Spatial extent of the singlet and triplet excitons in luminescent angular-shaped transition-metal diynes and polyynes comprising non-pi-conjugated group 16 main group elements

A novel approach based on conjugation interruption has been developed and is presented for a series of luminescent and thermally stable chalcogen-bridged platinum(II) polyyne polymers trans-[{-Pt(PBu3)2C[triple bond]C(C6H4)E(C6H4)C[triple bond]C-}n] (E = O, S, SO, SO2). Particular attention was focused on the photophysical properties of these Group 10 polymetallaynes and comparison was made to their binuclear model complexes trans-[Pt(Ph)(PEt3)2C[triple bond]C(C6H4)E(C6H4)C[triple bond]CPt(Ph)(PEt3)2] and their closest Group 11 gold(I) and Group 12 mercury(II) neighbours, [MC[triple bond]C(C6H4)E(C6H4)C[triple bond]CM] (M = Au(PPh3), HgMe; E = O, S, SO, SO2). The regiochemical structures of these angular-shaped molecules were studied by NMR spectroscopy and single-crystal X-ray structural analyses. Upon photoexcitation, each one has an intense purple-blue fluorescence emission near 400 nm in dilute fluid solutions at room temperature. Harvesting of the organic triplet emissions harnessed through the strong heavy-atom effects of Group 10-12 transition metals was studied in detail. These metal-containing aryleneethynylenes spaced by chalcogen units were found to have large optical gaps and high-energy triplet states. The influence of metal- and chalcogen-based conjugation interrupters on the intersystem crossing rate and on the spatial extent of the lowest singlet and triplet excitons was fully elucidated. We discuss and compare the phosphorescence spectra of these transition-metal diynes and polyynes in terms of the nature of the metal centre, conjugated chain length and Group 16 spacer unit. Our work here indicates that high-energy triplet states in these materials intrinsically give rise to very efficient phosphorescence with fast radiative decays and one could readily observe room-temperature phosphorescence for the platinum polyynes.     

Molecular Switching in the Near Infrared (NIR) to Visible/NIR f-f emission with a Functional-Lanthanide Complexes

We report the first observation of three photon induced NIR emission (890-1,400 nm) with NIR excitation (800 nm) from a newly synthesized organic neodymium complex with known molecular structure, suggests the potential use of lanthanide probes for use in three-dimensional imaging and further the study of multi- photon induced emission process in organic-lanthanide complexes.     

Identification of novel microsatellite markers <1 Mb from the HBB gene and development of a single‐tube pentadecaplex PCR panel of highly polymorphic markers for preimplantation genetic diagnosis of beta‐thalassemia

Beta (β)‐thalassemia is one of the most common monogenic diseases worldwide. Affected pregnancies can be avoided through preimplantation genetic diagnosis (PGD), which commonly involves customized assays to detect the different combinations of β‐globin (HBB) gene mutations present in couples, in conjunction with linkage analysis of flanking microsatellite markers. Currently, the limited number of reported closely linked markers hampers their utility in indirect linkage‐based PGD for this disorder. To increase the available markers closely flanking the HBB gene, an in silico search was performed to identify all markers within 1 Mb flanking the HBB gene. Fifteen markers with potentially high polymorphism information content (PIC) and heterozygosity values were selected and optimized into a single‐tube pentadecaplex PCR panel. Allele frequencies and polymorphism and heterozygosity indices of each marker were assessed in five populations. A total of 238 alleles were observed from the 15 markers. PIC was >0.7 for all markers, with expected heterozygosity and observed heterozygosity values ranging from 0.74 to 0.90 and 0.72 to 0.88, respectively. Greater than 99% of individuals were heterozygous for at least seven markers, with at least two heterozygous markers on either side of the HBB gene. The pentadecaplex marker assay also performed reliably on single cells either directly or after whole genome amplification, thus validating its use in standalone linkage‐based β‐thalassemia PGD or in conjunction with HBB mutation detection.     

