Synthesis and characterization of polybrominated fluorenes and their conversion to polyphenylated fluorenes and cyclopenta[def]triphenylene

We report the synthesis and characterization of polyphenylated fluorene derivatives and a ring cyclized product containing cyclopenta[def]triphenylene core. Polybromination on fluorene was achieved either by solid state reaction with bromine or utilizing Br₂/KBrO₃ in AcOH/H₂SO₄ mixture. The bromofluorenes were converted to the corresponding polyphenylated fluorenes by Suzuki coupling protocol. A hexabromofluorene underwent a multifold Suzuki coupling followed by C–H activation to produce a cyclopenta[def]triphenylene derivative. Fluorene ring showed a severe distortion from planarity beyond tetra-substitution which manifested in the optical properties.     

A pyrone remodeling strategy to access diverse heterocycles: application to the synthesis of fascaplysin natural products

The synthesis of diverse N-fused heterocycles, including the pyrido[1,2-a]indole scaffold, using an efficient pyrone remodeling strategy is described. The pyrido[1,2-a]indole core was demonstrated to be a versatile scaffold that can be site-selectively functionalized. The utility of this novel annulation strategy was showcased in a concise formal synthesis of three fascaplysin congeners.

The synthesis of diverse N-fused heterocycles, including the pyrido[1,2-a]indole scaffold, using an efficient pyrone remodeling strategy is described.     

Assembly of tetra, di and mononuclear molecular cadmium phosphonates using 2,4,6-triisopropylphenylphosponic acid and ancillary ligands

The reaction of ArPO(3)H(2) (Ar = 2,4,6-iPr(3)-C(6)H(2)) with Cd(CH(3)COO)(2).2H(2)O using various co-ligands such as methanol, dimethylformamide (DMF) and 3,5-dimethylpyrazole (DMPZH) resulted in the formation of tetranuclear assemblies [Cd(4)(ArPO(3))(2)(ArPO(3)H)(4)(CH(3)OH)(4)].3(CH(3)OH) (1), [Cd(4)(ArPO(3))(2)(ArPO(3)H)(4)(DMF)(4)].3(DMF) (2) and [Cd(4)(ArPO(3))(2)(ArPO(3)H)(4)(DMF)(2)(DMPZH)(2)].2(DMF).2(H(2)O) (3). In all of these compounds the tetranuclear cadmium array, containing two five-coordinate and two six-coordinate cadmium atoms, is held together by two mu(4) capping [ArPO(3)](2-) and four anisobidentate mu(2) [ArPO(2)(OH)](-) ligands. Each cadmium atom is bound to an additional ancillary ligand. The reaction of ArPO(3)H(2) with Cd(CH(3)COO)(2).2H(2)O in the presence of the chelating ligand 2,2'-bipyridine (bipy) leads to the exclusive formation of the dinuclear assembly [Cd(2)(ArPO(3)H)(4)(bipy)(2)].(CH(3)OH)(H(2)O) (4). The latter contains an eight-membered Cd(2)P(2)O(4) inorganic ring formed as a result of the bridging coordination action of two anisobidentate mu(2) [ArPO(2)(OH)](-) ligands. Each cadmium atom is bound by one chelating bipy and one monodentate [ArPO(2)(OH)](-) ligands. Use of four equivalents of 3,5-dimethylpyrazole leads to the formation of the mononuclear derivative [Cd(ArPO(3)H)(2)(DMPZH)(4)] (5). The molecular structure of the latter comprises of a central cadmium atom surrounded by six monodentate ligands. Four of these are neutral pyrazole ligands that occupy the equatorial plane; the remaining two are anionic phosphinate ligands which are present trans to each other. The thermal analysis of 1 and 4 reveals that the char residue obtained at 600 degrees C consists predominantly of Cd(2)P(2)O(7).     

Communicating with noise: How chaos and noise combine to generate secure encryption keys

An approach for the secure transmission of encrypted messages using chaos and noise is presented in this paper. The method is based on the synchronization of certain types of chaotic oscillators in response to a common noise input. This allows two distant oscillators to generate identical output which can be used as a key for encryption and decryption of a message signal. The noiselike synchronizing input-which contains no message information-is communicated to identical oscillators in the transmitter and the receiver over a public channel. The encrypted message is also sent over a public channel, while the key is never transmitted at all. The chaotic nature of the oscillators which generate the key and the randomness of the signal driving the process combine to make the recovery of the key by an eavesdropper extremely difficult. We evaluate system performance with respect to security and robustness and show that a robust and secure system can be obtained. (c) 1998 American Institute of Physics.     

