Ultra-Small Air-Stable Triplet-Triplet Annihilation Upconversion Nanoparticles for Anti-Stokes Time-Resolved Imaging

Image contrast is often limited by background autofluorescence in steady-state bioimaging microscopy. Upconversion bioimaging can overcome this by shifting the emission lifetime and wavelength beyond the autofluorescence window. Here we demonstrate the first example of triplet-triplet annihilation upconversion (TTA-UC) based lifetime imaging microscopy. A new class of ultra-small nanoparticle (NP) probes based on TTA-UC chromophores encapsulated in an organic–inorganic host has been synthesised. The NPs exhibit bright UC emission (400–500 nm) in aerated aqueous media with a UC lifetime of ≈1 μs, excellent colloidal stability and little cytotoxicity. Proof-of-concept demonstration of TTA-UC lifetime imaging using these NPs shows that the long-lived anti-Stokes emission is easily discriminable from typical autofluorescence. Moreover, fluctuations in the UC lifetime can be used to map local oxygen diffusion across the subcellular structure. Our TTA-UC NPs are highly promising stains for lifetime imaging microscopy, affording excellent image contrast and potential for oxygen mapping that is ripe for further exploitation.     

Reactivity of superoxide radical anion with cyclic nitrones: role of intramolecular H-bond and electrostatic effects

Limitations exist among the commonly used cyclic nitrone spin traps for biological free radical detection using electron paramagnetic resonance (EPR) spectroscopy. The design of new spin traps for biological free radical detection and identification using EPR spectroscopy has been a major challenge due to the lack of systematic and rational approaches to their design. In this work, density functional theory (DFT) calculations and stopped-flow kinetics were employed to predict the reactivity of functionalized spin traps with superoxide radical anion (O2*-). Functional groups provide versatility and can potentially improve spin-trap reactivity, adduct stability, and target specificity. The effect of functional group substitution at the C-5 position of pyrroline N-oxides on spin-trap reactivity toward O2*- was computationally rationalized at the PCM/B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) and PCM/mPW1K/6-31+G(d,p) levels of theory. Calculated free energies and rate constants for the reactivity of O2*- with model nitrones were found to correlate with the experimentally obtained rate constants using stopped-flow and EPR spectroscopic methods. New insights into the nucleophilic nature of O2*- addition to nitrones as well as the role of intramolecular hydrogen bonding of O2*- in facilitating this reaction are discussed. This study shows that using an N-monoalkylsubstituted amide or an ester as attached groups on the nitrone can be ideal in molecular tethering for improved spin-trapping properties and could pave the way for improved in vivo radical detection at the site of superoxide formation.     

Determination of twenty-five elements in lichens by sector field inductively coupled plasma mass spectrometry and microwave-assisted acid digestion

A simple and efficient digestion method for rapid sample preparation and quantification of 25 chemical elements in lichens by sector field inductively coupled plasma mass spectrometry is described. A microwave (MW)-assisted acid digestion was carried out at atmospheric pressure simultaneously handling up to 80 samples in screw-capped disposable polystyrene tubes. This digestion procedure was compared with the established MW digestion in closed vessels in order to examine its potential applicability in routine analysis for environmental monitoring. Three certified reference materials, i.e. BCR 482 (lichens), BCR 62 (olive leaves) and BCR 100 (beech leaves), as well as a small set of real samples were analyzed. Limits of quantification, accuracy and precision of the method were assessed. The majority of the elements were totally recovered from the lichens and from the other vegetable matrices. Low contamination risk, simplicity, time-saving, and applicability in routine analyses make this method very suitable for use in extensive screening campaigns.     

Polymerization Isomerism in Co-M (M = Cu,Ag, Au) Carbonyl Clusters: Synthesis,Structures and Computational Investigation

The reaction of [Co(CO)₄]⁻ (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)₄}₂]⁻ (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt₄][M{Co(CO)₄}₂] salts. [NEt₄](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag₂{Co(CO)₄}₄]²⁻ (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na₂(5)·C₄H₆O₂, [PPN]₂(5)·C₅H₁₂ (PPN = N(PPh₃)₂]⁺), [NBu₄]₂(5) and [NMe₄]₂(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.     

The application of low energy ion scattering spectroscopy (LEIS) in sub 28‐nm CMOS technology

With the transition to ≤28‐nm CMOS technology nodes, the surface analytical challenges with regard to steadily decreasing dimensions and still growing materials options raise the demand of high performing surface analysis techniques. Characterization of ultrathin films and multilayer stacks, especially in high‐k metal gate stacks, by means of low energy ion scattering spectroscopy (LEIS) with its monolayer sensitivity has been established as a very useful analysis technique next to Auger electron spectroscopy, X‐ray photoelectron spectroscopy , and time‐of‐flight secondary ion mass spectrometry. Questions regarding film nucleation, growth, coverage, and diffusion can be answered, thereby enabling those processes to be controlled appropriately. In this work, growth studies of ALD HfO₂ and TiN are shown, as well as film thickness determination based on surface spectra. PVD aluminum and lanthanum, acting as work function metals on the gate oxide, were deposited, and their film formation and closure were investigated. Further application fields of LEIS have emerged from the characterization of in‐die features on patterned wafers. As presented on test arrays, it is possible to detect material deep in trenches. This is an advantage if residues need to be identified after etch or clean processes.     