A cyanine based fluorophore emitting both single photon near-infrared fluorescence and two-photon deep red fluorescence in aqueous solution

Optical imaging provides an indispensable way to locate tumors in their early stages with high sensitivity and signal to background ratio. A heptamethine cyanine based fluorophore that emits both single photon near-infrared fluorescence and two-photon deep red fluorescence under physiological conditions was developed. Linear and nonlinear photophysical properties of this fluorophore were investigated and it demonstrated the capability to label lysosomes in cancer cells. The advantages of this fluorophore, including tolerable cytotoxicity, high fluorescence quantum yield, and the ability to emit both near-infrared single photon fluorescence and deep red two photon fluorescence in aqueous solution, give it potential to be used in intra-operatively optical image-guided tumor excision followed by two-photon fluorescence microscopy biopsy analysis after a single administration.     

(-)-Kunstleramide, a new antioxidant and cytotoxic dienamide from the bark of Beilschmiedia kunstleri gamble

A new dienamide, (2E,4E)-7-(3',4'-dimethoxyphenyl)-N-ethyl-6-(R)-hydroxyhepta- 2,4-dienamide, named (-)-kunstleramide (1), were isolated from the bark of Beilschmiedia kunstleri Gamble together with one neolignan: (+)-kunstlerone (2) and seven known alkaloids: (+)-nornuciferine (3), (-)-isocaryachine (4), (+)-cassythicine (5), (+)-laurotetanine (6), (+)-boldine (7), noratherosperminine (8), (+)-N-demethylphyllocaryptine (9). Their structures were established from spectroscopic techniques, most notably 1D- and 2D-NMR, UV, IR, OR, circular dichroism (CD) spectra and LCMS-IT-TOF. (-)-Kunstleramide (1) exhibited very poor dose-dependent inhibition of DPPH activity, with an IC?? value of 179.5 ± 4.4 μg/mL, but showed a moderate cytotoxic effect on MTT assays of A375, A549, HT-29, PC-3 and WRL-68 with EC?? values of 64.65, 44.74, 55.94, 73.87 and 70.95 μg/mL, respectively.     

Vibrational and valence photoelectron spectroscopies, matrix photochemistry, and conformational studies of ClC(O)SSCl

ClC(O)SSCl was prepared by an improved method by the reaction of [(CH(3))(2)CHOC(S)](2)S with SO(2)Cl(2) in hexane. The photoelectron spectra in the gas phase present four distinct regions, corresponding to ionizations from electrons formally located at the S, O, and Cl atoms and at the C═O bond. The vibrational IR and Raman spectra of the liquid were interpreted in terms of the most stable syn-gauche conformer (the O═C double bond syn with respect to the S-S single bond and the C-S single bond gauche with respect to the S-Cl single bond) in equilibrium with the less stable anti-gauche form, both occurring in two enantiomeric forms. The randomization process between the conformers was induced by broad-band UV-visible irradiation in matrix conditions, and several photoproducts were identified by FTIR spectroscopy. The experimental results were complemented by theoretical calculations.     

Efficient two- to five-photon excited violet emission of calix[4]arene-based multiple donor-acceptor assembly

Remarkably strong multiphoton, from two- to five-photon, upconverted violet fluorescence is first observed on a calix[4]arene-based multi-dipolar assembly which is strongly enhanced as compared to that of the corresponding dipolar counterparts.     

Synthesis and Characterization of HgII/Se/CuI Multinuclear Compounds from Mercury(II) Bis(p‐aminobenzeneselenolate) – Hg(SeC6H4NH2‐p)2

In this paper we explore an amino functionalized selenolate unit for the synthesis of new multinuclear compounds with promising interesting properties and potential precursors of semiconductors. We present for the first time the X‐ray crystallographic structure of [Hg(SeC₆H₄NH₂)₂]₂ · diox ( 1· diox) and its copper(I) derivatives: HgCu₂X₂(SeC₆H₄NH₂)₂(PPh₃)₄ · 4diox [X = Br ( 2· 4diox) and I ( 3· 4diox)]. The compounds 1 and 2 , 3 can be considered as the starting material and intermediates, respectively, for the synthesis of ternary Hg^II/Se/Cu^I nanoclusters. We also provide IR and NMR spectroscopic data and evaluate the optical features of these compounds by difuse reflectance UV/Vis spectroscopy.