Near-infrared-emitting phthalocyanines. A combined experimental and density functional theory study of the structural, optical, and photophysical properties of Pd(II) and Pt(II) α-butoxyphthalocyanines

The structural, optical, and photophysical properties of 1,4,8,11,15,18,22,25-octabutoxyphthalocyaninato-palladium(II), PdPc(OBu)(8), and the newly synthesized platinum analogue PtPc(OBu)(8) are investigated combining X-ray crystallography, static and transient absorption spectroscopy, and relativistic zeroth-order regular approximation (ZORA) Density Functional Theory (DFT)/Time Dependent DFT (TDDFT) calculations where spin-orbit coupling (SOC) effects are explicitly considered. The results are compared to those previously reported for NiPc(OBu)(8) (J. Phys. Chem. A 2005, 109, 2078) in an effort to highlight the effect of the central metal on the structural and photophysical properties of the group 10 transition metal octabutoxyphthalocyanines. Different from the nickel analogue, PdPc(OBu)(8) and PtPc(OBu)(8) show a modest and irregular saddling distortion of the macrocycle, but share with the first member of the group similar UV-vis spectra, with the deep red and intense Q-band absorption experiencing a blue shift down the group, as observed in virtually all tetrapyrrolic complexes of this triad. The blue shift of the Q-band along the MPc(OBu)(8) (M = Ni, Pd, Pt) series is interpreted on the basis of the metal-induced electronic structure changes. Besides the intense deep red absorption, the title complexes exhibit a distinct near-infrared (NIR) absorption due to a transition to the double-group 1E (π,π*) state, which is dominated by the lowest single-group (3)E (π,π*) state. Unlike NiPc(OBu)(8), which is nonluminescent, PdPc(OBu)(8) and PtPc(OBu)(8) show both deep red fluorescence emission and NIR phosphorescence emission. Transient absorption experiments and relativistic spin-orbit TDDFT calculations consistently indicate that fluorescence and phosphorescence emissions occur from the S(1)(π,π*) and T(1)(π,π*) states, respectively, the latter being directly populated from the former, and the triplet state decays directly to the S(0) surface (the triplet lifetime in deaerated benzene solution was 3.04 μs for Pd and 0.55 μs for Pt). Owing to their triplet properties, PdPc(OBu)(8) and PtPc(OBu)(8) have potential for use in photodynamic therapy (PDT) and are potential candidates for NIR light emitting diodes or NIR emitting probes.     

A novel mixed valent Cu(II)-Cu(I) 2D framework made of a hydrazone and μ-SCN bridged metallacyclic loops cross-linked by μ(3)-SCN chains

A mixed valent copper complex [Cu(II)Cu(I)(L)(μ-SCN)(μ(3)-SCN)](n) (LH = N'-((pyridin-2-yl)methylene)acetohydrazide) has been synthesized and characterized. It is a unique example of a 2D mixed valent Cu(II)-Cu(I) interlinked molecular assembly with a very unusual bridging property of the hydrazone ligand. An extraordinary in situ partial Cu(II)→ Cu(I) reduction is observed in this system at room temperature.     

Carbon ceramic nanoparticulate film electrode prepared from oppositely charged particles by layer-by-layer approach

Carbon ceramic nanoparticulate film electrode was prepared from negatively charged sulfonated carbon nanoparticles and positively charged silicate submicrometre particles with appended imidazolium groups. They were immobilized on an indium tin oxide surface by layer-by-layer method: alternative immersion into suspension of positive and negative particles. The film formation is confirmed by scanning electron microscopy – after larger number of immersion and withdrawal steps more material is deposited on the electrode substrate. The nanoparticulate film is stable and the obtained electrode exhibits a significant increase of capacitive current and faradaic current corresponding to hydrogen peroxide electroreduction. The effect of the number of immersion and withdrawal steps is strikingly visible on dioxygen bioelectrocatalytic reduction current after adsorption of the enzyme laccase.     

Evaluation of the performance of sensors based on optical imaging of a chemically sensitive layer

Interest in the use of the optical properties of chemical indicators is growing steadily. Among the optical methods that can be used to capture changes in sensing layers, those producing images of large-area devices are particularly interesting for chemical sensor array development. Until now, few studies addressed the characterization of image sensors from the point of view of their chemical sensor application. In this paper, a method to evaluate such performance is proposed. It is based on the simultaneous measurement of absorption events in a metalloporphyrin layer with an image sensor and a quartz microbalance (QMB). Exploiting the well-known behaviour of QMB, comparison of signals enables estimation of the minimum amount of absorbed molecules that the image sensor can detect. Results indicate that at the single pixel level a standard image sensor (for example a webcam) can easily detect femtomoles of absorbed molecules. It should therefore be possible to design sensor arrays in which the pixels of images of large-area sensing layers are regarded as individual chemical sensors providing a ready and simple method for large sensor array development.     

