Chemical functionality of poly(methylenephosphine): phosphine-borane adducts and methylphosphonium ionomers

The chemical functionality of poly(methylenephosphine) n-Bu[MesP-CPh(2)](n)H () is examined in reactions with two isoelectronic species, namely BH(3) and CH(3)(+). The potential reactivity of polymer is modelled by examining the reactivity of molecular phosphines bearing similar substituents as the polymer. In particular, the phosphine-borane adducts Mes(Me)P(BH(3))-CPh(2)H () and Mes(Me)P(BH(3))-CPh(2)SiMe(2)H () are prepared from the reaction of BH(3).SMe(2) with Mes(Me)P-CPh(2)H () or Mes(Me)P-CPh(2)SiMe(2)H (), respectively. Treating with MeOTf affords the methylated model compound, [Mes(Me)(2)P-CPh(2)H]OTf (). X-Ray crystal structures are reported for each model compound. The reaction of n-Bu[MesP-CPh(2)](n)H (M(n) = 3.89 x 10(4), PDI = 1.34) with BH(3).SMe(2) affords the phosphine-borane polymer n-Bu[MesP(BH(3))-CPh(2)](n)H () (M(n) = 4.13 x 10(4), PDI = 1.26). In contrast, methylation of phosphine polymer gives n-Bu[MesP-CPh(2)](x)-/-[MesP(Me)-CPh(2)](y)H.(OTf)(y) () where approximately 50% of the phosphine moieties are methylated (from (31)P NMR).     

Functionalized BODIPY with various sensory units - a versatile colorimetric and luminescent probe for pH and ions

A series of BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) derivatives containing ion- and pH-sensory units have been successfully designed and synthesized. One of the compounds was structurally characterized by X-ray crystallography. Owing to the presence of an ICT absorption band, one of the compounds was found to show pronounced solvatochromic behavior in different organic solvents. Their emission energies in various solvents show a linear dependence on the Lippert solvent parameter. The cation-binding properties of the complexes with different metal ions (alkali metal, alkaline earth metal and transition metal ions) have been studied using UV-vis and emission spectroscopies. A 1?:?1 complexation to metal ions (Li(+), Na(+), Mg(2+), Ba(2+), Zn(2+), Cd(2+)) was found for the compound with one azacrown moiety in acetonitrile while another one with two azacrown moieties was shown to form 1?:?2 complexes with Zn(2+) and Mg(2+) cations. Their stability constants have been determined by both UV-vis and emission spectrophotometric methods. By introducing triarylborane moieties into the meso position and the 2-position of the BODIPY skeleton, different electronic absorption spectral changes together with an emission diminution were observed in response to fluoride ions. Ditopic binding study of 5, which was functionalized with both azacrown and triarylborane moieties, showed emission enhancement in the presence of Mg(2+) and F(-). These findings suggest that these BODIPY derivatives are capable of serving as versatile colorimetric and luminescence probes for pH, cations and F(-).     

Arsenic trioxide targets Hsp60, triggering degradation of p53 and survivin

The mechanisms of action of arsenic trioxide (ATO), a clinically used drug for the treatment of acute promyelocytic leukemia (APL), have been actively studied mainly through characterization of individual putative protein targets. There appear to be no studies at a system level. Herein, we integrate metalloproteomics through a newly developed organoarsenic probe, As-AC (C₂₀H₁₇AsN₄O₃S₂) with quantitative proteomics, allowing 37 arsenic binding and 250 arsenic regulated proteins to be identified in NB4, a human APL cell line. Bioinformatics analysis reveals that ATO disrupts multiple physiological processes, in particular, chaperone-related protein folding and cellular response to stress. Furthermore, we discover heat shock protein 60 (Hsp60) as a vital target of ATO. Through biophysical and cell-based assays, we demonstrate that ATO binds to Hsp60, leading to abolishment of Hsp60 refolding capability. Significantly, the binding of ATO to Hsp60 disrupts the formation of Hsp60-p53 and Hsp60-survivin complexes, resulting in degradation of p53 and survivin. This study provides significant insights into the mechanism of action of ATO at a systemic perspective, and serves as guidance for the rational design of metal-based anticancer drugs.

A highly selective organoarsenic fluorescent probe As-AC and quantitative proteomics were employed to track arsenic-binding and regulating proteins in live leukemia cells. Hsp60 was validated as a new target of ATO.     

Antihydrogen formation by autoresonant excitation of antiproton plasmas

In efforts to trap antihydrogen, a key problem is the vast disparity between the neutral trap energy scale ( $\sim\!50\,\upmu\mathrm{eV}$ ), and the energy scales associated with plasma confinement and space charge (~1 eV). In order to merge charged particle species for direct recombination, the larger energy scale must be overcome in a manner that minimizes the initial antihydrogen kinetic energy. This issue motivated the development of a novel injection technique utilizing the inherent nonlinear nature of particle oscillations in our traps. We demonstrated controllable excitation of the center-of-mass longitudinal motion of a thermal antiproton plasma using a swept-frequency autoresonant drive. When the plasma is cold, dense and highly collective in nature, we observe that the entire system behaves as a single-particle nonlinear oscillator, as predicted by a recent theory. In contrast, only a fraction of the antiprotons in a warm or tenuous plasma can be similarly excited. Antihydrogen was produced and trapped by using this technique to drive antiprotons into a positron plasma, thereby initiating atomic recombination. The nature of this injection overcomes some of the difficulties associated with matching the energies of the charged species used to produce antihydrogen.     

New functional inorganic polymers containing phosphorus

The C=C bond plays numerous roles in polymer science. This moiety is used as a precursor to polymers by addition polymerization and has been incorporated into π-conjugated polymers. The addition polymerization reaction has been extended to P=C bonds and the first example of a poly(methylenephosphine) has been prepared. The new macromolecule is of moderate molecular weight (ca. 10⁴ g/mol) and the oxidized polymers are air-stable. Poly(p-phenylenephosphaalkene), the first π-conjugated polymer containing P=C bonds in the backbone, has been prepared. The UV/Vis spectrum of this polymer shows a red shift in λ_max when compared with molecular model systems.