Membrane association of active genes organizes the chloroplast nucleoid structure.

DNA is organized into chromatin-like structures that support the maintenance and regulation of genomes. A unique and poorly understood form of DNA organization exists in chloroplasts, which are organelles of endosymbiotic origin responsible for photosynthesis. Chloroplast genomes, together with associated proteins, form membrane-less structures known as nucleoids. The internal arrangement of the nucleoid, molecular mechanisms of DNA organization, and connections between nucleoid structure and gene expression remain mostly unknown. We show that Arabidopsis thaliana chloroplast nucleoids have a unique sequence-specific organization driven by DNA binding to the thylakoid membranes. DNA associated with the membranes has high protein occupancy, has reduced DNA accessibility, and is highly transcribed. In contrast, genes with low levels of transcription are further away from the membranes, have lower protein occupancy, and have higher DNA accessibility. Membrane association of active genes relies on the pattern of transcription and proper chloroplast development. We propose a speculative model that transcription organizes the chloroplast nucleoid into a transcriptionally active membrane-associated core and a less active periphery.

Anionic lipids facilitate membrane development and protochlorophyllide biosynthesis in etioplasts.

Dark-germinated angiosperm seedlings develop chloroplast precursors called etioplasts in cotyledon cells. Etioplasts develop lattice membrane structures called prolamellar bodies (PLBs), where the chlorophyll intermediate protochlorophyllide (Pchlide) forms a ternary complex with NADPH and light-dependent NADPH:Pchlide oxidoreductase (LPOR). The lipid bilayers of etioplast membranes are mainly composed of galactolipids, which play important roles in membrane-associated processes in etioplasts. Although etioplast membranes also contain 2 anionic lipids, phosphatidylglycerol (PG) and sulfoquinovosyldiacylglycerol (SQDG), their roles are unknown. To determine the roles of PG and SQDG in etioplast development, we characterized etiolated Arabidopsis (Arabidopsis thaliana) mutants deficient in PG and SQDG biosynthesis. A partial deficiency in PG biosynthesis loosened the lattice structure of PLBs and impaired the insertion of Mg2+ into protoporphyrin IX, leading to a substantial decrease in Pchlide content. Although a complete lack of SQDG biosynthesis did not notably affect PLB formation and Pchlide biosynthesis, lack of SQDG in addition to partial PG deficiency strongly impaired these processes. These results suggested that PG is required for PLB formation and Pchlide biosynthesis, whereas SQDG plays an auxiliary role in these processes. Notably, PG deficiency and lack of SQDG oppositely affected the dynamics of LPOR complexes after photoconversion, suggesting different involvements of PG and SQDG in LPOR complex organization. Our data demonstrate pleiotropic roles of anionic lipids in etioplast development.

Orchestration of Photosynthesis-Associated Gene Expression and Galactolipid Biosynthesis during Chloroplast Differentiation in Plants.

The chloroplast thylakoid membrane is composed of membrane lipids and photosynthetic protein complexes, and the orchestration of thylakoid lipid biosynthesis and photosynthesis-associated protein accumulation is considered important for thylakoid development. Galactolipids consist of ∼80% of the thylakoid lipids, and their biosynthesis is fundamental for chloroplast development. We previously reported that the suppression of galactolipid biosynthesis decreased the expression of photosynthesis-associated nuclear-encoded genes (PhAPGs) and photosynthesis-associated plastid-encoded genes (PhAPGs). However, the mechanism for coordinative regulation between galactolipid biosynthesis in plastids and the expression of PhANGs and PhAPGs remains largely unknown. To elucidate this mechanism, we investigated the gene expression patterns in galactolipid-deficient Arabidopsis seedlings during the de-etiolation process. We found that galactolipids are crucial for inducing both the transcript accumulation of PhANGs and PhAPGs and the accumulation of plastid-encoded photosynthesis-associated proteins in developing chloroplasts. Genetic analysis indicates the contribution of the GENOMES UNCOUPLED1 (GUN1)-mediated plastid-to-nucleus signaling pathway to PhANG regulation in response to galactolipid levels. Previous studies suggested that the accumulation of GUN1 reflects the state of protein homeostasis in plastids and alters the PhANG expression level. Thus, we propose a model that galactolipid biosynthesis determines the protein homeostasis in plastids in the initial phase of de-etiolation and optimizes GUN1-dependent signaling to regulate the PhANG expression. This mechanism might contribute to orchestrating the biosynthesis of lipids and proteins for the biogenesis of functional chloroplasts in plants.

