Bis-thiosemicarbazones derived from the β-diketone benzoylacetone (H3banR, R = Me, Et, Ph) are potentially tetradentate N2S2 ligands whose coordination chemistry with copper is reported. In the absence of oxygen and in the presence of base they form anionic CuII complexes of the fully deprotonated ligands [CuII(banR)]–. Upon exposure to atmospheric oxygen they undergo a complex series of reactions

Peptide nucleic acid (PNA) microarrays are expected to be developed as a new generation of gene detection tools. However, poor water solubility and the limitation of the sequence design of achiral PNA probes mainly hinder their application. Accordingly, (R)-diethylene glycol containing a chiral PNA (miniPEG-γPNA) has been developed to solve these problems. Light-directed synthesis is an effective method

Few comparisons have been made between low-aromaticity marine and lacustrine oil shales and their kerogens, because the reliability of structural analyses has been limited by a reliance on only one method of kerogen isolation, HCl-HF. Therefore, a detailed analysis by 13C NMR and X-ray photoelectron spectroscopy (XPS) was made for Attrat marine oil shale (Jordan) and Colorado (Green River) lacustrine

Lewis base catalysed halofunctionalisation reactions of alkenes are well established and allow access to, among others, various oxygen containing heterocycles. By exploiting the known conversion of N-heterocyclic carbenes into the corresponding thioureas it has been possible to prepare and study a range of chiral and non-chiral Lewis base catalysts for such reactions. Although all thiourea catalysts

The reversible diffusion controlled cyclic voltammetry for the reduction of TCNQF­n0/1–/2– (where n = 0, 1, 2, 4) changes significantly on addition of Co2+ and Ni2+ transition metal ions (M2+) because the kinetics associated with electrocrystallisation of the resulting coordination polymers [M(TCNQF2)2(H2O)2] and [M(TCNQF2)] are rapid on the voltammetric time scale. The voltammetry of solutions containing

Colloidal two-dimensional (2D) semiconductor nanocrystals are of great importance due to their remarkable optical and electronic properties. Herein, shape-controllable synthesis of 2D wurtzite CdTe nanoplatelets (NPLs) by simply tailoring the reactivity of a tellurium (Te) precursor is reported. Ribbon-, shield-, and bullet-like 2D CdTe NPLs were prepared by a stepwise conversion from CdTe magic-size

Rare earth (RE) complexes of 3-benzoylpropanoate (bp), [RE(bp)3(H2O)n] (RE = La, n = 2; RE = Y, Ce, Pr, Nd, Yb, n = 1) and 3-phenylpropanoate (pp), [RE(pp)3] (RE = Y, La, Ce, Nd, Yb), have been prepared by metathesis reactions between the corresponding rare earth chloride and the appropriate sodium carboxylate. Analysis by single-crystal X-ray diffraction finds that both RE bp and pp complexes favour

A new ionic liquid was synthesised, and its chemical structure was elucidated by FT-IR, 1D NMR, 2D NMR, and mass analyses. Some physical properties, thermal behaviour, and thermal stability of this ionic liquid were investigated. The formation of a two-protonic acid salt namely 4,4′-trimethylene-N,N′-dipiperidinium sulfate instead of 4,4′-trimethylene-N,N′-dipiperidinium hydrogensulfate was evidenced

The reactivity and synthesis of new analogues of pyrido[1,2-a]benzimidazoles have been explored. Twenty-three derivatives bearing phenoxy, thiophenoxy, aniline, and aryl groups at the 1-position were successfully synthesised in 25–91 % yield, via nucleophilic substitution, Buchwald–Hartwig amination, and Suzuki coupling type processes. Solvent free synthetic protocols were employed to achieve the nucleophilic

Quinacridone chemistry has been developed which provides a source of new compounds that have potential application in organic photovoltaic (OPV) devices. Phosphoryl chloride is used for the conversion of carbonyl groups in N,N′-dialkylquinacridones, generating reactive intermediates that enable selective condensation with either one or two nucleophilic molecules under mild conditions.

In an ongoing study of the products formed on pyrolysis of chitin (4) under a range of conditions, we now detail the isolation and characterisation of the crystalline and hitherto undetected pyridine N-oxide 18 and enamide 19. Pathways for the formation of these products have been proposed and subjected to both experimental and computational assessment.

