Hydrocarbon Soluble Alkali-Metal-Aluminium Hydride Surrog[ATES]

A series of group 1 hydrocarbon-soluble donor free aluminates [AM(^tBuDHP)(TMP)Al(ⁱBu)₂] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2-^tBuC₅H₅N)AM)] containing a surrogate hydride (sp³ C−H) with [(ⁱBu)₂Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li(^tBuDHP)(TMP)Al(ⁱBu)₂] and [(TMEDA)Na(^tBuDHP)(TMP)Al(ⁱBu)₂] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].     

Coherent heterodyne-assisted pulsed spectroscopy: sub-Doppler two-photon spectra of krypton, characterizing a tunable nonlinear-optical ultraviolet light source

A chirp-minimized, nanosecond-pulsed system has been developed to generate tunable coherent ultraviolet light at ∼212.5 nm by fourth-harmonic conversion of output from an amplified, injection-seeded optical parametric oscillator (OPO). Our CHAPS (coherent heterodyne-assisted pulsed spectroscopy) method is used to characterize the frequency stability and optical bandwidth of the system’s output radiation by recording sub-Doppler two-photon excitation spectra of krypton. In our new scanned-reference variant of CHAPS, the central frequency for each amplified OPO pulse is logged by the optical-heterodyne chirp-analysis software, with the frequency of the seed laser slowly tuned and monitored by a high-resolution wavemeter, unlike our previous implementation of CHAPS where the seed-laser frequency was fixed. For the amplified, up-converted pulses at ∼212.5 nm, our CHAPS measurements indicate an optical bandwidth of ∼100 MHz, consistent with the Fourier-transform limit of their duration (∼4.5 ns).     

First Higher‐Order Photocycloaddition to a CN Bond: 1,3‐Diazepines from Maleimides

A light touch is all that is required to cleave a maleimide C? N bond to effect a [5+2] photocycloaddition with a sterically encumbered C?N moiety (see scheme).

     

Formation of mixed monolayers of silsesquioxanes and alkylsilanes on gold

The formation of mixed monolayers of hydridospherosilsesquioxane clusters (H(8)Si(8)O(12)) and alkylsilanes (H(2n+1)C(n)SiH(3)) on Au has been investigated using X-ray photoelectron and reflection-absorption infrared spectroscopies and scanning tunneling microscopy. All of the techniques indicate the displacement of the majority of the siloxane clusters from the surface in favor of the alkylsilane.     

Determination of ceruloplasmin in human serum by SEC-ICPMS

This paper describes an analytical method for the determination of ceruloplasmin (Cp) in human serum. The method uses immunoaffinity chromatography and size-exclusion chromatography (SEC) to “purify” the serum sample prior to analysis of ⁶³Cu and ⁶⁵Cu by inductively-coupled plasma mass spectrometry (ICPMS). By removing the six most abundant proteins from serum with immunoaffinity chromatography and by using SEC to separate Cu bound by Cp from any free Cu that might be present in the serum sample, we demonstrated that SEC-ICPMS can accurately and reproducibly measure Cp in the ERM DA470 reference serum. Cp identification is based on retention time match of the unknown in the serum sample with the Cp external standard and the presence of ⁶³Cu and ⁶⁵Cu at a ratio of 2.2±0.1. This method was used to analyze a reference serum certified for Cp, 47 serum samples from four different diseases and a set of normal controls. The reference serum and a serum sample from a patient with myocardial infarction, as well as a Cp standard, were also analyzed by electrospray mass spectrometry to confirm the presence of Cp in the SEC fraction known to contain ⁶³Cu.     

Perturbation theory of the non-linear optical polarization of an isolated system

The non-linear optical polarization of an isolated atom or molecule is treated, giving careful consideration to secular and resonant terms in the perturbation expansion. The Method of Averages introduced by Bogoliubov and Mitropolsky is used. The case where resonance-induced excited state populations are negligible, which is relevant to a wide range of non-linear optical experiments, is examined in detail for polarizations through third order in the perturbing fields. This yields concise expressions which are valid for any combination of applied field frequencies, including static fields.     

Poisson Summation,the Ambiguity Function,and the Theory of Weyl-Heisenberg Frames

In the early 1960s research into radar signal synthesis produced important formulas describing the action of the two-dimensional Fourier transform on auto- and crossambiguity surfaces. When coupled with the Poisson Summation formula, these results become applicable to the theory of Weyl-Heisenberg systems, in the form of lattice sum formulas that relate the energy of the discrete crossambiguity function of two signals f and g over a lattice with the inner product of the discrete autoambiguity functions of f and g over a "complementary" lattice. These lattice sum formulas provide a framework for a new proof of a result of N.J. Munch characterizing tight frames and for establishing an important relationship between l¹-summability (condition A) of the discrete ambiguity function of g over a lattice and properties of the Weyl-Heisenberg system of g over the complementary lattice. This condition leads to formulas for upper frame bounds that appear simpler than those previously published and provide guidance in choosing lattice parameters that yield the most snug frame at a stipulated density of basis functions.     

Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles

Control over the spatial distribution of components in metal–organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal–organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core–shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core–shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition. Particle formation is investigated by in situ X-ray diffraction, which reveals that the spatial distribution of components evolves with time and is determined by the interplay of phase stability, crystallisation kinetics and diffusion. This work opens up new possibilities for the control and characterisation of functionality, component distribution and interfaces in MOF-based materials.

Core–shell metal–organic framework nanoparticles have been synthesised in which the internal interface and distribution of components is found to be highly tunable using simple variations in reaction conditions.     

New and practical method for synthesis of 1- and 1,3-substituted xanthines.

[reaction: see text] A new and practical method for the synthesis of 1- and 1,3-substituted xanthines is reported. Direct base-promoted condensation of the imidazole precursor 1 with carbamates 2 gives 1-substituted 7-PMB xanthines 7 in good yields. Alkylation of these derivatives or their potassium salts proceeds under mild conditions to give functionalized 1,3-substituted 7-PMB xanthines 9 in good to excellent yields. The obtained 7-PMB-protected derivatives can be readily deprotected to give the parent 1- and 1,3-substituted xanthines.