Investigation of Phosphazene Superbase Interactions with [PClN].

In this study, the reaction between phosphazene superbases and a chlorophosphazene trimer ([PClN]) has been investigated. In this room temperature reaction, the phosphazene superbase (MeN)PN(MeN)P═NEt, commonly known as PEt, was shown to behave as a nucleophile, displacing one of the chlorides from [PClN] and producing the tadpole-like structure . The reaction described herein is one of the few instances of a phosphazene superbase behaving as a nucleophile rather than a Brønsted base.

Synthesis, characterization, in vitro SAR study, and preliminary in vivo toxicity evaluation of naphthylmethyl substituted bis-imidazolium salts.

A series of novel bis-imidazolium salts was synthesized, characterized, and evaluated in vitro against a panel of non-small cell lung cancer (NSCLC) cells. Two imidazolium cores were connected with alkyl chains of varying lengths to develop a structure activity relationship (SAR). Increasing the length of the connecting alkyl chain was shown to correlate to an increase in the anti-proliferative activity.

Synthesis of highly selective lysosomal markers by coupling 2-(2'-hydroxyphenyl)benzothiazole (HBT) with benzothiazolium cyanine (Cy): the impact of substituents on selectivity and optical properties.

HBT-Cy 1 has been previously reported as a highly selective fluorescent probe for lysosome visualization in live cells. To further investigate the role of the structural components of HBT-Cy in lysosome selectivity, cyanine based fluorescent probe series (2-5) have been synthesized in good yields by connecting benzothiazolium cyanine (Cy) with 2-hydroxyphenylbenzothiazole (HBT) via a meta phenylene ring. Probes 2-5 exhibited exceptional photophysical properties including bright red-emission (λ≈ 630-650 nm), a large Stokes shift (Δλ > 130 nm) and high fluorescence quantum yields (φ≈ 0.

Synthesis, characterization, in vitro SAR and in vivo evaluation of N,N'bisnaphthylmethyl 2-alkyl substituted imidazolium salts against NSCLC.

Alkyl- and N,N'-bisnaphthyl-substituted imidazolium salts were tested in vitro for their anti-cancer activity against four non-small cell lung cancer cell lines (NCI-H460, NCI-H1975, HCC827, A549). All compounds had potent anticancer activity with 2 having IC values in the nanomolar range for three of the four cell lines, a 17-fold increase in activity against NCI-H1975 cells when compared to cisplatin. Compounds 1-4 also showed high anti-cancer activity against nine NSCLC cell lines in the NCI-60 human tumor cell line screen.

Synthesis, characterization, and in vitro SAR evaluation of N,N'-bis(arylmethyl)-C-alkyl substituted imidazolium salts.

A series of C-alkyl substituted N,N'-bis(arylmethyl)imidazolium salts were synthesized, characterized, and tested for their in vitro anti-cancer activity against multiple non-small cell lung cancer cell lines by our group and the National Cancer Institute's-60 human tumor cell line screen to establish a structure-activity relationship. Compounds are related to previously published N,N'-bis(arylmethyl)imidazolium salts but utilize the historical quinoline motif and anion effects to increase the aqueous solubility. Multiple derivatives displayed high anti-cancer activity with IC values in the nanomolar to low micromolar range against a panel of non-small cell lung cancer cell lines.

Synthesis, anti-proliferative activity, SAR study, and preliminary in vivo toxicity study of substituted N,N'-bis(arylmethyl)benzimidazolium salts against a panel of non-small cell lung cancer cell lines.

A series of N,N'-bis(arylmethyl)benzimidazolium salts have been synthesized and evaluated for their in vitro anti-cancer activity against select non-small cell lung cancer cell lines to create a structure activity relationship profile. The results indicate that hydrophobic substituents on the salts increase the overall anti-proliferative activity. Our data confirms that naphthylmethyl substituents at the nitrogen atoms (N(N)) and highly lipophilic substituents at the carbon atoms (C and C(C)) can generate benzimidazolium salts with anti-proliferative activity that is comparable to that of cisplatin.

Group 13 Superacid Adducts of [PCl2N]3.