High-resolution map of plastid-encoded RNA polymerase binding patterns demonstrates a major role of transcription in chloroplast gene expression.

Plastids contain their own genomes, which are transcribed by two types of RNA polymerases. One of those enzymes is a bacterial-type, multi-subunit polymerase encoded by the plastid genome. The plastid-encoded RNA polymerase (PEP) is required for efficient expression of genes encoding proteins involved in photosynthesis. Despite the importance of PEP, its DNA binding locations have not been studied on the genome-wide scale at high resolution. We established a highly specific approach to detect the genome-wide pattern of PEP binding to chloroplast DNA using plastid chromatin immunoprecipitation-sequencing (ptChIP-seq). We found that in mature Arabidopsis thaliana chloroplasts, PEP has a complex DNA binding pattern with preferential association at genes encoding rRNA, tRNA, and a subset of photosynthetic proteins. Sigma factors SIG2 and SIG6 strongly impact PEP binding to a subset of tRNA genes and have more moderate effects on PEP binding throughout the rest of the genome. PEP binding is commonly enriched on gene promoters, around transcription start sites. Finally, the levels of PEP binding to DNA are correlated with levels of RNA accumulation, which demonstrates the impact of PEP on chloroplast gene expression. Presented data are available through a publicly available Plastid Genome Visualization Tool (Plavisto) at https://plavisto.mcdb.lsa.umich.edu/.

Fabrication of Polypropylene Nanoplastics Via Thermal Oxidation Reaction for Human Cells Responsiveness Studies.

With the current worldwide increasing use of plastics year by year, nanoplastics (NPs) have become a global threat to environmental and public health concerns. Among plastics, polypropylene (PP) is widely used in industrial and medical applications. Owing to the lack of validated detection methods and standard materials for PP NPs, understanding the impact of PP NPs on the environmental and biological systems is still limited. Here, isotactic polypropylene (iPP) was fabricated into oxidized polypropylene micro/nanoplastics (OPPs) via a thermal oxidation using hydrogen peroxide (H2O2) under various heating temperatures. The resulting OPPs were investigated in terms of the size distribution, surface chemistry, morphology, and thermal property as well as their concentration-dependent cytotoxicity to a human intestinal epithelial cell line (Caco-2), which could be a route to uptake NPs into the body through the food chain. The average diameters of the OPPs decrease with increasing reaction temperature. The OPPs obtained at 175 °C (OPP175) were spherical in shape and had a rough surface, with size distributions of approximately 0.14 ± 0.02 µm. A significant increase in the carbonyl content of the oxidized product was confirmed by Fourier transform infrared and X-ray photoelectron spectroscopy analyses. Caco-2 cells were exposed to OPP175 in a dose-dependent manner, and a significant loss of cell viability occurred at the concentration of 100 µg/mL. Thus, this study provides a fundamental approach for the fabrication of a model of NPs for the urgently demanded in vitro and in vivo studies to assess the potential impact of NPs on biological systems.

Impacts of phosphatidylglycerol on plastid gene expression and light induction of nuclear photosynthetic genes.

