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Directly linked porphyrin dimers have attracted considerable attention because of their intriguing electronic features. Most emphasis has been placed on either dimers with large dihedral angles between the constituent planar monomeric subunits or those with overall planarity, referred to as "Planar-Twisted-Planar" and "Planar-Planar-Planar", respectively. Herein, we report a "Twisted-Planar-Twisted" framework, the hexaphyrin dimer D that exists in a trans configuration. Treatment of D with MeOH affords two isomeric dimers, MD1 and MD2, both of which incorporate a methoxy moiety and exist in cis orientations with respect to the tethering linkage. The methanol-promoted conversion is accompanied by a readily discernible color change from green to brown and is not induced to an appreciable level by other alcohols. Dimer D thus acts as a rudimentary, albeit highly selective, reaction-based methanol indicator. This work provides a promising approach for constructing reaction-based chemosensors using porphyrinoid dimers of nonplanar subunits with biased reactivity. Directly linked porphyrin dimers show intriguing electronic features but emphasis has been placed on planar monomeric units. Here, the authors report a Twisted-Planar-Twisted framework which can undergo a cis-trans transformation accompanied by a colour change in presence of methanol, making this framework applicable as a methanol sensor. [ABSTRACT FROM AUTHOR]

Three new porphyrin dyes XW45-XW47 have been synthesized employing a dialkoxy-wrapped phenothiazine donor, a tetraalkoxy-wrapped porphyrin π-framework, a benzothiadiazole (BTD)-based auxiliary acceptor, and an anchoring benzoic acid group. On the basis of our previously reported dye XW36, XW45 was synthesized by introducing a BTD unit to broaden the absorption spectrum, further introducing a hexy1-substituent into the BTD unit afforded XW46, and an additional fluorine atom was introduced to the carboxypheny1 acceptor to afford XW47. As expected, the BTD unit obviously broadens and red-shifts the absorption threshold of XW45-XW47 to ca.750 nm. Dye-sensitized solar cells (DSSCs) were fabricated based on a cobalt electrolyte using chenodeoxycholic acid (CDCA) as the coadsorbent. Under full sun illumination, XW45 exhibits an efficiency of 9.73%, which is slightly lower than that of 10.19% obtained for the reference dye SM315. By contrast, XW46 and XW47 show higher efficiencies than SM315 owing to the improved anti-aggregation ability associated with the hexy1 group on the BTD unit and better ICT effect induced by the fluorine atom on the carboxypheny1 unit. Thus, XW47 exhibits the highest efficiency of 10.41% among the porphyrin dyes. Furthermore, PT-C6 was used as the cosensitizer to improve the light harvesting ability and efficiencies of the cells due to its broad absorption within 350–560 nm. Thus, high efficiencies of 10.32%, 11.38% and 10.90% were achieved for the cosensitized solar cells based on XW45-XW47, respectively, owing to the obviously enhanced photo-current density (JSC). In addition, under 30% full sun illumination, XW46+PT-C6 exhibits a high efficiency of 13.08%. These results give an effective method for building high performance DSSCs through the cosensitization of porphyrin dyes containing a wrapped donor, a wrapped porphyrin framework and a properly substituted auxiliary benzothiadiazole unit. [ABSTRACT FROM AUTHOR]

Two fluorescence 'turn-on' Zn probes were developed by introducing an anthracenyl fluorophore through the linkage of a diphenylamino moiety at the 5-position of a dipyrrin moiety. Thus, two compounds with weak fluorescence were designed, synthesized, and employed as CHEF (chelation enhanced fluorescence) type fluorescence 'turn-on' Zn probes, which exhibit dramatic fluorescence enhancement upon addition of Zn, showing high sensitivities and impressive detection limits of 13 and 12 nM, respectively, better than their analogues containing simple aryl substituents at the 5 positions of a di- or tripyrrin moiety. In addition, both of the probes exhibit good selectivity, short response time of less than 10 s and wide applicable pH ranges. Furthermore, the weak fluorescence nature of the probes was rationalized based on viscosity dependence measurements and theoretical calculations. These results provide further insight into the development of selective and sensitive zinc probes. [ABSTRACT FROM AUTHOR]

A supramolecular fluorescent sensor of F− based on intermolecular energy transfer is described. The maximum absorption wavelength of a pyrrolic compound 1 is 472 nm, which is coincident with the emission wavelength of a dipyridylamine-anthracene compound 2. In the CH2Cl2 solution of 1 and 2, the fluorescence of 2 was quenched because of the presence of intermolecular energy transfer from 2 to 1. When F− was added to this solution, the absorption maximum wavelength of 1 shifted from 472 to 594 nm due to a deprotonation process. Simultaneously, the fluorescence of 2 was recovered because of the interruption of the intermolecular energy transfer. Based on these observations, the combination of 1 and 2 can be regarded as a novel supramolecular fluorescence enhancing F− probe. [ABSTRACT FROM AUTHOR]