Irrespective of the order of the addition of reagents, the reactions of [PCl2N]3 with MX3 (MX3 = AlCl3, AlBr3, GaCl3) in the presence of water or gaseous HX give the air- and light-sensitive superacid adducts [PCl2N]3·HMX4. The reactions are quantitative when HX is used. These reactions illustrate a Lewis acid/Brønsted acid dichotomy in which Lewis acid chemistry can become Brønsted acid chemistry in the presence of adventitious water or HX.

Anti-tumor activity of lipophilic imidazolium salts on select NSCLC cell lines.

The anti-tumor activity of imidazolium salts is highly dependent upon the substituents on the nitrogen atoms of the imidazolium cation. We have synthesized and characterized a series of naphthalene-substituted imidazolium salts and tested them against a variety of non-smallcell lung cancer cell lines. Several of these complexes displayed anticancer activity comparable to cisplatin.

Structure and conformation of the medium-sized chlorophosphazene rings.

Medium-sized cyclic oligomeric phosphazenes [PCl2N]m (where m = 5-9) that were prepared from the reaction of PCl5 and NH4Cl in refluxing chlorobenzene have been isolated by a combination of sublimation/extraction and column chromatography from the predominant products [PCl2N]3 and [PCl2N]4. The medium-sized rings [PCl2N]m have been characterized by electrospray ionization-mass spectroscopy (ESI-MS), their (31)P chemical shifts have been reassigned, and their T1 relaxation times have been obtained. Crystallographic data has been recollected for [PCl2N]5, and the crystal structures of [PCl2N]6, and [PCl2N]8 are reported.

Synthesis, characterization, and antimicrobial activity of silver carbene complexes derived from 4,5,6,7-tetrachlorobenzimidazole against antibiotic resistant bacteria.

Silver N-heterocyclic carbene complexes have been shown to have great potential as antimicrobial agents, affecting a wide spectrum of both Gram-positive and Gram-negative bacteria. A new series of three silver carbene complexes (SCCs) based on 4,5,6,7-tetrachlorobenzimidazole has been synthesized, characterized, and tested against a panel of clinical strains of bacteria. The imidazolium salts and their precursors were characterized by elemental analysis, mass spectrometry, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction.

Nanoparticle encapsulated silver carbene complexes and their antimicrobial and anticancer properties: a perspective.

This perspective discusses the uses of silver for both antimicrobial and anticancer applications. It focuses on the synthesis of silver N-heterocyclic carbene complexes (SCCs) and their in vitro efficacy against a broad spectrum of bacteria, as well as their antitumor properties. Finally, different polymeric nanoparticles are discussed as delivery vehicles for the encapsulation of SCCs and other therapeutic agents for use in vivo.

Group 13 Lewis acid adducts of [PCl2N]3.

Phosphazene polymers are classically synthesized by the high-temperature, ring-opening polymerization (ROP) of [PCl(2)N](3) to give [PCl(2)N](n), followed by functionalization of [PCl(2)N](n) with different side groups. We investigated the interactions of [PCl(2)N](3) with Lewis acids because Lewis acids have been used to induce the high-temperature ROP of [PCl(2)N](3). The reactions of [PCl(2)N](3) with MX(3) (M = group 13, X = halides), under strict anaerobic conditions gave adducts [PCl(2)N](3)·MX(3).

Synthesis and antimicrobial studies of silver N-heterocyclic carbene complexes bearing a methyl benzoate substituent.

Due to the properties of silver as an antimicrobial, our research group has synthesized many different silver carbene complexes. Two new silver N-heterocyclic carbene complexes derived from 4,5-dichloroimidazole and theobromine bearing methyl benzoate substituents were synthesized by in situ carbene formation using silver acetate as the base in the reaction. The new compounds were fully characterized by several methods including NMR spectroscopy and X-ray crystallography.

Synthesis, stability, and antimicrobial studies of electronically tuned silver acetate N-heterocyclic carbenes.

A series of methylated imidazolium salts with varying substituents on the 4 and 5 positions of the imidazole ring were synthesized. These salts were reacted with silver acetate to afford their corresponding silver N-heterocyclic carbene (NHC) complexes. These complexes were then evaluated for their stability in water as well as for their antimicrobial efficacy against a variety of bacterial strains associated with cystic fibrosis and chronic lung infections.

A crystallographically isolated dimeric hydrolyzed chloro-phosphazene dianion.