A synthetic method to prepare 1H-indenes and partially hydrogenated methanonaphtho[1,2-c]furan-1,3(4H)-diones from gold(i)-catalysed 1,4-enyne acetate cycloisomerisation and oxidation or Diels–Alder reaction with maleic anhydride is described. The proposed mechanism involves Rautenstrauch rearrangement of the 1,4-enyne motif to give an in situ formed 1,3-cyclopentadiene intermediate. This is followed

One new furoquinoline alkaloid, leptanoine D (1) and nine known alkaloids 2–10 were isolated from Pitaviaster haplophyllus. Leptanoine D (1) contains a typically unstable vinyl ether moiety and was structurally elucidated based on 2D NMR, (+)-HR-ESI-MS, and ECD data. The structures of the known furoquinoline alkaloids leptanoine A (11) and B (12) have also been revised. Compounds 1–10 were screened

Multi-responsive materials have received extensive interest in many areas due to their smart characteristics. This paper presents rationally designed multi-responsive spherical polyelectolyte brushes composed of a solid polystyrene (PS) core and a poly (2-(dimethylamino) ethyl methacrylate) (PDMAEMA) shell synthesized by photoemulsion polymerization. Based on dynamic light scattering, Zeta potential

We report on the synthesis and structural features of NMe2-modified β-diketiminate-supported boron difluoride compounds (LArBF2: LAr = [HC(NAr)2(CNMe2)2]–; LPh: Ar = Ph; LTol: Ar = p-tolyl; LXyl: Ar = m-xylyl). The title compounds were prepared in moderate yields (~65 %) by in situ deprotonation of the corresponding ligands LArH using KH, followed by the addition of BF3OEt2. According to solid-state

Biorefineries are a new concept in chemical manufacturing in which naturally occurring, sustainable biomass resources such as forestry and agricultural waste are converted to diverse fuel and chemical product streams, akin to the processing of non-renewable fossil fuels by petrochemical refineries. Biomass derived from waste agricultural and forestry materials or non-food crops offers the most easily

The utility of dendrimers as effective carriers for targeted drug delivery and imaging has been facilitated by a high degree of molecular uniformity, narrow molecular weight distribution, tunable size and shape characteristics, and multivalency. Dendrimer–quantum dot (QD) nanocomposites have traditionally been synthesised by electrostatic self-assembly of preformed dendrimers and QDs, but higher generations

The effect of TiCl4 concentration on the phase transformations among the TiO2 polymorphs was studied using in situ powder X-ray diffraction and Raman spectroscopy. Interestingly, the primarily amorphous TiO2 solid obtained after thermolysis of TiCl4 at 80°C contained some anatase and rutile phases for low (≤18 mM) and high (≥27 mM) TiCl4 concentrations, respectively. These samples produced anatase

Therapeutic delivery of neuropeptides including oxytocin and somatostatin is associated with numerous difficulties including low stability, low oral bioavailability, and a short half-life in vivo. For delivery to the brain, these issues are exacerbated by difficulties in crossing the blood–brain barrier. Lipid-based nanomaterials may offer specific advantages for the delivery of therapeutic peptides

Protein-based materials are widely used in biomedical applications. Often the proteins need to be crosslinked in order to be stable for application. Here, we explored the use of 5,5′-bisvanillin as a potentially non-toxic crosslinker that can react with lysine residues on proteins. To demonstrate the success of the crosslinking reaction, polymer–protein conjugates based on bovine serum albumin (BSA)

A safer route than that previously published for the synthesis of [BeI2(OEt2)2] has been developed. Reactions of beryllium dihalide complexes [BeX2(OEt2)2] (X = Br or I) with either LiMe or LiBun lead to mixtures of products, which have been shown to act as sources of ‘BeR2’ (R = Me or Bun) in previous synthetic studies. Here, a titration method has been developed to determine the quantity of metal

In this work, we present novel kinds of γ-Fe2O3@SiO2-NH2-CMC/MOF5 and γ-Fe2O3@SiO2-NH2-CMC/IRMOF3 magnetic metal–organic framework (MOF) nanoparticles which possess both magnetic characteristics and fluorescent properties. Here, [Zn4O(bdc)3] (MOF-5, bdc = 1,4-benzenedicarboxylate) is a kind of shell. IRMOF3, a known MOF with a cubic topology prepared from Zn(NO3)24H2O and 2-amino-1,4-benzene dicarboxylic

On account of their efficacy as µ-opioid receptor agonists, fentanyl and fentanyl analogues (‘fentanyls’) have fallen into favour within the illicit drug community. Consequently, there has been a significant public health crisis, unfolding across many countries, involving fentanyls and other synthetic opioids. Because of the potency of these opioids, even low-level contamination represents an immediate

