Cloning, sequencing, analysis, and heterologous expression of the fredericamycin biosynthetic gene cluster from Streptomyces griseus

Fredericamycin (FDM) A, a pentadecaketide featuring two sets of peri-hydroxy tricyclic aromatic moieties connected through a unique chiral spiro carbon center, exhibits potent cytotoxicity and has been studied as a new type of anticancer drug lead because of its novel molecular architecture. The fdm gene cluster was localized to 33-kb DNA segment of Streptomyces griseus ATCC 49344, and its involvement in FDM A biosynthesis was proven by gene inactivation, complementation, and heterologous expression experiments. The fdm cluster consists of 28 open reading frames (ORFs), encoding a type II polyketide synthase (PKS) and tailoring enzymes as well as several regulatory and resistance proteins. The FDM PKS features a KSalpha subunit with heretofore unseen tandem cysteines at its active site, a KSbeta subunit that is distinct phylogenetically from KSbeta of hexa-, octa-, or decaketide PKSs, and a dedicated phosphopantetheinyl transferase. Further study of the FDM PKS could provide new insight into how a type II PKS controls chain length in aromatic polyketide biosynthesis. The availability of the fdm genes, in vivo characterization of the fdm cluster in S. griseus, and heterologous expression of the fdm cluster in Streptomyces albus set the stage to investigate FDM A biosynthesis and engineer the FDM biosynthetic machinery for the production of novel FDM A analogues.     

锌酞菁类染料荧光寿命的非瞬态实验估算

合成了一系列的锌酞菁染料。用循环伏安法测定了它们的氧化还原电位, 并测定了用典型的电子受体猝灭它们的荧光动力学数据。按电子转移模式确定了各染料-电子受体对的荧光猝灭速率常数κ_q对电子从染料向受体转移的自由能变化⊿G函数关系。根据测得的氧化还原电位和光谱数据计算出⊿G, 根据函数关系计算出κ_q, 代入到猝灭动力学数据κ_qτ。这样,就用非瞬态的实验估算出染料的荧光寿命r。与已知的实测文献值进行比较, r的大致范围是可信的。     

Syntheses and Crystal Structures of Two Metal Succinates Modified by Bipyridines

Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C₄H₄O₄)·1/4H₂O ( 1 ) and Cu(2, 2′‐bpy)(C₄H₄O₄)_0.5(NO₃)(H₂O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) ų, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) ų, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the Cu^II atom adopts a distorted octahedral in which the Cu^II atoms are bridged by two H₂O molecules into an infinite zigzag chain, [Cu₂(H₂O)₂(C₄H₄O₄)]_n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure.     

Steroidal saponins from rhizomes of Tupistra wattii Hook. f

Chemical examination of the fresh rhizomes of Tupistra wattii HOOK. f. led to the isolation of three new steroidal saponins, wattoside G (1), H (2), and I (3), together with one known steroidal saponin, (25S)-1beta,3beta,4beta-trihydroxyspirotan-5beta-yl-O-beta-D-glucopyranoside (4). The structures of 1-3 were established to be (25R)-1beta,2beta,3beta,5beta-tetrahydroxyspirostan-4beta-yl-O-beta-D-xylopyranoside (1), (24S,25S)-24-[(beta-D-glucopyranosyl)oxy]-1beta,2beta,3beta,4beta,5beta,7beta-hexahydroxyspirostan-6-one (2), and (24S,25S)-1beta,3beta-dihydroxy-5beta-spirostan-24-yl-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (3) on the basis of detailed analyses of physical, chemical, and spectral data. The isolated compounds were evaluated for cytotoxic activity against the cancer cell line K562 in vitro.     