Efficient and regioselective synthesis of pyrimido[5,4-d]pyrimidine-2,4,6,8(1H,3H,5H,7H)-tetraones with diversified substitutions

A highly regioselective synthesis of N3-, N5-, and N7-substituted pyrimidopyrimidinetetraones is reported. The synthesis of N5-monosubstituted and N5-, N7-disubstituted compounds was achieved through selective alkylation and urea mediated pyrimidinedione formation reactions. For the more synthetically challenging N3-, N5-, and N7-trisubstituted structures, in combination with computational studies, a palladium catalyzed cascade reaction was successfully employed for the simultaneous formation of the pyrimidinedione ring and functionalization of the N3 position, which provided the trisubstituted products in high yields with full control of regioselectivity. By applying this methodology, key intermediate 26 was prepared in a few synthetic steps in good overall yield for further functionalization and quick SAR development.     

Zn(OTf)2—catalyzed direct cyanation of benzylic alcohols—a novel synthesis of α-aryl nitriles

This work demonstrates an efficient method to prepare α-aryl nitriles by direct cyanation of benzylic alcohol with TMSCN in the presence of a catalytic amount of Zn(OTf)₂ under heating condition. A variety of benzylic alcohols can be converted into the corresponding α-aryl nitriles in good to excellent yields.     

Lanthanide(III) Complexes of Bis‐semicarbazone and Bis‐imine‐Substituted Phenanthroline Ligands: Solid‐State Structures,Photophysical Properties,and Anion Sensing

Phenanthroline‐based hexadentate ligands L¹ and L² bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La^III, Eu^III, Tb^III, Lu^III, and Y^III metal ions, were synthesized, and the crystal structures of [ML¹Cl₃] (M=La^III, Eu^III, Tb^III, Lu^III, or Y^III) complexes were determined. Solvent or water molecules act as coligands for the rare‐earth metals in addition to halide anions. The big Ln^III ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu^III, Tb^III, Lu^III, and Y^III centers with smaller ionic radii show CN=9. Complexes of L², namely [ML²Cl₃] (M=Eu^III, Tb^III, Lu^III, or Y^III) ions could also be prepared. Only the complex of Eu^III showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine‐5′‐triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine‐5′‐diphosphate (ADP) and adenosine‐5′‐monophosphate (AMP) was found. ³¹P NMR spectroscopic studies revealed the formation of a [EuL²(ATP)] coordination species.     

Storage performance of LiFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> nanoplates (<Emphasis Type="Italic">x </Emphasis>= 0, 0.5, and 1)

Although LiFePO₄ (LFP) is considered to be a potential cathode material for the lithium-ion batteries, its rate performance is significantly restricted by sluggish kinetics of electrons and lithium ions. Several attempts have been made so far to improve the performance of LiFePO₄ by reducing the grain size, doping with aliovalent atoms, and coating conductive materials such as carbon or RuO₂. We report here synthesis of LFP nanoplates by solvothermal method, tailoring the thickness as well as carbon coverage at surfaces to explore their influence on the storage performance. Due to the fact that Li⁺ ion diffuses along the b-axis, solvothermal method was aimed to control the thickness of nanoplates across the b-axis. We synthesized several nanoplates with various plate thicknesses along b-axis; among those, nanoplates of LFP with ～30-nm-thick b-axis having thin (2–5 nm) and uniform layer of carbon coating exhibits high storage capacity as well as high rate performances. Thus, a favorable morphology for LiFePO₄ has been achieved via solvothermal method for fast insertion/extraction of Li⁺ as compared to spherical nanoparticles of carbon-coated LFP. Galvanostatic cycling shows a capacity of 164?±?5 mAh g^?1 at 0.1 C rate, 100?±?5 mAh g^?1 at 10 C rate, and 46?±?5 mAh g^?1 at 30 C rate, with excellent capacity retention of up to 50 cycles. Further attempts have been made to synthesize LiMnPO₄ (LMP) as well as Li(Fe_1???x Mn _x )PO₄/C (x?=?0.5) nanoplates using solvothermal method. Although LiMnPO₄ does not exhibit high storage behavior comparable with that of LiFePO₄, the mixed systems have shown an impressive storage performance.     

A bacterial one-hybrid selection system for interrogating zinc finger-DNA interactions

We have developed two bacterial one-hybrid systems for interrogating and selecting zinc finger-DNA interactions. Our systems utilize two plasmids: a zinc finger-plasmid containing the gene for the zinc finger fused to a fragment of the alpha subunit of RNA polymerase and a reporter plasmid where the zinc finger-binding site is located upstream of a reporter gene-either the gene encoding the green fluorescent protein (GFP) or chloramphenicol acetyltransferase (CAT). Binding of the zinc finger domain to the target binding site results in a 10-fold increase in chloramphenicol resistance with the CAT reporter and an 8- to 22-fold increase in total cell fluorescence with the GFP reporter. The CAT reporter allows for sequence specific zinc fingers to be isolated in a single selection step whereas the GFP reporter enables quantitative evaluation of libraries using flow cytometry and theoretically allows for both negative and positive selection. Both systems have been used to select for zinc fingers that have affinity for the motif 5'-GGGGCAGAA-3' from a library of approximately 2 x 10(5) variants. The systems have been engineered to report on zinc finger-DNA binding with dissociation constants less than about 1 microM in order to be most applicable for evaluating binding specificity in an in vivo setting.