Effects of novel organoantimony compounds on the fungal pathogen .

is an opportunistic fungal pathogen that causes pulmonary cryptococcosis, or an acute or chronic infection in the lungs, and cryptococcal meningitis, an infection of the brain and spinal column, in immunocompromised individuals. Fungal infections are responsible for ~1.7 million deaths each year.

Synthesis, Characterization and Antimicrobial Activity of Trimethylantimony(V) Biscyanoximates, a New Family of Antimicrobials.

Antimicrobial compounds play a critical role in combating microbial infections. However, the emergence of antibiotic and antifungal resistance and the scarcity of new antibiotic developments pose a significant threat and demand the discovery of new antimicrobials for both bacterial and fungal pathogens. Our previous work described the first generation () of organoantimony-based compounds that showed antimicrobial activity against several bacterial and fungal pathogens.

Novel antimony-based antimicrobial drug targets membranes of Gram-positive and Gram-negative bacterial pathogens.

Unlabelled: Antimicrobial resistance (AMR) poses a significant worldwide public health crisis that continues to threaten our ability to successfully treat bacterial infections. With the decline in effectiveness of conventional antimicrobial therapies and the lack of new antibiotic pipelines, there is a renewed interest in exploring the potential of metal-based antimicrobial compounds. Antimony-based compounds with a long history of use in medicine have re-emerged as potential antimicrobial agents.

Use of Unprecedented Intramolecular 1, 3-Dipolar Cycloaddition Reaction in meso-Nitrile Oxide-Containing BODIPYs as a New Pathway for the Preparation of Fused NIR Platforms.

Meso-nitrile oxide group in 1,7-Diphenyl-containing BODIPYs can be involved in highly unusual [3+2] intramolecular cycloaddition reaction with the formation of the dihydrobenzo[d]isoxazole-containing BODIPYs. Oxidation of these compounds results in the formation of unprecedented either benzisoxazole- or benzo[b]azepine-fused fully conjugated NIR absorbing BODIPYs. The photophysical properties and electronic structures of the target compounds were studied by an array of experimental and theoretical methods.

Rational Design of Iron Spin-Crossover Complexes Using Heteroscorpionate Chelates.

The optical, structural, and magnetic properties of iron(II,III) sandwich complexes, Fe(Tp') (Tp' = bis(3,5-dimethylpyrazolyl)benzotriazolylborate), are described. The intensely colored Fe(Tp') (orange) and Fe(Tp') (purple) show strong MLCT bands. Geometric isomerism for M(Tp') is established crystallographically in the racemate of chiral -Fe(Tp').

Non-Antibiotic Antimony-Based Antimicrobials.

A series of the eight novel organoantimony(V) cyanoximates of Sb(CH)L composition was synthesized using the high-yield heterogeneous metathesis reaction between solid AgL (or TlL) and Sb(CH)Br in CHCN at room temperature. Cyanoximes L were specially selected from a large group of 48 known compounds of this subclass of oximes on the basis of their water solubility and history of prior biological activity. The synthesized compounds are well soluble in organic solvents and were studied using a variety of conventional spectroscopic and physical methods.

Lithium selenometallates of triel elements, LiMSe (M = Al and Ga), aliovalent doping and their ionic conductivity.

Ternary selenometallates, LiMSe (M = Al(I) and Ga(II)), have been synthesized for the first time through high temperature solid-state reactions combining elements and LiSe in stoichiometric compositions. LiMSe crystallizes in the 2/ space group, forming a pseudo-2D layer type structure with edge sharing LiSe and MSe tetrahedra along the -axis. These layers are interleaved by octahedrally coordinated Li ions located in the interlayer space.

Ternary alkali ion thiogallates, AGaS (A = Li and Na), with isolated tetrahedral building units and their ionic conductivities.

Two new ternary thiogallates in the A5GaS4 (A = Li (i) and Na (ii)) series have been synthesized for the first time employing a gas passing route using oxide precursors and a high temperature solid state route using stoichiometric combinations of elements, respectively. Li5GaS4 crystallizes in the P21/m space group and the structure is built up of layers of corner sharing tetrahedra of LiS4 and GaS4 stacked along the a-axis and the octahedrally coordinated Li ions residing in the interlayer space. Na5GaS4 crystallizes in the Pbca space group and the structure consists of isolated (GaS4)5- tetrahedra held together by charge balancing sodium ions in distorted tetrahedral and octahedral coordination geometries.

New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties.

Interactions between well-mixed fine powders of AsO, PO, MoO, WO and NbO at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N and air atmosphere, and single crystals electrical conductivity studies.

Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered.

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X-azulene ligands (X = H, Me, COEt, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)Cr(2-isocyano-1,3-X-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime "workhorse" aryl isocyanide ligand in coordination chemistry.

Planochromism of cyanoxime anions: computational and mechanistic studies in solid state and solutions.

The benzoylcyanoxime, NC-C(=N-OH)-C(O)-CH (later H(BCO)), represents a new ampolydentate ligand that received attention in the light of useful biological properties of its coordination compounds. Colorless H(BCO), upon deprotonation, gains color that depends on the counter-cation and the system in general. Five derivatives of H(BCO), with colorless organic and inorganic mono-cations - Cs, Tl, Ag, N(CH) and As(CH) - were synthesized and characterized by the X-ray analysis, vibrational and electronic spectroscopy.

New in vitro highly cytotoxic platinum and palladium cyanoximates with minimal side effects in vivo.

Several biologically active bivalent Pd and Pt complexes with two structurally similar cyanoxime ligands abbreviated as H(DECO): 2-oximino-2-cyano-N,N'-diethylacetamide, and H(PyrCO): 2-oximino-2-cyan-N-pyrrolidine acetamide were synthesized and characterized using spectroscopic methods, thermal analysis and X-ray crystallography. Structures revealed planar cis-geometry of studied complexes. Freshly obtained Pt(DECO), Pd(DECO), Pt(PyrCO) and Pd(PyrCO) complexes were used in for in vitro cytotoxicity assays using two different etiology human cancer cell lines HeLa and WiDr cells.

Chemistry and applications of cyanoximes and their metal complexes.

During the past three decades, considerable research effort has been dedicated to a new class of organic ligands - cyanoximes - which have the general formula NC-C([double bond, length as m-dash]NOH)-R, where R is an electron-withdrawing group. The presence of the CN group makes cyanoximes ∼10 000 times more acidic and better ligands than other known conventional monoximes and dioximes. Also, in numerous cases, this group provides extra nitrogen donor atoms to support the formation of bridges between metal centres in the obtained coordination polymers.

Nanomedicine-Assisted Combination Therapy of NSCLC: New Platinum-Based Anticancer Drug Synergizes the Therapeutic Efficacy of Ganetespib.

K-RAS is the most common mutated oncogene associated with Non-Small-Cell Lung Cancer (NSCLC). So far, there are no promising chemotherapies for the direct inhibition of K-RAS, and considered to be undruggable. In this work, we have introduced a new platinum-based cyanoximate complex, Pt(MCO) as an anti-cancer drug to enhance the therapeutic efficacy of Hsp90 inhibitor drug, ganetespib for the combination therapy of NSCLC.

Soft chemical routes to electrochemically active iron phosphates.

New iron phosphates with related structures have been synthesized using hydrothermal and ion-exchange routes, and their electrochemical properties were investigated. First, NaFe(HPO) was synthesized employing a hydrothermal route and its structure was determined from single-crystal X-ray diffraction data. Subsequent Na and partial proton ion exchange with Li ion produced a known phase, LiFe(HPO), and complete deprotonation of LiFe(HPO) with Li by employing a solid-state ion-exchange route produced the new phase LiFe(PO).

Synthesis and Characterization of Anionic Lanthanide(III) Complexes with a Bidentate Sulfonylamidophosphate (SAPh) Ligand.

A series of new anionic lanthanide(III) complexes with the general formula NEt[Ln] (; H = dimethyl[(4-methylphenyl)sulfonyl]amidophosphate; Ln = La, Nd, Eu), were synthesized and characterized by IR, UV-vis, and NMR spectroscopies, the differential scanning calorimetry method, thermogravimetric and X-ray analysis, and photoluminescence measurements. Single-crystal structures of NEt[Eu] () were determined at 293 and 100 K and evidenced the phase transition. Both phases are in the monoclinic crystal system in centrosymmetric groups of the same Laue class.

Crystal and electronic structure of a hexacarbonyldiiron cluster tethered to naphthalene-2-thiolate ligands.

The structure of the previously reported complex bis(μ-naphthalene-2-thiolato-κS:S)bis(tricarbonyliron)(Fe-Fe), [Fe(CHS)(CO)], has been characterized by X-ray diffraction. In the solid state, the dinuclear complex adopts a butterfly-like shape, with an equatorial-axial spatial orientation of the naphthalene groups covalently coupled to the [SFe(CO)] unit. The asymmetric unit contains three independent [(μ-naphthalene-2-thiolato)Fe(CO)] molecules.