Anticoagulation factor I (ACF I) isolated from the venom of Agkistrodon acutus is an activated coagulation factor X-binding protein with marked anticoagulant activity. Present studies show that holo-ACF I assumes a compactly folded structure in the range of pH 5–6, in which the most interior Trp residues and quenchers are adjacent. Tb3+ ions can completely replace both Ca2+ ions in holo-ACF I, as determined by equilibrium dialysis. Although the two Tb3+ ions in Tb3+-ACF I have slightly different luminescence efficiencies, both have similar quenching effects on the intrinsic fluorescence, suggesting that probably there are same numbers of Trp residues close to both Tb3+-binding sites. Two Tb3+-binding sites with similar apparent Tb3+ association constant values, (1.69 ± 0.02) × 107 M−1 and (1.42 ± 0.01) × 107 M−1, respectively, were further identified through Tb3+ fluorescence titration. In addition, it has been confirmed from the titration of holo-ACF I and Tb3+-ACF I with NBS that only interior Trp residues are involved in the energy transfer to Tb3+ ions and that all accessible Trp residues located in the surface of holo-ACF I have similar affinity to NBS, while those located in the surface of Tb3+-ACF I have two different kinds of affinity to NBS, which strongly suggests a conformational change of holo-ACF I upon substitution of Tb3+ for Ca2+. The results show that although the Tb3+-altered conformation of ACF I cannot support the binding of Tb3+-ACF I with FXa, determined by nondenaturing PAGE, Tb3+ ions are effective and useful fluorescence probes to analyze the structures and properties of Ca2+-binding sites in ACF I. [ABSTRACT FROM AUTHOR]

Spectroscopy studies of absorption and circular dichroism of native PPO II and azide PPO II complex demonstrate two new absorptions at 375 nm and 500 nm after azide's binding with PPO II, which are assigned as the terminal azide to copper charge transfer transitions Πo nb-to-copper and Πv nb-to-copper charge transfer transitions respectively. FT-IR spectra also demonstrate that the azide binds in terminal geometry with one of type-3 coppers. The interaction between azide and PPO II is discussed. One terminal azide's binding with one type-3 copper improves the activity of PPO II and the other three azides' further binding in terminal geometry with the type-3 coppers decreases the activity. We theorize that steric hindrance of azides makes oxygen difficult to bind in the active site. [ABSTRACT FROM AUTHOR]

Anticoagulation factor I (ACF I) from the venom of Agkistrodon acutus forms a 1:1 complex with activated coagulation factor X (FXa) in a Ca2+-dependent fashion and thereby prolongs the clotting time. In the present study, the dependence of the binding of ACF I with FXa on the concentration of Ca2+ ions was quantitatively analyzed by HPLC, and the result showed that the maximal binding of ACF I to FXa occurred at concentration of Ca2+ ions of about 1 mM. The binding of Ca2+ ions to ACF I was investigated by equilibrium dialysis and two Ca2+-binding sites with different affinities were identified. At pH 7.6, the apparent association constants K1 and K2 for these two sites were (1.8 ± 0.5) × 105 and (2.7 ± 0.6) × 104 M−1 (mean ± SE, n = 4), respectively. It was evident from the observation of Ca2+-induced changes in the intrinsic fluorescence of ACF I that ACF I underwent a conformational change upon binding of Ca2+ ions. The occupation of both Ca2+-binding sites in ACF I required a concentration of Ca2+ ions of about 1 mM, which is equal to the effective concentration of Ca2+ ions required both for maximal binding of ACF I to FXa and for the maximal enhancement of emission fluorescence of ACF I. It could be deduced from these results that the occupation of both Ca2+-binding sites in ACF I with Ca2+ ions and subsequent conformational rearrangement might be essential for the binding of ACF I to FXa. [ABSTRACT FROM AUTHOR]

Presents an abstract of a study which reported the purification of polyphenol oxidase from leaves of tobacco (Nicotiana tabacum) using acetone powder, ammonium sulfate precipitation and column chromatography.

Light-driven transcription, replication and enzyme catalysis are critically dependent upon a delicate transfer between molecular and supramolecular chirality. Chemists have well realized the impressive stereospecificity over many thermally accessible cycloaddition with chiral catalysts, but making light work in the enantiomer control of diarylethene photocyclization has proved to be more challenging. Here, we report a unique sterically hindered diarylethene (BBTE) system with absolute enantiospecific photocyclization and cycloreversion. Moreover, we have fully separated all the five thermally stable isomers, consisting of one achiral parallel conformer, one pair of anti-parallel ring-open enantiomers, and another pair of ring-closed enantiomers, whose absolute chiral configurations are entirely elucidated by single X-ray crystallographic analyses. The photo-responsive feature exhibits a reversible, complete enantio-control transformation without racemism, offering an unrivaled unimolecular enantiospecific platform for potential applications as bistable chiroptical switches and all-photonic photomemories with optical rotation as non-destructive readout. [ABSTRACT FROM AUTHOR]