Phosphatidylglycerol (PG) is the only major phospholipid in the thylakoid membrane of chloroplasts. PG is essential for photosynthesis, and loss of PG in Arabidopsis thaliana results in severe defects of growth and chloroplast development, with decreased chlorophyll accumulation, impaired thylakoid formation, and down-regulation of photosynthesis-associated genes encoded in nuclear and plastid genomes. However, how the absence of PG affects gene expression and plant growth remains unclear. To elucidate this mechanism, we investigated transcriptional profiles of a PG-deficient Arabidopsis mutant pgp1-2 under various light conditions. Microarray analysis demonstrated that reactive oxygen species (ROS)-responsive genes were up-regulated in pgp1-2. However, ROS production was not enhanced in the mutant even under strong light, indicating limited impacts of photooxidative stress on the defects of pgp1-2. Illumination to dark-adapted pgp1-2 triggered down-regulation of photosynthesis-associated nuclear-encoded genes (PhANGs), while plastid-encoded genes were constantly suppressed. Overexpression of GOLDEN2-LIKE1 (GLK1), a transcription factor gene regulating chloroplast development, in pgp1-2 up-regulated PhANGs but not plastid-encoded genes along with chlorophyll accumulation. Our data suggest a broad impact of PG biosynthesis on nuclear-encoded genes partially via GLK1 and a specific involvement of this lipid in plastid gene expression and plant development.

Nano-confined electrochemical reaction studied by electrochemical surface forces apparatus.

Electrochemical reactions in a nano-space are different from those in bulk solutions due to structuring of the liquid molecules and peculiar ion behavior at the electric double layer and are important for applications involving sensors and energy devices. The electrochemical surface forces apparatus (EC-SFA) we developed enabled us to study the electrochemical reactions in a solution nano-confined between the electrodes with varying distance (D) at nm resolution. We recorded measurements of the current-distance profiles due to the electrochemical reaction of the redox couples in the electrolyte nano-confined between Pt electrodes using our EC-SFA. We observed a long-range feedback current due to redox cycling and the sudden current increase at a short distance, the latter for the first time. This sudden current increase was two orders greater than the conventional feedback current and was observed at D < 5 nm when the electrodes were approaching and D < 200 nm on separation. We simultaneously measured the electric double layer force and the current between the electrodes in the solution to study the mechanisms of this sudden current increase in the short distance range. The results revealed a molecular insight as to how the redox species affect the current between two electrodes under nano-confinement. This study demonstrated that EC-SFA is a powerful tool for obtaining fundamental knowledge about the nano-confined electrochemical reactions for nanoelectrodes which can be applied to sensors and energy devices.

Dumbbell-Shaped 2,2'-Bipyridines: Controlled Metal Monochelation and Application to Ni-Catalyzed Cross-Couplings.

2,2'-Bipyridine ligands (dsbpys) with dumbbell-like shapes and differently substituted triarylmethyl groups at the C5 and C5' positions showed high ligand performance in the Ni-catalyzed cross-electrophile coupling and the Ni/photoredox-synergistically catalyzed decarboxylative coupling reactions. The superior ligand effects of dsbpys compared to the conventional bpy ligands were attributed to the monochelating nature of dsbpys.

Construction of Ultrathin Layer-by-Layer Films of Oligothiophene Derivatives on an Electrode.

Oligothiophene derivatives, which are known as p-type materials, have been synthesized, and their ultrathin layer-by-layer films have been constructed on an electrode using a simple and convenient dipping method. The stepwise deposition behavior of quaterthiophene and sexithiophene derivatives on the electrode via hydrogen bonding was monitored by electronic spectra measurement, and the constructed films were evaluated by X-ray photoelectron spectroscopy, grazing-incidence small-angle X-ray scattering, and cyclic voltammetry. It has been clarified that the constructed layer-by-layer films were electroactive and photoelectroactive.

Evolutionary History and Activity of RNase H1-Like Proteins in Arabidopsis thaliana.