On Automorphisms of Flag Spaces

We show that the automorphisms of the flag space associated with a 3-dimensional projective space can be characterized as bijections preserving a certain binary relation on the set of flags in both directions. From this we derive that there are no other automorphisms of the flag space than those coming from collineations and dualities of the underlying projective space. Further, for a commutative ground field, we discuss the corresponding flag variety and characterize its group of automorphic collineations.     

On the rank of 3×3×3-tensors

Let U, V and W be finite dimensional vector spaces over the same field. The rank of a tensor τ in U???V???W is the minimum dimension of a subspace of U???V???W containing τ and spanned by fundamental tensors, i.e. tensors of the form u???v???w for some u in U, v in V and w in W. We prove that if U, V and W have dimension three, then the rank of a tensor in U???V???W is at most six, and such a bound cannot be improved, in general. Moreover, we discuss how the techniques employed in the proof might be extended to prove upper bounds for the rank of a tensor in U???V???W when the dimensions of U, V and W are higher.     

Laser desorption/ionization techniques in the characterization of high molecular weight oil fractions. Part 1: asphaltenes

The molecular weight distribution of the asphaltene fractions of two types of crude oils from two different Italian fields (samples 1 and 2) was investigated. The analytical tools used to perform these analyses were matrix assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) mass spectrometry. After observing that the use of the matrix (as well as the addition of Ag+) did not improve the quality of the data compared to that obtained in LDI conditions, all further measurements were performed with the latter technique. Operating under usual conditions of laser power and delay time, a very low resolution was observed, showing only macroscopic differences between the two samples in the molecular weight distribution of the different components. An accurate study on the possible reasons of this undesirable behavior indicates that it can originate from space charge phenomena occurring either in the ion source region or during the flight. A valid parameterization of the delay time and the laser power allowed higher quality spectra to be obtained. Surface-enhanced laser desorption ionization (SELDI) measurements were also performed using normal phase (silica) as the sample holder surface. Under these conditions, better results are obtained, proving that the sample-surface interaction is important to achieve, by means of laser irradiation, a homogeneous set of product ions. Both asphaltene samples were fractionated in five subfractions by gel-permeation chromatography (GPC) to obtain a better separation of the molecular weight distributions; the related spectra confirmed these findings. By using different approaches, relevant and reproducible differences between the asphaltene fractions of the two oil samples were observed.     

Wavelength dispersive X-ray analysis and cathodoluminescence techniques for monitoring the chemical removal of AlInN on an N-face GaN surface

This paper shows the selective etching process of an AlInN sacrificial layer, lattice-matched to GaN, on N-face GaN by an aqueous solution of 1,2-diaminoethane. Using the wavelength dispersive X-ray (WDX) spectrometers on an electron probe micro-analyser, together with an optical spectrometer and silicon CCD array added to the light microscope, and sharing the same focus as the electron microscope, cathodoluminescence spectra are collected from exactly the same spot as sampled by the WDX spectrometers. This technique allows the compositional properties of the etched AlInN layer and the optical properties of the semiconductor layers underlying the sacrificial layer to be scrutinised, verifying the etching selectivity and the efficiency of the process.     

Capillary zone electrophoresis of glycopeptides under controlled electroosmotic flow conditions coupled to electrospray and matrix-assisted laser desorption/ionization mass spectrometry

Defined conditions of EOF along with different pH values of the BGE were compared for the purpose of analyzing glycopetides by CZE coupled to MS (CZE-MS). Hyphenation to MS involved ESI as well as MALDI, and single-stage and multistage MS were applied. Variation of the EOF was accomplished by selecting appropriate coatings for the capillary, namely hexadimethrine bromide (HDMB) and HDMB/dextran sulfate. A high and reproducible anodic and cathodic EOF, respectively, was obtained in both approaches, allowing the detection of analytes with net positive as well as negative charge in one single run. Thus, a fast and sensitive determination of the glycopeptides in a tryptic digest of antithrombin, chosen as a test sample, was achieved. Ionization suppression effects, a phenomenon typically observed with glycopeptides in MS analysis, were minimized thanks to separation from other peptides present. The high stability of the coatings permitted the generation of mass spectra without interfering peaks originating from the coating polymers. The high EOF generated by the coatings facilitated the maintenance of a stable spray when coupling to ESI-MS, and a stable CZE current when working with a sheath flow-assisted analyte deposition onto MALDI targets, respectively. In conclusion, CZE-MS could be demonstrated as a robust complementary method to capillary RP-HPLC-MS in combination with both soft-ionization techniques, ESI and MALDI, generally, and particularly in the context of glycopeptide analysis.