Strong convergence of the discontinuous Galerkin scheme for the low regularity miscible displacement equations

Strong convergence of the numerical solution to a weak solution is proved for a nonlinear coupled flow and transport problem arising in porous media. The method combines a mixed finite element method for the pressure and velocity with an interior penalty discontinuous Galerkin method in space for the concentration. Using functional tools specific to broken Sobolev spaces, the convergence of the broken gradient of the numerical concentration to the weak solution is obtained in the L² norm. © 2016 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 489–513, 2017     

Synthesis,Characterization, and Reactivity of a Series of Homo- and Hetero-dinuclear Complexes based on an Asymmetric FloH Ligand System

In a previous communication we reported the site-directed generation of a heterodinuclear Fe^IIICu^II complex ( 1 ) by using an asymmetric dinucleating ligand FloH. The iron(III) ion was introduced first on the preferential metal-binding site of the ligand that led to the formation of the thermodynamically favored five-membered chelate ring upon metal-binding. Copper(II) was introduced in the next step. The stepwise metalation strategy reported previously has now been extended to synthesize a series of heterodinuclear Fe^IIIM^II [M = Mn ( 2 ), Fe ( 3 ), Co ( 4 ), and Ni ( 5 )] and Fe^IICu^I ( 1a ) as well as the homodinuclear Cu^ICu^I ( 6 ) complexes. The complexes were characterized by X-ray crystallography (except for 1a and 6 ), and by a limited number of spectroscopic methods. Complex 1 with a labile solvent binding site at Fe^III reacted with H₂O₂ to form a transient intermediate that showed reactivity typical of metal peroxide complexes. The metal centers in the complexes 2 – 5 are coordinatively saturated, and hence they showed no reactivity with H₂O₂. Complex 1a reacted with O₂ via an intermolecular pathway to form a μ-oxo bridged tetrameric complex 1b , which was structurally characterized. This is in contrast to the homodinuclear Cu^ICu^I and heme Fe^IICu^I cores, which prefer an intramolecular pathway for O₂ activation.     

Solving matrix polynomial equations arising in queueing problems

The matrix equation ∑_i=0ⁿA_iXⁱ=0, where the A_i's are m×m matrices, is encountered in the numerical solution of Markov chains which model queueing problems. We provide here a unifying framework in terms of Möbius' mapping to relate different resolution algorithms having a quadratic convergence. This allows us to compare algorithms like logarithmic reduction (LR) and cyclic reduction (CR), which extend Graeffe's iteration to matrix polynomials, and the invariant subspace (IS) approach, which extends Cardinal's algorithm. We devise new iterative techniques having quadratic convergence and present numerical experiments.     

Dinuclear copper complexes based on parallel β-diiminato binding sites and their reactions with O2: evidence for a Cu-O-Cu entity

Investigations concerning the system β-diketiminato-Cu(I)/O(2) have revealed valuable insights that may be discussed in terms of the behavior of mononuclear oxygenases containing copper. On the other hand nature also employs dinuclear Cu enzymes for the activation of O(2). With this background the ligand system [(Me(2))(C(6)H(3))Xanthdim](2-) containing two parallel β-diiminato binding sites linked by a xanthene backbone with 2,3-dimethylphenyl residues at the diiminato units was investigated with respect to its copper coordination chemistry. The diimine [(Me(2))(C(6)H(3))Xanthdim]H(2) was treated with CuOtBu in the presence of acetonitrile, PPh(3), and PMe(3) to yield the corresponding complexes [(Me(2))(C(6)H(3))Xanthdim](Cu(L))(2) (L = CH(3)CN, 1, PPh(3), 2, and PMe(3), 3) that proved to be stable and were fully characterized. Single crystal X-ray diffraction analyses performed for the three complexes showed that considerable steric crowding within the binding pockets of 2 leads to a very long Cu-Cu distance while the structures of 1 and 3 are relaxed. Compounds 2 and 3 are relatively robust toward air, whereas 1 is very sensitive and quantitatively reacts with O(2) at room temperature (r.t.) within less than 2 min to give intractable compounds. At low temperatures the formation of a green intermediate was observed that was identified as a Cu(II)-O-Cu(II) species spectroscopically and chemically. This finding is of relevance also in the context of the results obtained testing 1 as a catalyst for phenol oxidation using O(2): 1 efficiently catalyzes phenol coupling, while there was no evidence for any oxygenation reactions occurring.