Mild and efficient Cs2CO3-promoted synthesis of phosphonates

A mild and convenient synthesis for phosphonates using cesium carbonate (Cs₂CO₃), tetrabutylammonium iodide (TBAI) and DMF was developed at room temperature. Numerous dialkyl phosphites were screened using a diverse array of alkyl halides and these reaction conditions were found to be highly efficient producing various phosphonates exclusively in moderate to high yields.     

Protected Amine Labels: A Versatile Molecular Scaffold for Multiplexed Nominal Mass and Sub-Da Isotopologue Quantitative Proteomic Reagents

We assemble a versatile molecular scaffold from simple building blocks to create binary and multiplexed stable isotope reagents for quantitative mass spectrometry. Termed Protected Amine Labels (PAL), these reagents offer multiple analytical figures of merit including, (1) robust targeting of peptide N-termini and lysyl side chains, (2) optimal mass spectrometry ionization efficiency through regeneration of primary amines on labeled peptides, (3) an amino acid-based mass tag that incorporates heavy isotopes of carbon, nitrogen, and oxygen to ensure matched physicochemical and MS/MS fragmentation behavior among labeled peptides, and (4) a molecularly efficient architecture, in which the majority of hetero-atom centers can be used to synthesize a variety of nominal mass and sub-Da isotopologue stable isotope reagents. We demonstrate the performance of these reagents in well-established strategies whereby up to four channels of peptide isotopomers, each separated by 4 Da, are quantified in MS-level scans with accuracies comparable to current commercial reagents. In addition, we utilize the PAL scaffold to create isotopologue reagents in which labeled peptide analogs differ in mass based on the binding energy in carbon and nitrogen nuclei, thereby allowing quantification based on MS or MS/MS spectra. We demonstrate accurate quantification for reagents that support 6-plex labeling and propose extension of this scheme to 9-channels based on a similar PAL scaffold. Finally, we provide exemplar data that extend the application of isotopologe-based quantification reagents to medium resolution, quadrupole time-of-flight mass spectrometers.

Thermal‐ and Light‐Induced Spin Crossover in a Guest‐Dependent Dinuclear Iron(II) System

We previously reported the dinuclear material [Fe^II₂(ddpp)₂(NCS)₄] ? 4 CH₂Cl₂ ( 1? 4 CH₂Cl₂; ddpp=2,5‐di(2′,2′′‐dipyridylamino)pyridine) and its partially desolvated analogue ( 1? CH₂Cl₂), which undergo two‐ and one‐step spin‐crossover (SCO) transitions, respectively. Here, we manipulate the type and degree of solvation in this system and find that either a one‐ or two‐step spin transition can be specifically targeted. The chloroform clathrate 1? 4 CHCl₃ undergoes a relatively abrupt one‐step SCO, in which the two equivalent Fe^II sites within the dinuclear molecule crossover simultaneously. Partial desolvation of 1? 4 CHCl₃ to form 1? 3 CHCl₃ and 1? CHCl₃ occurs through single‐crystal‐to‐single‐crystal processes (monoclinic C2/c to P2₁/n to P2₁/n) in which the two equivalent Fe^II sites become inequivalent sites within the dinuclear molecule of each phase. Both 1? 3 CHCl₃ and 1? CHCl₃ undergo one‐step spin transitions, with the former having a significantly higher SCO temperature than 1? 4 CHCl₃ and the latter, and each has a broader SCO transition than 1? 4 CHCl₃, attributable to the overlap of two SCO steps in each case. Further magnetic manipulation can be carried out on these materials through reversibly resolvating the partially desolvated material with chloroform to produce the original one‐step SCO, or with dichloromethane to produce a two‐step SCO reminiscent of that seen for 1? 4 CH₂Cl₂. Furthermore, we investigate the light‐induced excited spin state trapping (LIESST) effect on 1? 4 CH₂Cl₂ and 1? CH₂Cl₂ and observe partial LIESST activity for the former and no activity for the latter.     