RNase H1 is an endonuclease specific toward the RNA strand of RNA:DNA hybrids. Members of this protein family are present in most living organisms and are essential for removing RNA that base pairs with DNA. It prevents detrimental effects of RNA:DNA hybrids and is involved in several biological processes. Arabidopsis thaliana has been previously shown to contain three genes encoding RNase H1 proteins that localize to three distinct cellular compartments. We show that these genes originate from two gene duplication events. One occurred in the common ancestor of dicots and produced nuclear and organellar RNase H1 paralogs. Second duplication occurred in the common ancestor of Brassicaceae and produced mitochondrial- and plastid-localized proteins. These proteins have the canonical RNase H1 activity, which requires at least four ribonucleotides for endonucleolytic digestion. Analysis of mutants in the RNase H1 genes revealed that the nuclear RNH1A and mitochondrial RNH1B are dispensable for development under normal growth conditions. However, the presence of at least one organellar RNase H1 (RNH1B or RNH1C) is required for embryonic development. The plastid-localized RNH1C affects plastid DNA copy number and sensitivity to replicative stress. Our results present the evolutionary history of RNH1 proteins in A. thaliana, demonstrate their canonical RNase H1 activity and indicate their role in early embryonic development.

Synthesis, Structures, and Photoluminescent Properties of Tricyanidonitridorhenium(V) Complexes with Bipyridine-Type Ligands.

Tricyanidonitridorhenium(V) complexes with 2,2'-bipyridine (bpy) derivatives in which the 4 and 4' positions were substituted by X, [ReN(CN)3(X2bpy)]- (X = NMe2, NH2, OMe, Me, Cl, and Br), were newly synthesized and characterized. The structures of the new complexes were determined by single-crystal X-ray analysis. UV-vis spectra of the complexes in dimethyl sulfoxide (DMSO) showed that the peak maximum wavelengths of rhenium-to-π* bpy-type-ligand charge transfer were in the range of 474-542 nm. Cyclic voltammograms in n-(C4H9)4NPF6-DMSO showed one-electron oxidation and reduction waves corresponding to the Re(VI/V) and X2bpy0/- processes, respectively. The new complexes and [ReN(CN)3bpy]- showed photoluminescence in the crystalline phase at 295 and 80 K and in DMSO at 295 K. The origin of the emission in DMSO was attributed to the triplet nature of the rhenium-to-π* bpy-type-ligand charge-transfer transition. Density functional theory calculations showed that the highest occupied and lowest unoccupied molecular orbitals were primarily localized on the dxy orbital of the rhenium and π* orbitals of the bpy-type ligand, respectively.

Further enhancement of the near-field on Au nanogap dimers using quasi-dark plasmon modes.

Metallic nanogap dimers are extremely useful for enhancing surface-enhanced Raman scattering and various nonlinear optical effects employing near-field enhancement effects induced by the localized surface plasmon resonance. However, the metallic nanogap dimers exhibit an intense light scattering due to the strong dipole-dipole interaction between two metallic nanostructures and, therefore, are not necessarily a structural design that exhibits the highest near-field enhancement due to the radiation loss. Here, we propose further enhancement of the near-field on metallic nanogap dimers using quasi-dark plasmon modes. By coupling with gold (Au) nanorods having the same plasmon resonant wavelength, but completely different sizes, a quasi-dark plasmon mode, which reduces the radiation loss slightly, is induced, resulting in the elongation of the plasmon dephasing time. As a result, the signal of surface-enhanced Raman scattering of crystal violet molecules adsorbed on the Au nanogap dimer is enhanced up to about three times as compared to that measured using the Au nanogap dimer without the Au nanorods. Scattering spectrum measurements as well as electromagnetic simulations were performed to clarify the mechanism for further enhancement of the near-field. The proposed coupled plasmonic system is expected to be advantageous, especially in enhancing nonlinear optical effects using plasmonic enhancement effects.

Galactolipids Are Essential for Internal Membrane Transformation during Etioplast-to-Chloroplast Differentiation.

