel tricyclic diamines (1,7-diazaisoadamantane, 1,5-diazaisoadamantane and 1,6-diazahomobrendane) were prepared. A flexible synthetic strategy was employed which used flat, aromatic azaindoles as the starting materials. The requisite azaindoles were prepared by a tandem Sonogashira coupling/intramolecular cyclization reaction. Ring saturation, appropriate functionalization and intramolecular alkylation provided the three novel tricyclic diamines cores.