The quest for modular nanocages: tbo-MOF as an archetype for mutual substitution, functionalization, and expansion of quadrangular pillar building blocks

A new blueprint network for the design and synthesis of porous, functional 3D metal-organic frameworks (MOFs) has been identified, namely, the tbo net. Accordingly, tbo-MOFs based on this unique (3,4)-connected net can be exclusively constructed utilizing a combination of well-known and readily targeted [M(R-BDC)](n) MOF layers [i.e., supermolecular building layers (SBLs)] based on the edge-transitive 4,4 square lattice (sql) (i.e., 2D four-building units) and a novel pillaring strategy based on four proximal isophthalate ligands from neighboring SBL membered rings (i.e., two pairs from each layer) covalently cross-linked through an organic quadrangular core (e.g., tetrasubstituted benzene). Our strategy permits the rational design and synthesis of isoreticular structures, functionalized and/or expanded, that possess extra-large nanocapsule-like cages, high porosity, and potential for gas separation and storage, among others. Thus, tbo-MOF serves as an archetypal tunable, isoreticular MOF platform for targeting desired applications.     

Strong-stability-preserving 3-stage Hermite-Birkhoff time-discretization methods

Strong-stability-preserving (SSP) time-discretization methods have a nonlinear stability property that makes them particularly suitable for the integration of hyperbolic conservation laws. A collection of SSP explicit 3-stage Hermite-Birkhoff methods of orders 3 to 7 with nonnegative coefficients are constructed as k-step analogues of third-order Runge-Kutta methods, incorporating a function evaluation at two off-step points. Generally, these new methods have larger effective CFL coefficients than the hybrid methods of Huang with the same step number k. They have larger maximum scaled step sizes than hybrid methods on Burgers' equations.     

Nuclear spectroscopy in 48V via the 34S(16O,pn)48V reaction

The electromagnetic decays of 18 bound states in ⁴⁸V have been studied via the ³⁴S(¹⁶O, pn)⁴⁸V reaction, at incident ion energies of 30–36 MeV. At these energies pn, 2pn, 2p, αp, αn and 2n exit channels were open. Spins and parities of the levels as well as the branching and mixing ratios of their decay γ-rays have been obtained from angular distribution, excitation function, and high resolution γ-γ and n-γ coincidence measurements. Six, and possibly seven, members of a very pure rotational negative parity band have been identified. This band is based on a 1^? low-lying core excited state with probable configuration $\text{(π}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{)}{}^{\mathrm{?1}}\text{(π}\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{)}{}^4\text{(ν}\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{)}{}^5$.     

Bounded pseudo-differential operators

This lecture gives an inside look into the proof of the continuity of pseudo-differential operators of orderm and typep, δ₁, δ₂ for 0≦p≦δ₁=1, 0≦p≦δ₂<1, andm/n≦p≦(δ₁+δ₂)/2. Applications are mentioned.     

Hermite–Birkhoff–Obrechkoff four-stage four-step ODE solver of order 14 with quantized step size

A four-stage Hermite–Birkhoff–Obrechkoff method of order 14 with four quantized variable steps, denoted by HBOQ(14)4, is constructed for solving non-stiff systems of first-order differential equations of the form y^′=f(t,y)$y^{\prime }=f(t,y)$ with initial conditions y(_t0)=_y0$y\left(t_0\right)=y_0$. Its formula uses y^′$y^{\prime }$, y^″$y^{″}$ and y^?$y^{?}$ as in Obrechkoff methods. Forcing a Taylor expansion of the numerical solution to agree with an expansion of the true solution leads to multistep- and Runge–Kutta-type order conditions which are reorganized into linear Vandermonde-type systems. To reduce overhead, simple formulae are derived only once to obtain the values of Hermite–Birkhoff interpolation polynomials in terms of Lagrange basis functions for 16 quantized step size ratios. The step size is controlled by a local error estimator. When programmed in C ++, HBOQ(14)4 is superior to the Dormand–Prince Runge–Kutta pair DP(8,7)13M of order 8 in solving several problems often used to test higher order ODE solvers at stringent tolerances. When programmed in Matlab, it is superior to ode113 in solving costly problems, on the basis of the number of steps, CPU time, and maximum global error. The code is available on the URL www.site.uottawa.ca/~remi.