Etioplasts developed in angiosperm cotyledon cells in darkness rapidly differentiate into chloroplasts with illumination. This process involves dynamic transformation of internal membrane structures from the prolamellar bodies (PLBs) and prothylakoids (PTs) in etioplasts to thylakoid membranes in chloroplasts. Although two galactolipids, monogalactosyldiacylglycerol (MGDG) and digalactosyldiacylglycerol (DGDG), are predominant lipid constituents of membranes in both etioplasts and chloroplasts, their roles in the structural and functional transformation of internal membranes during etioplast-to-chloroplast differentiation are unknown. We previously reported that a 36% loss of MGDG by an artificial microRNA targeting major MGDG synthase (amiR-MGD1) only slightly affected PLB structures but strongly impaired PT formation and protochlorophyllide biosynthesis. Meanwhile, strong DGDG deficiency in a DGDG synthase mutant (dgd1) disordered the PLB lattice structure in addition to impaired PT development and protochlorophyllide biosynthesis. In this study, thylakoid biogenesis after PLB disassembly with illumination was strongly perturbed by amiR-MGD1. The amiR-MGD1 expression impaired the accumulation of Chl and the major light-harvesting complex II protein (LHCB1), which may inhibit rapid transformation from disassembled PLBs to the thylakoid membrane. As did amiR-MGD1 expression, dgd1 mutation impaired the accumulation of Chl and LHCB1 during etioplast-to-chloroplast differentiation. Furthermore, unlike in amiR-MGD1 seedlings, in dgd1 seedlings, disassembly of PLBs after illumination was retarded. Because DGDG but not MGDG prefers to form the bilayer lipid phase in membranes, the MGDG-to-DGDG ratio may strongly affect the transformation of PLBs to the thylakoid membrane during etioplast-to-chloroplast differentiation.

Digalactosyldiacylglycerol Is Essential for Organization of the Membrane Structure in Etioplasts.

Angiosperms germinated in the dark develop etioplasts, the chloroplast precursors, in cotyledon cells. Etioplasts contain lattice membrane structures called prolamellar bodies (PLBs) and lamellar prothylakoids as internal membrane systems. PLBs accumulate the chlorophyll intermediate protochlorophyllide (Pchlide) in a complex with NADPH and light-dependent NADPH:Pchlide oxidoreductase (LPOR). Two galactolipids, monogalactosyldiacylglycerol and digalactosyldiacylglycerol (DGDG), are major constituents of etioplast membranes. We previously reported that monogalactosyldiacylglycerol facilitates the synthesis of Pchlide and the formation of the Pchlide-LPOR-NADPH complex in etioplasts, but the importance of DGDG in etioplasts is still unknown. To determine the role of DGDG in etioplast development and functions, we characterized a knockout mutant (dgd1) of Arabidopsis (Arabidopsis thaliana) DGD1, which encodes the major isoform of DGDG synthase, in the etioplast development stage. In etiolated dgd1 seedlings, DGDG content decreased to 20% of the wild-type level, the lattice structure of PLBs was disordered, and the development of prothylakoids was impaired. In addition, membrane-associated processes of Pchlide biosynthesis, formation of the Pchlide-LPOR-NADPH complex, and dissociation of the complex after the photoconversion of Pchlide to chlorophyllide were impaired in dgd1, although the photoconversion reaction by LPOR was not affected by the DGDG deficiency. Total carotenoid content also decreased in etiolated dgd1 seedlings, but the carotenoid composition was unchanged. Our data demonstrate a deep involvement of DGDG in the formation of the internal membrane structures in etioplasts as well as in membrane-associated processes of pigment biosynthesis and pigment-protein complex organization.

Terminal Ligand (L) Effects on Zero-Magnetic-Field Splitting in the Excited Triplet States of [{Mo6Br8}L6]2- (L = Aromatic Carboxylates).

We report the emission properties of the octahedral hexamolybdenum(II) bromide-core ({Mo6Br8}4+) clusters having a series of terminal aromatic carboxylate ligands (RCOO), [{Mo6Br8}(RCOO)6]2-, in solution and crystalline phases. The acid dissociation constant of RCOOH (p Ka(L)) was shown to govern the redox and emission properties of the clusters. Temperature ( T)-controlled emission experiments (3-300 K) demonstrated that the clusters showed large T-dependent emission energies (ν̃em) and lifetimes (τem) because of zero-magnetic-field splitting in the emissive excited triplet (T1) states. The spin sublevel (Φ n, n = 1-4) model in the T1 state of the cluster explained very well the T-dependent emission characteristics (ν̃em and τem), irrespective of the clusters studied. Furthermore, we revealed that the energy difference between the lowest-energy (Φ1) and energetically upper-lying third (Φ3) or fourth spin sublevels (Φ4), Δ E13 or Δ E14, respectively, correlated very well with p Ka( L). The results are discussed in terms of the variation of the effective nuclear charge of the Mo metal center(s) in [{Mo6Br8}(RCOO)6]2- with that of p Ka(L).