Zinc Complexes with Cyanoxime: Structural, Spectroscopic, and Catalysis Studies in the Pivaloylcyanoxime-Zn System.

Reaction of 2-hydroxyimino-4,4-dimethyl-3-oxo-pentanenitrile (common abbreviation HPiCO, pivaloyl-cyanoxime) with zinc sulfate in an aqueous solution results in the formation of the two new complexes: [Zn(PiCO){H(PiCO)}(HO)] (I) and tetranuclear Zn complex [Zn(μ-OH)(PiCO) (HO)] (II). Both complexes were characterized by elemental analysis, IR- and UV-visible spectra, DSC/TGA studies, and X-ray analysis. In complex II, the PiCO cyanoxime anion adopts three bidentate binding modes: O-monodentate, chelating (κ), and bridging (η) coordinations.

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state.

Several complexes of "PtL" composition containing two cyanoxime anions - 2-oximino-2-cyano-N-piperidineacetamide (PiPCO) and 2-oximino-2-cyano-N-morpholylacetamide (MCO) - have been obtained and characterized both in solution and in the solid state. Complexes exist as two distinct polymorphs: monomeric yellow complexes and dark-green [PtL] 1D polymers, while for the MCO anion a red, solvent containing dimeric [Pt(MCO)·DMSO] complex has also been isolated. The interconversion of polymorphs was investigated.

Temperature-dependent shape-responsive fluorescent nanospheres for image-guided drug delivery.

Temperature-responsive nanoparticles used in conjunction with hyperthermia promise to provide synergistic effects for increasing drug efficacy. We propose a near-infared (NIR) fluorescent system based on a upper critical solution temperature (UCST) polymer, ISP2, integrated with a NIR fluorescent dye HITC for in vivo tracking. The system forms a nanoparticle that increases its volume as temperature increases, similar to the expansion of a Hoberman sphere.

Conjugated foldamers with unusually high space-charge-limited current hole mobilities.

Charge carrier mobility and its optimization play a critical role in the development of cutting-edge organic electronic and optoelectronic devices. Even though space-charge-limited current (SCLC) hole mobilities as high as 1.4 cm(2) V(-1) s(-1) have been reported for microscopically sized highly ordered liquid-crystalline conjugated small molecules, the SCLC hole mobility of device-sized thin films of conjugated polymers is still much lower, ranging from 10(-6) to 10(-3) cm(2) V(-1) s(-1).

1D polymeric platinum cyanoximate: a strategy toward luminescence in the near-infrared region beyond 1000 nm.

We report the synthesis and properties of the first representative of a new class of PtL2 complexes with ambidentate mixed-donor cyanoxime ligands [L = 2-cyano-2-oximino-N,N'-diethylaminoacetamide, DECO (1)]. Three differently colored polymorphs of "Pt(DECO)2" (3-5) were isolated, with the first two being crystallographically characterized. The dark-green complex [Pt(DECO)2]n (5) spontaneously forms in aqueous solution via aggregation of yellow monomeric complex 3 into the red dimer [Pt(DECO)2]2 (4), followed by further oligomerization into coordination polymer 5.

Synthesis and Characterization of Two Cyanoxime Ligands, Their Precursors, and Light Insensitive Antimicrobial Silver(I) Cyanoximates.

High-yield syntheses of N-piperidine-cyanacetamide (), N-morpholyl-cyanacetamide () and their oxime derivatives N-piperidine-2-cyano-2-oximino-acetamide (HPiPCO, ) and N-morpholyc-2-cyano-2-oximino-acetamide (HMCO, ) were developed using two-step preparations. At first, the reactions of neat cyanoacetic acid esters and the respective cyclic secondary amines such as piperideine and morpholine afforded pure cyanacetamides, which were converted into cyanoximes at room temperature using the nitrosation reaction with gaseous CHONO. The synthesized compounds were investigated by means of IR, H, C and UV-visible spectroscopy.

Dual control of the selectivity in the formal nucleophilic substitution of bromocyclopropanes en route to densely functionalized, chirally rich cyclopropyl derivatives.

Densely substituted cyclopropanol and cyclopropylazole derivatives with three stereogenic carbons in the small cycle are obtained via a highly diastereoselective formal nucleophilic substitution of bromocyclopropanes. The chiral center at C-2 in bromocyclopropane dictates the configuration of the other two stereocenters that are successively installed via a sterically controlled addition of a nucleophile, followed by a thermodynamically driven epimerization of the resulting enolate intermediate.