A new metal-organic framework (MOF) based on CoII ions as nodes, [Co2(H2O)3(cada)](DMF)4, which has coordinated water molecules at the occupied CoII sites along with a suitable pore environment, was constructed by reaction of 5,5′-(9H-carbazole-2,7-diyl)diisophthalic acid (H4cada) and Co(NO3)2·6H2O in a water and DMF mixed solvent. The resulting activated MOF 1ais able to uptake considerable amounts

A new bis(rhodamine) B hydrazone L, bearing two rhodamine chromophores, has been designed and synthesised in 70 % yield. The chemical structure of the new ligand L was characterised using different spectroscopic techniques. The receptor L was utilised for rapid ‘naked eye’ detection of Fe3+, Bi3+, Cu2+, and Hg2+ in THF–H2O (1 : 1, v/v) by displaying significant colour changes. The mechanism of detection

A new ionic liquid containing a 1H,4H-piperazine-diium ring and chlorosulfonate as a 1,4-dicationic core and counter ion, respectively, was designed and synthesised. The structure elucidation of this ionic liquid was conducted by 1D and 2D NMR, FT-IR, Raman, and mass spectrum analysis. The physical properties of this ionic liquid were determined and reported. Furthermore, the dual solvent–catalyst

A new magnetic nanoparticle supported ionic liquid phase (SILP) catalyst containing perruthenate anions was prepared by a multistep procedure. The various analytical techniques such as FT-IR spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, thermogravimetric analysis, energy dispersive X-ray analysis, and vibrating sample magnetometer analysis ascertained the successful

Ruthenium-catalysed ethenolysis occurs in a vortex fluidic device (VFD) – a scalable, thin-film microfluidic continuous flow process. This process takes advantage of the efficient mass transfer of gaseous reagents into the dynamic thin film of liquid. Also reported is the rapid quenching of the ruthenium-based olefin metathesis catalyst by the addition of a saturated solution of N-acetyl-l-cysteine

This account is written for general users of time-dependent density functional theory (TD-DFT) methods as well as chemists who are unfamiliar with the field. It includes a brief overview of conventional TD-DFT approaches and recommendations for applications to organic molecules based on our own experience. The main emphasis of this work, however, lies in providing the first in-depth review of time-dependent

A series of six new, bidentate ligands based on N-(2-(R-sulfonamido)benzyl)R-sulfonamide have been isolated as dianionic or monoanionic chelators via condensation of 2-(aminomethyl)aniline with sulfonyl chloride reagents; R = methyl (1 and 1′), tolyl (2 and 2′), 2,4,6-trimethylphenyl (3), or 2,4,6-triisopropylphenyl (4). Complexes of ligands 2–4 reacted at room temperature with palladium(ii) acetate

A series of photochemical transformations has been successfully conducted under continuous-flow conditions in a concentrating solar trough reactor. Photoacylations and [2+2]-photocycloadditions involving 1,4-naphthoquinones gave the corresponding photoproducts in moderate to high yields with residence times of 70 min. Likewise, acetone-sensitized photodecarboxylations involving phthalimides furnished

The structural characterisation of bis(8-sulfanylquinolinium) hexachloridostannate(iv) (2) is reported and the variable reaction behaviour of this compound in different solvents has been explored. In particular, attempted recrystallization of 2 from chloroform and dichloromethane affords two polymorphs of cis-dichloridobis(8-quinolinethiolato)tin(iv), 3m and 3t, respectively. Attempted recrystallization

Chiral lanthanide helicates with circularly polarized luminescence (CPL) properties have found potential application in bioanalyses and chirality sensing. However, the preparation of the enantiopure helicates through a coordination-directed self-assembly strategy is challenging due to the greatly labile coordination geometries of lanthanide ions. Herein, a pair of enantiopure triple-stranded EuIII

A novel compound has been synthesised and characterised by various spectroscopic techniques. Analysing the crystal structures of the compound shows that multiple molecular interactions exist. The compound exhibits distinct aggregation-induced emission activity in EtOH/H2O accompanying a 2-fold enhancement of fluorescence intensity at ~609 nm. In addition, the cytotoxicity assay and confocal microscopy

Temozolomide (TMZ) is a significant anticancer agent especially for chemotherapy of glioblastoma. In order to reduce the recurrence rate of cancer, in this work an injectable hydrogel composed of TMZ-loaded solid lipid nanoparticles (SLNs) was designed for filling the cavity of a glioblastoma operation. First, TMZ-loaded SLNs (T-SLNs) were prepared by emulsion solvent diffusion and evaporation technology

