A Photo-Triggered Traceless Staudinger-Bertozzi Ligation Reaction.

The use of light to control the course of a chemical/biochemical reaction is an attractive idea because of its ease of administration with high precision and fine spatial resolution. Staudinger ligation is one of the commonly adopted conjugation processes that involve a spontaneous reaction between azides and arylphosphines to form iminophosphoranes, which further hydrolyze to give stable amides. We designed an anthracenylmethyl diphenylphosphinothioester (1) that showed promising Staudinger ligation reactivity upon photo-excitation. Broadband photolysis at 360-400 nm in aqueous organic solvents induced heterolytic cleavage of its anthracenylmethyl-phosphorus bond, releasing a diphenylphosphinothioester (2) as an efficient traceless Staudinger-Bertozzi ligation reagent. The quantum yield of such a photo-induced heterolytic bond-cleavage at the optimal wavelength of photolysis (376 nm) at room temperature is ≥0.07. This work demonstrated the feasibility of photocaging arylphosphines to realize the photo-triggering of the Staudinger ligation reaction.

Heterobimetallic Ru(II)-Eu(III) complex as chemodosimeter for selective biogenic amine odorants detection in fish sample.

Gaseous biogenic amines such as putrescine, spermidine, aniline, and trimethylamine are important biomolecules that play many crucial roles in metabolism and medical diagnostics. A chemodosimetric detection assay has been developed for those gaseous amines by Ru(II)-Eu(III) heterobimetallic complexes, K{[Ru(II)((t)Bubpy)(CN)(4)](2)Eu(III)(H(2)O)(4)} (where (t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Synthesis, X-ray crystal characterization, and spectroscopic properties of this Ru(II)-Eu(III) heterobimetallic complex were reported. Binding properties of the Ru(II)-Eu(III) complex with common gases revealed that this complex is very selective to gaseous amine molecules. Sensitivity of this complex toward the amines was found as ∼log k() = 4.5-4.8. Real time monitoring of gaseous biogenic amines was applied to real fish samples (Atlantic mackerel) by studying the spectrofluorimetric responses of the Ru(II)-Eu(III) complex toward different biogenic amine concentration. GC/MS studies were also used as a reference for the studies. A linear spectrofluorimetric response was found toward biogenic amine concentration in real fish samples. This complex was found to respond specifically to those biogenic amines down to 10 ppb.

A triphenylphosphonium-functionalised cyclometalated platinum(II) complex as a nucleolus-specific two-photon molecular dye.

An organometallic cyclometalated platinum(II) complex, [Pt(L(3))Cl][PF(6)], has been synthesised from a specially designed cyclometalating ligand, HL(3) (triphenyl{5-[3-(6-phenylpyridin-2-yl)-1H-pyrazol-1-yl]pentyl}phosphonium chloride), that contains a pendant carbon chain carrying a terminal cationic triphenylphosphonium moiety. Aside from its room temperature single-photon luminescent properties in solution, [Pt(L(3))Cl](+) can also produce two-photon-induced luminescence at room temperature upon excitation at 700 nm from a mode-locked Ti:sapphire laser. Its two-photon absorption cross-section in DMF at room temperature was measured to be 28.0x10(-50) cm(4) s photon(-1). [Pt(L(3))Cl](+) is able to selectively stain the cell nucleolus. This has been demonstrated by two-photon confocal imaging of live and methanol-fixed HeLa (human cervical carcinoma) and 3T3 (mouse skin fibroblasts) cells. This organelle specificity is likely to be related to its special affinity for proteins within cell nucleoli. As a result of such protein affinity, [Pt(L(3))Cl](+) is an efficient RNA transcription inhibitor and shows rather profound cytotoxicity. On the other hand, the organelle-specific labelling and two-photon-induced luminescent properties of [Pt(L(3))Cl](+) renders it a useful nuclear dye for the 3-dimensional reconstruction of optical sections of thick tissues, for example, mouse ileum tissues, by multiphoton confocal microscopy.