Monogalactosyldiacylglycerol Facilitates Synthesis of Photoactive Protochlorophyllide in Etioplasts.

Cotyledon cells of dark-germinated angiosperms develop etioplasts that are plastids containing unique internal membranes called prolamellar bodies (PLBs). Protochlorophyllide (Pchlide), a precursor of chlorophyll, accumulates in PLBs and forms a ternary complex with NADPH and light-dependent NADPH:protochlorophyllide oxidoreductase (LPOR), which allows for the rapid formation of chlorophyll after illumination while avoiding photodamage. PLBs are 3D lattice structures formed by the lipid bilayer rich in monogalactosyldiacylglycerol (MGDG). Although MGDG was found to be required for the formation and function of the thylakoid membrane in chloroplasts in various plants, the roles of MGDG in PLB formation and etioplast development are largely unknown. To analyze the roles of MGDG in etioplast development, we suppressed MGD1 encoding the major isoform of MGDG synthase by using a dexamethasone-inducible artificial microRNA in etiolated Arabidopsis (Arabidopsis thaliana) seedlings. Strong MGD1 suppression caused a 36% loss of MGDG in etiolated seedlings, together with a 41% decrease in total Pchlide content. The loss of MGDG perturbed etioplast membrane structures and impaired the formation of the photoactive Pchlide-LPOR-NADPH complex and its oligomerization, without affecting LPOR accumulation. The MGD1 suppression also impaired the formation of Pchlide from protoporphyrin IX via multiple enzymatic reactions in etioplast membranes, which suggests that MGDG is required for the membrane-associated processes in the Pchlide biosynthesis pathway. Suppressing MGD1 at several germination stages revealed that MGDG biosynthesis at an early germination stage is particularly important for Pchlide accumulation. MGDG biosynthesis may provide a lipid matrix for Pchlide biosynthesis and the formation of Pchlide-LPOR complexes as an initial step of etioplast development.

Shoot Removal Induces Chloroplast Development in Roots via Cytokinin Signaling.

The development of plant chloroplasts is regulated by various developmental, environmental, and hormonal cues. In Arabidopsis (Arabidopsis thaliana), chloroplast development is repressed in roots via auxin signaling. However, roots develop chloroplasts when they are detached from the shoot. In contrast to auxin, cytokinin positively affects chloroplast development in roots, but the role and signaling pathway of cytokinin in the root greening response remain unclear. To understand the regulatory pathways of chloroplast development in the plant stress response, we examined the mechanisms underlying the conditional greening of detached roots. In wild-type Arabidopsis roots, shoot removal activates type B ARABIDOPSIS RESPONSE REGULATOR (ARR)-mediated cytokinin signaling and induces chlorophyll accumulation and photosynthetic remodeling. ARR1 and ARR12 are essential for up-regulating nucleus- and plastid-encoded genes associated with chloroplast development in detached roots. In this process, WOUND INDUCED DEDIFFERENTIATION1 and class B GATA transcription factors (B-GATAs) act upstream and downstream of ARRs, respectively. Overexpression of B-GATAs promotes root greening, as does shoot removal, dependent on a light signaling transcription factor, LONG HYPOCOTYL5. Auxin represses the root greening response independent of ARR signaling. GNC-LIKE (GNL), a B-GATA, is strongly up-regulated in detached roots via ARR1 and ARR12 but is repressed by auxin, so GNL may function at the point of convergence of cytokinin and auxin signaling in the root greening response.