Single crystals of the title compound bis[bis-(1-ethyl-3-methyl-imidazol-2-yl-idene)silver(I)] 1,5,5,7,11,11-hexa-chloro-2,8-di-oxa-4,6,10,12,13,14-hexa-aza-1λ(5),3,5λ(5),7λ(5),9,11λ(5)-hexa-phospha-tricyclo-[7.3.1.

Ovarian cancer activity of cyclic amine and thiaether metal complexes.

A thiaether metal complex 1-aza-4,7-dithiacyclononane-RhCl3, 2, and cyclic amine metal complexes tacn-CuBr2, 3, and Me3tacn-RuCl3, 4, have been evaluated for anticancer activity against the ovarian cancer cell line NuTu-19 and for cell toxicity against the noncancerous ovarian tissue cell line OVepi. Specifically, metal complex 2 is active when compared to cisplatin at micromolar concentrations using the MTT and cell invasion assay. The in vitro results reported warrant further evaluation of metal complex 2 in living systems.

Synthesis from caffeine of a mixed N-heterocyclic carbene-silver acetate complex active against resistant respiratory pathogens.

The bis(N-heterocyclic carbene) (NHC) silver complex, 3, with a methyl carbonate anion was formed from the reaction of the iodide salt of methylated caffeine, 1, with silver (I) oxide in methanol. Attempts to crystallize this complex from a mixture of common alcohols and ethyl acetate led to the formation of an NHC-silver acetate complex, 4. The more direct synthesis of 4 was accomplished by the in-situ deprotonation of 1 by silver acetate in methanol.

Synthesis and characterization of a trigonal bipyramidal supramolecular cage based upon rhodium and platinum metal centers.

The reaction of 4-ethynyl-pyridine with tert-butyl lithium followed by its addition to (Me3tacn)RhCl3 affords the facial octahedral complex (Me3tacn)Rh(CCPy)3, condensation of which with the square planar complex cis-(DCPE)Pt(NO3)2 results in a self-assembled trigonal bipyramidal cage with Rh(III) and Pt(II) atoms occupying the vertices.

Lewis acid adducts of [PCl2N]3.

Reaction of aluminum trichloride or gallium trichloride with the extremely weak base hexachlorotriphosphazene gives adducts in which the group 13 element is bound to a phosphazene nitrogen atom. In solution, the adducts exhibit fluxional behavior. The phosphazene ring of the adducts is distorted into a slight chair conformation.

Anion directed synthesis of paddlane and trisilver tweezer complexes based upon silver coordination chemistry.

Addition of AgBF4 or Ag(O3SCF3) to the tripodal ligand, Me3tacnRh(CCPh)3, yields a paddlane complex as well as a novel trinuclear silver "tweezer" complex based upon silver acetylene coordination chemistry. The paddlane is composed of two Me3tacnRh(CCPh)3 moieties held together by silver acetylene interactions. The tweezer complex is composed of one tripodal moiety with three silver atoms coordinated to each acetylene-Rh-acetylene face.

Silver(I)-imidazole cyclophane gem-diol complexes encapsulated by electrospun tecophilic nanofibers: formation of nanosilver particles and antimicrobial activity.

Silver(I)-imidazole cyclophane gem-diol complex, 3 [Ag2C36 N10(O)4](2+)2(x)-, where x = OH- or CO3(2-), was synthesized and well characterized. The minimum inhibition concentration tests showed that the aqueous form of 3 is 2 times less effective as an antibiotic than 0.5% AgNO3, with about the same amount of silver.

Formation of water-soluble pincer silver(I)-carbene complexes: a novel antimicrobial agent.

Silver(I)-2,6-bis(ethanolimidazolemethyl)pyridine hydroxide (4a) and silver(I)-2,6-bis(propanolimidazolemethyl)pyridine hydroxide (4b) are water-soluble silver(I)-carbene complexes that were synthesized in high yield by reacting silver(I) oxide with N-substituted pincer ligands 3 (a = 2,6-bis(ethanolimidazoliummethyl)pyridine diiodide, b = 2,6-bis(propanolimidazoliummethylpyridine)pyridine dibromide). The X-ray crystal structure of 4a is a one-dimensional linear polymer, whereas the mass spectroscopy confirms a monomer in the gas phase. A change in the anion of 4a from a hydroxide to a hexafluorophosphate formed a silver(I)-carbene complex 4c that is dimeric in structure and insoluble in water.