The controlled formation and cleavage of an intramolecular d8-d8 Pt-Pt interaction in a dinuclear cycloplatinated molecular "pivot-hinge".

The bis(diphenylphosphino)methane (dppm)-bridged dinuclear cycloplatinated complex {[Pt(L)](2)(mu-dppm)}(2+) (Pt(2)dppm; HL: 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine) demonstrates interesting reversible "pivot-hinge"-like intramolecular motions in response to the protonation/deprotonation of L. In its protonated "closed" configuration, the two platinum(II) centers are held in position by intramolecular d(8)-d(8) Pt-Pt interaction. In its deprotonated "open" configuration, such Pt-Pt interaction is cleaved. To further understand the mechanism behind this hingelike motion, an analogous dinuclear cycloplatinated complex, {[Pt(L)](2)(mu-dchpm)}(2+) (Pt(2)dchpm) with bis(dicyclohexylphosphino)methane (dchpm) as the bridging ligand, was synthesized. From its protonation/deprotonation responses, it was revealed that aromatic pi-pi interactions between the phenyl moieties of the mu-dppm and the deprotonated pyrazolyl rings of L was essential to the reversible cleavage of the intramolecular Pt-Pt interaction in Pt(2)dppm. In the case of Pt(2)dchpm, spectroscopic and spectrofluorometric titrations as well as X-ray crystallography indicated that the distance between the two platinum(II) centers shrank upon deprotonation, thus causing a redshift in its room-temperature triplet metal-metal-to-ligand charge-transfer emission from 614 to 625 nm. Ab initio calculations revealed the presence of intramolecular hydrogen bonding between the deprotonated and negatively charged 1-pyrazolyl-N moiety and the methylene CH and phenyl C-H of the mu-dppm. The "open" configuration of the deprotonated Pt(2)dppm was estimated to be 19 kcal mol(-1) more stable than its alternative "closed" configuration. On the other hand, the open configuration of the deprotonated Pt(2)dchpm was 6 kcal mol(-1) less stable than its alternative closed configuration.

Two-photon plasma membrane imaging in live cells by an amphiphilic, water-soluble cyctometalated platinum(II) complex.

An amphiphilic, water-soluble cyclometalated Pt(II) complex with two-photon emission properties has been developed as a molecular marker specific for in vitro plasma membrane staining.

A bioaccumulative cyclometalated platinum(II) complex with two-photon-induced emission for live cell imaging.

The cyclometalated platinum(II) complex [Pt(L)Cl], where HL is a new cyclometalating ligand 2-phenyl-6-(1H-pyrazol-3-yl)pyridine containing C(phenyl), N(pyridyl), and N(pyrazolyl) donor moieties, was found to possess two-photon-induced luminescent properties. The two-photon-absorption cross section of the complex in N,N-dimethylformamide at room temperature was measured to be 20.8 GM. Upon two-photon excitation at 730 nm from a Ti:sapphire laser, bright-green emission was observed. Besides its two-photon-induced luminescent properties, [Pt(L)Cl] was able to be rapidly accumulated in live HeLa and NIH3T3 cells. The two-photon-induced luminescence of the complex was retained after live cell internalization and can be observed by two-photon confocal microscopy. Its bioaccumulation properties enabled time-lapse imaging of the internalization process of the dye into living cells. Cytotoxicity of [Pt(L)Cl] to both tested cell lines was low, according to MTT assays, even at loadings as high as 20 times the dose concentration for imaging for 6 h.

The synthesis and photophysical studies of cyclometalated Pt(II) complexes with C,N,N-ligands containing imidazolyl donors.