The biosynthetic gene cluster for the antitumor drug bleomycin from Streptomyces verticillus ATCC15003 supporting functional interactions between nonribosomal peptide synthetases and a polyketide synthase

BACKGROUND: The structural and catalytic similarities between modular nonribosomal peptide synthetases (NRPSs) and polyketide synthases (PKSs) inspired us to search for a hybrid NRPS-PKS system. The antitumor drug bleomycin (BLM) is a natural hybrid peptide-polyketide metabolite, the biosynthesis of which provides an excellent opportunity to investigate intermodular communication between NRPS and PKS modules. Here, we report the cloning, sequencing, and characterization of the BLM biosynthetic gene cluster from Streptomyces verticillus ATCC15003. RESULTS: A set of 30 genes clustered with the previously characterized blmAB resistance genes were defined by sequencing a 85-kb contiguous region of DNA from S. verticillus ATCC15003. The sequenced gene cluster consists of 10 NRPS genes encoding nine NRPS modules, a PKS gene encoding one PKS module, five sugar biosynthesis genes, as well as genes encoding other biosynthesis, resistance, and regulatory proteins. The substrate specificities of individual NRPS and PKS modules were predicted based on sequence analysis, and the amino acid specificities of two NRPS modules were confirmed biochemically in vitro. The involvement of the cloned genes in BLM biosynthesis was demonstrated by bioconversion of the BLM aglycones into BLMs in Streptomyces lividans expressing a part of the gene cluster. CONCLUSION: The blm gene cluster is characterized by a hybrid NRPS-PKS system, supporting the wisdom of combining individual NRPS and PKS modules for combinatorial biosynthesis. The availability of the blm gene cluster has set the stage for engineering novel BLM analogs by genetic manipulation of genes governing BLM biosynthesis and for investigating the molecular basis for intermodular communication between NRPS and PKS in the biosynthesis of hybrid peptide-polyketide metabolites.     

Magnetic Properties of Pt-Based Nanoalloys: A Critical Review

In recent years, magnetic nanoalloys (MNAs) have attracted many attentions from all over the world, due to their potential applications in the broad fields of magneto-optics, data storage, engineering, and biology. Among these MNAs, Pt–M (M = Fe, Co, Ni) MNAs have been considered to be the most promising ones, due to their superparamagnetism and response to a magnetic field. Here, we firstly review the experimental work on the synthesis, characterization, and magnetic properties of Pt–Fe, Pt–Co, and Pt–Ni MNAs. Then, we discuss the recent theoretical work on Pt–Fe, Pt–Co, and Pt–Ni MNAs. Moreover, we also review the main applications of Pt–Fe, Pt–Co, and Pt–Ni MNAs in the fields of biology, information storage, and magnetic separation. It is found that the size, shape, and composition of Pt–Fe, Pt–Co, and Pt–Ni MNAs play a critical role on their fundamental magnetic properties from both the experimental and theoretical points of view. It is expected that this review could be a valuable resource for both experimental and theoretical researchers, who are interested in Pt-based MNAs.     

Effects of pattern dependence on high-power polarization-division-multiplexing applications

High-power polarization-division-multiplexing (PDM) systems or functional modules, such as self-phase-modulation (SPM)-based all-optical regenerators, cross-phase-modulation (XPM)-based wavelength convertors or format convertors, all-optical logical gate, and so on, may suffer from the effects of pattern dependence. Such effects are experimentally investigated using relative time delay variation between bit sequences with orthogonal polarization states in a 2 × 10.65 Gb/s high-power on-off keying (OOK) PDM system. Eye-diagram-based signal-to-noise ratio (SNR) and bandwidth of broadened spectrum are measured and compared. An eye-diagram-based SNR fluctuation of up to 4 dB may occur as the delay changes.     

Effect of Arylmethylene Substitutions on Molecular Structure,Optoelectronic Properties and Photovoltaic Performance of Dithienocyclopentafluorene-Based Small-Molecule Acceptors

Two dithienocyclopentafluorene-based small-molecule acceptors (SMAs) were developed that feature methylene-functionalized conjugated side chains, to study the effect of arylmethylene substitution and its number on structure, optoelectronic properties and device performance. Results showed that two SMAs have better absorption properties and planarity, lower bandgaps and higher LUMOs compared with the control SMA without conjugated side chains. The synthesized SMAs were tested in polymer solar cells for examples of their applicability. This work argues that the introduction of methylene-functionalized conjugated side chains has great potential in tuning molecular structure, optoelectronic properties, device physics and photovoltaic performance of SMAs.