Emission Tuning of Heteroleptic Arylborane-Ruthenium(II) Complexes by Ancillary Ligands: Observation of Strickler-Berg-Type Relation.

Novel heteroleptic arylborane-ruthenium(II) complexes having a series of ancillary ligands L' ([Ru(B2bpy)L'2]2+) in CH3CN showed low-energy/intense metal-to-ligand charge transfer (MLCT)-type absorption and intense/long-lived emission compared to the reference complexes. The spectroscopic and photophysical properties of [Ru(B2bpy)L'2]2+ were shown to be manipulated synthetically by the electron-donating ability of the ancillary ligand(s). The intense and long-lived emission observed for [Ru(B2bpy)L'2]2+ in CH3CN at 298 K is responsible for the accelerated radiative and decelerated nonradiative decay processes, which are controllable through the electronic structures of the ancillary ligand(s). On the basis of the present systematic study, furthermore, we succeeded in demonstrating the Strickler-Berg-type relation between the molar absorption coefficients of the MLCT bands and the radiative rate constants of the complexes.

Zero-Magnetic-Field Splitting in the Excited Triplet States of Octahedral Hexanuclear Molybdenum(II) Clusters: [{Mo6X8}Y6]2- (X, Y = Cl, Br, I).

The temperature ( T) dependences of the emissions from the tetra- n-butylammonium salts of [{Mo6X8}Y6]2- (X, Y = Cl, Br, and I) in optically transparent polyethylene glycol dimethacrylate matrixes were studied in the T range of 3-300 K. [{Mo6Cl8}Y6]2-, [{Mo6Br8}Y6]2-, and [{Mo6I8}I6]2- showed the T-dependent emission characteristics similar to those of other hexanuclear Mo(II), Re(III), and W(II) clusters reported previously, while [{Mo6I8}Br6]2- and [{Mo6I8}Cl6]2- exhibited the emission properties different from those of other [{Mo6X8}Y6]2- clusters. The photophysical behavior of these clusters was explained by the excited triplet state spin-sublevel ( Φn, n = 1-4) model irrespective of the nature of X and Y. The zero-magnetic-field splitting energies between the lowest energy (Φ1) and the higher energy spin sublevels (Φ4 or Φ3) caused by the first- or second-order spin-orbit coupling, Δ E14 or Δ E13, were evaluated to be 620-870 or 50-99 cm-1, respectively. We found the linear correlation between the Δ E14 or Δ E13 value and the fourth power of the atomic number ( Z) of the inner halide X: Δ E14 or Δ E13 vs { Z(X)}4 (correlation coefficient: cc = ∼ 0.999). Furthermore, we also found the correlation between Δ E14 or Δ E13 and the 95Mo NMR chemical shift of the cluster. These findings gave very important insight into the spin-orbit coupling and zero-magnetic-field splitting in the excited triplet states of transition metal complexes.

A novel multimode sensor showing cation-dependent fluorescence colour.

A novel sensor, 4-[2-(9-anthryl)ethynyl]-1,10-phenanthroline (1), exhibits highly intense fluorescent in the wavelength region of 440-600 nm (maximum wavelength (λf) = 470 nm) with the quantum yield (Φf) and lifetime (τf) being 0.90 and 4.2 ns, respectively, in CH3CN at 298 K. In the presence of a divalent cation (M2+ = Ba2+, Ca2+, Mg2+, or Zn2+) in CH3CN, sensor 1 can tightly bind M2+ and shows intense fluorescent (Φf = 0.90-0.19, τf = 2.1-6.9 ns) with the color being dependent on the nature of M2+ (λf = 514-584 nm). The results demonstrate that a single fluorescent sensor 1 is capable of simultaneous identification and quantitation of M2+ based on λf and the fluorescent intensity (Φf), respectively. The fluorescence maximum energy of the [1-M2+] complex is shown to correlate linearly with the pKa value of M2+. The spectroscopic and photophysical properties of sensor 1 in the absence and presence of M2+ are also discussed.