Two new C,N,N-type ligands (HL(2) and HL(3)), containing a C(phenyl), a N(pyridyl), and a N(imidazolyl) donor, and their cycloplatinated complexes, [Pt(L(2))Cl] (1), [Pt(L(3))Cl] (2), [Pt(L(2))(PPh(3))](+) (3) and [Pt(L(3))(PPh(3))](+) (4), have been successfully synthesized and characterized. Spectroscopic and (3)MLCT luminescent properties of these Pt(II) cyclometalated complexes were found to be pH dependent. This was attributed to the protonation/deprotonation of the acidic 1-imidazolyl-NH moieties on the ligands. All the cycloplatinated complexes (both protonated and deprotonated forms) possessed two-photon excitability with two-photon absorption cross-sections ranging from 6.0 to 30.0 GM (protonated forms) and from 16.2 to 24.9 GM (deprotonated forms).

Fluorescent DNA chemosensors: identification of bacterial species by their volatile metabolites.

Polyfluorophores built on a DNA scaffold (ODFs) were synthesized and tested for fluorescence responses to the volatiles from M. tuberculosis, E. coli and P. putida in closed Petri dishes. Two sensors in a pattern-based response could distinguish the bacterial strains accurately, suggesting the use of ODFs in rapid identification of infectious agents.

Synthesis and spectroscopic studies of cyclometalated Pt(II) complexes containing a functionalized cyclometalating ligand, 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine.

Three new luminescent cyclometalated Pt(II) complexes, [Pt(L)Cl] (1), [Pt2(L-)2] (2), and [Pt(L)(PPh3)]ClO4 (3.ClO4) (where HL=2-phenyl-6-(1H-pyrazol-3-yl)-pyridine), were synthesized and characterized by X-ray crystallography. HL represents a new class of C,N,Npyrazolyl cyclometalating ligands containing a Cphenyl, a Npyridyl, and a Npyrazolyl donor moiety, as well as a 1-pyrazolyl-NH, that can also be available for metal coordination and other chemical interactions. Complex 1 possesses intense intraligand transitions at 275-375 nm and moderately intense metal-to-ligand charge transfer (1MLCT) (dpi(Pt)-->pi*(L)) transition at 380-410 nm. The room temperature solid-state emission lambdamax of 1 occurs at 580 nm and is attributable to the 3MMLCT (dsigma*(Pt)-->pi*(L)) transition. It also displays strong phosphorescence in acetonitrile solutions at room temperature with an emission lambdamax at 514 nm, which can be tentatively assigned to the 3MLCT (pi*(L)-->dpi(Pt)) transition. Complex 1 can be deprotonated in organic solvents to yield a cycloplatinated dimer 2, which shows a relatively high room-temperature luminescent quantum yield of 0.59 in DMF (lambdamax=509 nm). Substitution of the ancillary chloro-ligand in 1 by triphenylphosphine yields 3, which also possesses a good room-temperature luminescent quantum yield of 0.52 in DMF (lambdamax=504 nm) and a better solubility in water. Complex 3 is synthesized to demonstrate the pH dependence of luminescent properties of this C,N,Npyrazolyl cyclometalated Pt(II) system. Such a pH response is ascribable to the protonation/deprotonation of the 1-pyrazolyl-NH on the C,N,Npyrazolyl cyclometalating ligand. The pKa of the 1-pyrazolyl-NH in 3, measured in 1:2 (v/v) aqueous DMF solutions, is approximately 4.0.

A "molecular pivot-hinge" based on the pH-regulated intramolecular switching of Pt-Pt and pi-pi interactions.

The binuclear cycloplatinated complex {[Pt(L)]2(mu-dppm)}2+ (1), where HL is a new cyclometalating ligand 2-phenyl-6-(1H-pyrazol-3-yl)pyridine, is found to behave as a molecular pivot-hinge in which the closing and opening of the hinge is effected by the reversible formation and cleavage of the Pt-Pt d8-d8 interaction and the intramolecular pi-pi interaction mediated by the protonation/deprotonation of the 1-pyrazolyl-NH on the cyclometalating ligand L.