Direct optical detection of singlet oxygen from a single cell

Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level.     

Fluorescent pH sensors with negligible sensitivity to ionic strength

Optical pH determination has the fundamental disadvantage of measuring a signal that depends on the ionic strength of the sample. The problem originates from the complex relationship between the proton activity and the concentration of the pH-sensitive dye. The effect of ionic strength on the signal depends on the charge of the indicator and its environment, e.g. the immobilisation matrix. We present novel lipophilic fluorescein esters carrying one negative charge. They are embedded in an uncharged, highly proton-permeable hydrogel to give optical pH sensors that show a negligible cross-sensitivity towards ionic strength. The fluorescent dyes differ in their substituents. This variation of substituents results in dissociation constants between 5.5 and 8.5. The indicators were made lipophilic by esterification of the carboxy group with a C(18) alkyl chain. Since their spectral properties are quite similar, two indicators may be used in one sensor. This results in an optical pH sensor with a dynamic range that extends from pH 4.5 to 8.     

Preparation and characterization of poly(amidoamine) dendrimers functionalized with a rhenium carbonyl complex and PEG as new IR probes for carbonyl metallo immunoassay

The first poly(amidoamine) (PAMAM) dendrimers tethered with both (η⁵-cyclopentadienyl) rhenium tricarbonyl (CpRe(CO)₃) units and polyethylene glycol (PEG) chains were prepared and characterized by combining NMR spectroscopy and Fourier-transform IR spectroscopy. Grafting of CpRe(CO)₃ units was achieved by reductive amination of formyl-CpRe(CO)₃ with the peripheral amines of generation 3 and 4 PAMAMs to yield dendrimers labeled with a variable number of CpRe(CO)₃ units, ranging from 8 to 14 for PAMAM-G3 and 17-30 for PAMAM-G4. PEG chains of different lengths were then attached to some of the remaining peripheral amines, and their respective ability to improve the solubility of the metallodendrimers in aqueous buffered media was evaluated. These metallodendrimers represent new infrared probes designed to be coupled to immunological reagents for the amplification of the IR signal in carbonyl metallo immunoassay (CMIA).     

Strukturen von Bis(trifluormethyl)halogeno‐ und ‐thiocyanato‐mercuraten, [Hg(CF3)2X]— (X = Br,I, SCN), und ein Vergleich der Strukturparameter der CF3‐Gruppen

Structures of Bis(trifluoromethyl)halogeno and thiocyanato Mercurates, [Hg(CF₃)₂X]^— (X = Br, I, SCN), and a Comparison of the Structural Parameters of the CF₃ Groups [(18‐C‐6)K]₂[Hg(CF₃)₂SCN]₂ (1) and [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂X]₂ (X = Br (2) , I (3) ) are prepared and their crystal structures are determined. [(18‐C‐6)K]₂[Hg(CF₃)₂SCN]₂ (1) crystallizes in the monoclinic space group P2₁/c with Z = 2, [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂Br]₂ (2) in the monoclinic space group P2₁/n with Z = 2 and [P(CH₃)(C₆H₅)₃]₂[Hg(CF₃)₂I]₂ (3) in the triclinic space group P1¯ with Z = 1. In the solid state the three compounds form dimeric anions with planar Hg₂X₂ rings. The structural parameters of the Hg(CF₃)₂ units in the till now known bis(trifluoromethyl)halogeno mercurates are compared. In all compounds one nearly symmetric and one distorted CF₃ group exist. The largest differences of the C—F bond lengths is found for [(18‐C‐6)K][Hg(CF₃)₂I]. This can be regarded as the experimental evidence for the properties of trifluoromethyl mercury compounds to act as excellent difluorocarbene sources in the presence of alkali iodides.     

Er2S[SiO4]: Ein Erbiumsulfid‐ortho‐Oxosilicat mit ungewöhnlicher Sulfidionen‐Koordination

During the reaction of cadmium sulfide with erbium and sulfur in evacuated silica ampoules pink lath‐shaped crystals of Er₂S[SiO₄] occur as by‐product which were characterized by X‐ray single crystal structure analysis. The title compound crystallizes orthorhombically in the space group Cmce (a = 1070.02(8), b = 1235.48(9), c = 683.64(6) pm) with eight formula units per unit cell. Besides isolated ortho‐oxosilicate units [SiO₄]^4?, the crystal structure contains two crystallographically independent Er³⁺ cations which are both eightfold coordinated by six oxygen and two sulfur atoms. The sulfide anions are surrounded by four erbium cations each in the shape of very distorted tetrahedra. These excentric [SEr₄]¹⁰⁺ tetrahedra build up layers according to by vertex‐ and edge‐connection. They are piled parallel to (010) and separated by the isolated ortho‐oxosilicate tetrahedra.     

Three Lead(II) Complexes in One Coordination Polymer, [Pb(TpyCl)Cl][Pb(TpyCl)Cl2][PbCl3](CH3OH)

[Pb(TpyCl)Cl][Pb(TpyCl)Cl₂][PbCl₃](CH₃OH) ( 1 ), a new coordination polymer of divalent lead with the ligand 4′‐chloro‐2,2′:6′,2"‐terpyridine (TpyCl), was obtained as single crystals by the branched tube method. The crystal structure contains three complexes, the cationic [Pb(TpyCl)Cl]⁺, the neutral [Pb(TpyCl)Cl₂] and the anionic [PbCl₃]^–, which are connected through bridging chlorides and hydrogen bonds to a two‐dimensional coordination polymer. In all three complexes, the arrangement around the Pb²⁺ ion suggests the existence of a stereoactive lone pair.     

Bulky Cations and Four different Polyiodide Anions in [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I12)

Black single crystals of [Lu(Db18c6)(H₂O)₃(thf)₆]₄(I₃)₂(I₅)₆(I₈)(I₁₂) were obtained from lutetium, I₂ and Db18c6 (dibenzo‐18‐crown‐6) in THF solution. In the bulky cation, Lu³⁺ is surrounded by nine oxygen atoms, six of Db18c6 and three of water molecules to which two THF molecules are attached each. Meanwhile, four polyiodide anions, (I₃)^–, (I₅)^–, (I₈)^2– and (I₁₂)^2–, in a 2:6:1:1 ratio form a three‐dimensional network and leave space for the bulky cations.