Synthesis and Characterization of Luminescent Cyclometalated Platinum(II) Complexes of 1,3‐Bis‐Hetero‐Azolylbenzenes with Tunable Color for Applications in Organic Light‐Emitting Devices through Extension of π Conjugation by Variation of the Heteroatom

A series of luminescent cyclometalated platinum(II) complexes of N^C^N ligands [N^C^N=2,6‐bis(benzoxazol‐2′‐yl)benzene (bzoxb), 2,6‐bis(benzothiazol‐2′‐yl)benzene (bzthb), and 2,6‐bis(N‐alkylnaphthoimidazol‐2′‐yl)benzene (naphimb)] has been synthesized and characterized. Two of the platinum(II) complexes have been structurally characterized by X‐ray crystallography. Their electrochemical, electronic absorption, and luminescence properties have been investigated. In dichloromethane solution at room temperature, the cyclometalated N^C^N platinum(II) complexes exhibited rich luminescence with well‐resolved vibronic‐structured emission bands. The emission energies of the complexes are found to be closely related to the electronic properties of the N^C^N ligands. By varying the electronic properties of the cyclometalated ligands, a fine‐tuning of the emission energies can be achieved, as supported by computational studies. Multilayer organic light‐emitting devices have been prepared by utilizing two of these platinum(II) complexes as phosphorescent dopants, in which a saturated yellow emission with Commission International de I′Eclairage coordinates of (0.50, 0.49) was achieved.     

Cholesterol‐/Estradiol‐Appended Alkynylplatinum(II) Complexes as Supramolecular Gelators: Synthesis,Characterization, Photophysical and Gelation Studies

A series of cholesterol‐/estradiol‐appended alkynylplatinum(II) complexes with tridentate N‐donor ligands, based on 2,6‐bis(1‐alkylpyrazol‐3‐yl)pyridine, has been synthesized and characterized by ¹H NMR spectroscopy, FAB‐mass spectrometry, and elemental analysis. Their photophysical properties have also been investigated. Computational studies have been performed to provide insights into the nature of the electronic transitions. Some of the complexes have been found to form stable thermo‐ and mechanoresponsive supramolecular gels.     

A Robust Palladium(II)–Porphyrin Complex as Catalyst for Visible Light Induced Oxidative C?H Functionalization

A series of palladium(II)–porphyrin complexes that display dual emissions with lifetimes up to 437 μs have been synthesized. Among the four complexes, PdF₂₀TPP is an efficient and robust catalyst for photoinduced oxidative C? H functionalization by using oxygen as terminal oxidant. α‐Functionalized tertiary amines were obtained in good to excellent yields by light irradiation (λ>400 nm) of a mixture of PdF₂₀TPP , tertiary amine, and nucleophile (cyanide, nitromethane, dimethyl malonate, diethyl phosphite, and acetone) under aerobic conditions. Four examples of intramolecular cyclized amine compounds could be similarly prepared. Comparison of the UV‐visible absorption spectra before and after the photochemical reaction revealed that PdF₂₀TPP was highly robust (>95 % recovery). The practical application of PdF₂₀TPP has been revealed by the photochemical reactions performed by using a low catalyst loading (0.01 mol %) and on a 10 mmol scale. The PdF₂₀TPP catalyst could sensitize photoinduced oxidation of sulfides to sulfoxides in excellent yields. Mechanistic studies revealed that the photocatalysis proceeded by singlet‐oxygen oxidation.     

Positive definite binary hermitian forms with finitely many exceptions

Let E/F be a CM extension of number fields, and L be a positive definite binary hermitian lattice over the ring of integers of E. An element in F is called an exception of L if it is represented by every localization of L but not by L itself. We show that if E/F and a positive integer k are given, then there are only finitely many similarity classes of positive definite binary hermitian lattices with at most k exceptions. This generalizes the corresponding finiteness result by Earnest and Khosravani [A.G. Earnest, A. Khosravani, Representation of integers by positive definite binary hermitian lattices over imaginary quadratic fields, J. Number Theory 62 (1997) 368-374, Theorem 2.2] for the case F=Q. We also prove that for a fixed totally real field F of odd degree over Q, there are only finitely many CM extensions E/F for which there exists a positive definite regular normal binary hermitian lattice over the ring of integers of E.     

Observations on the detection of b‐ and y‐type ions in the collisionally activated decomposition spectra of protonated peptides

Tandem mass spectrometric data from peptides are routinely used in an unsupervised manner to infer product ion sequence and hence the identity of their parent protein. However, significant variability in relative signal intensity of product ions within peptide tandem mass spectra is commonly observed. Furthermore, instrument‐specific patterns of fragmentation are observed, even where a common mechanism of ion heating is responsible for generation of the product ions. This information is currently not fully exploited within database searching strategies; this motivated the present study to examine a large dataset of tandem mass spectra derived from multiple instrumental platforms. Here, we report marked global differences in the product ion spectra of protonated tryptic peptides generated from two of the most common proteomic platforms, namely tandem quadrupole‐time‐of‐flight and quadrupole ion trap instruments. Specifically, quadrupole‐time‐of‐flight tandem mass spectra show a significant under‐representation of N‐terminal b‐type fragments in comparison to quadrupole ion trap product ion spectra. Energy‐resolved mass spectrometry experiments conducted upon test tryptic peptides clarify this disparity; b‐type ions are significantly less stable than their y‐type N‐terminal counterparts, which contain strongly basic residues. Secondary fragmentation processes which occur within the tandem quadrupole‐time‐of‐flight device account for the observed differences, whereas this secondary product ion generation does not occur to a significant extent from resonant excitation performed within the quadrupole ion trap. We suggest that incorporation of this stability information in database searching strategies has the potential to significantly improve the veracity of peptide ion identifications as made by conventional database searching strategies. Copyright © 2009 John Wiley & Sons, Ltd.     

Whey protein concentrate production by continuous ultrafiltration: Operability under constant operating conditions

There is limited information available on quantifying the operability of continuous ultrafiltration plants used for the production of whey protein concentrates. Based on modelling of the process, the operability studies demonstrate that a standard 12 loop commercial ultrafiltration plant is able to produce the desired specifications of the concentrates. The studies also indicate that mid-run washing of the plant is necessary to reduce the effects of long-term membrane fouling. Although it becomes more difficult to achieve the desired product flowrate as protein concentration in the feed increases, proper knowledge of process variations makes it possible to compensate for the effects from fluctuations in whey composition in order to maintain the desired specifications of the concentrates.     

Synthesis and characterization of fluorene‐based copolymers containing benzothiadiazole derivative for light‐emitting diodes applications

Five new thermally robust electroluminescent fluorene‐based conjugated copolymers, including poly[2,7‐(9,9‐dioctylfluorene)‐co‐4,7‐{5,6‐bis(3,7‐dimethyloctyloxymethyl)‐2,1,3‐(benzothiadiazole)}] ( PFO‐P2C₁₀BT ) were synthesized and used to fabricate the efficient polymer light‐emitting diodes (PLEDs). The glass transition temperatures of the polymers were found to be higher than that of poly(9,9‐dialkylfluorenes) and are in the range 113–165 °C. We fabricated PLEDs in indium‐tin oxide/PEDOT/light‐emitting polymer/cathode configurations using either double‐layer LiF/Al or triple‐layer Alq₃/LiF/Al cathode structures. The new copolymers were found to have emission colors that vary from greenish blue (491 nm) to green (543 nm) depending on the copolymer composition. The maximum brightness and luminance efficiency of these PLEDs were found to be up to 5347 cd/m² and 1.51 cd/A at 10 V, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6762–6769, 2008     

High order Hybrid central—WENO finite difference scheme for conservation laws

In this article we present a high resolution hybrid central finite difference—WENO scheme for the solution of conservation laws, in particular, those related to shock–turbulence interaction problems. A sixth order central finite difference scheme is conjugated with a fifth order weighted essentially non-oscillatory WENO scheme in a grid-based adaptive way. High order multi-resolution analysis is used to detect the high gradients regions of the numerical solution in order to capture the shocks with the WENO scheme while the smooth regions are computed with the more efficient and accurate central finite difference scheme. The application of high order filtering to mitigate the dispersion error of central finite difference schemes is also discussed. Numerical experiments with the 1D compressible Euler equations are shown.     

Exploring 9‐arylcarbazole moiety as the building block for the synthesis of photoluminescent group 10–12 heavy metal diynes and polyynes with high‐energy triplet states

A new series of organic‐soluble and thermally stable group 10 platinum(II) polyyne polymers functionalized with 9‐arylcarbazole moiety trans‐[? Pt(PBu₃)₂C?CRC?C? ]_n (R = 9‐arylcarbazole‐3,6‐diyl; aryl = phenyl, p‐methylphenyl, p‐fluorophenyl) were prepared in good yields by Hagihara's dehydrohalogenative polymerization of trans‐[PtCl₂(PBu₃)₂] with HC?CRC?CH under ambient conditions. The regiochemical structures of the polymers were characterized by multinuclear NMR spectroscopy. We discuss the optical spectroscopy of these polymetallaynes and compare the results with their bimetallic molecular model complexes trans‐[Pt(Ph)(PEt₃)₂C?CRC?CPt(Ph)(PEt₃)₂] as well as its group 11 gold(I) and group 12 mercury(II) congeners [(PPh₃)AuC?CRC?CAu(PPh₃)] and [MeHgC?CRC?CHgMe]. The structural properties of several model complexes were studied by X‐ray crystallography. The influence of the heavy metal atom and the 9‐aryl substituent of carbazole on the phosphorescence behavior and the spatial distribution of the lowest singlet (S₁) and triplet (T₁) excitons in these metalated alkynyl systems are comprehensively elucidated. The present work indicates that the efficiency of organic triplet emissions harnessed through the heavy‐atom effect of group 10–12 transition metals in the main chain generally follows the order Pt > Au > Hg but the optical properties of the materials are relatively insensitive to the nature of the 9‐aryl group on the carbazolyl ring. All of these metallaynyl‐carbazole materials with high‐energy T₁ states of 2.68 eV or higher show high phosphorescence efficiencies at low temperatures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5588–5607, 2006