An air- and moisture-tolerant alternate synthetic pathway to the preparation of a cationic chelated bis(NHC) methylpalladium(ii) complex, [{(MesIm)2CH2}Pd(Me)(NCMe)][PF6], is described. The pathway involves the isolation of a bis(NHC) AgI complex, [{(MesIm)2CH2}2Ag2][PF6]2, via metallation of the corresponding diimidazolium salt with Ag2O followed by carbene transfer to [(COD)PdBrMe]. This new method

The variable oxygen probe has been applied to axial and equatorial 4-pyranols 4 and 5 and their ester and ether derivatives. Plots of C–OR bond distance versus pKa (ROH) provided evidence for slightly stronger donation into the σ*C–OR antibonding orbital in the equatorial derivatives 5 than in the axial derivatives 4, which is consistent with the presence of a through-bond nO–σCC–σ*CO interaction in

Australia has a rich and long history in the nuclear science and technology sector. Nuclear medicine involves the use of radioactive substances and molecular imaging equipment to diagnose and treat diseases and is an ever-growing field around the globe. In fact, it is estimated that one in two Australians will require a nuclear medicine procedure during their lifetime. Progress by Australian scientists

Catalysts were invented to speed up chemical reactions, helping to maximise yields from available resources. If the same logic is applied to chemists themselves, what impact would this have on helping us maximise Australian female talent in the chemistry sector? This article aims to provide information on the current problems faced by female chemists across categories of workplace culture, work–life

Novel 2-(2-furyl)imidazole derivatives were synthesised. 2-(2-Furyl)-1-methoxyimidazoles and 2-(2-furyl)-1-methylimidazole 3-oxides were used as model compounds in the study of the prototropic tautomerism of 2-(2-furyl)-1-hydroxyimidazoles by means of 1H, 13C NMR and UV/vis spectroscopies. It was demonstrated that the interaction of the π-excessive furyl moiety with an electron-withdrawing carbonyl

Organisms from all kingdoms of life have evolved a vast array of peptidic natural products to defend against microbes. These are known collectively as antimicrobial peptides (AMPs) or host defense peptides, reflecting their abilities to not only directly kill microbes, but also to modulate host immune responses. Despite decades of investigation, AMPs have yet to live up to their promise as lead therapeutics

In-solution conjugation is the most commonly used strategy to label peptides and proteins with fluorophores. However, lack of site-specific control and high costs of fluorophores are recognised limitations of this approach. Here, we established facile access to grams of Cy5-COOH via a two-step synthetic route, demonstrated that Cy5 is stable to HF treatment and therefore compatible with Boc-SPPS, and

Peptide-induced permeabilization of lipid vesicles has been measured for decades and has provided many insights into the sequence-structure-function relationships of membrane-active peptides. However, researchers in the field have noted that many experiments show transient permeabilization, in which a burst of leakage occurs immediately after peptide addition, followed by a slowdown or cessation of

The nickel-iron hydrogenase enzymes efficiently and reversibly interconvert protons, electrons, and dihydrogen. These redox proteins feature iron-sulfur clusters that relay electrons to and from their active sites. Reported here are synthetic models for nickel-iron hydrogenase featuring redox-active auxiliaries that mimic the iron-sulfur cofactors. The complexes prepared are NiII(μ-H)FeIIFeII species

In the fruit fly Drosophila melanogaster, there are eight insulin-like peptides (DILPs) with DILPs 1-7 interacting with a sole insulin-like receptor tyrosine kinase (DInR) while DILP8 interacts with a single G protein-coupled receptor (GPCR), Lgr3. Loss-of-function dilp mutation studies show that the neuropeptide DILP2 has a key role in carbohydrate and lipid metabolism as well as longevity and reproduction

Difluoroboron β-diketonates have impressive optical properties in both solution and the solid state. In particular, both fluorescence and room-temperature phosphorescence are present when the dyes are confined to a rigid matrix, such as poly(lactic acid) (PLA). To expand current knowledge and color range capabilities of this unique type of multi-emitting chromophore, a series of thienyl-substituted

The logic of total synthesis transformed a stagnant state of medicinal and synthetic organic chemistry when there was a paucity of methods and reagents to synthesize drug molecules and/or natural products. Molecular imaging by positron emission tomography (PET) is now experiencing a renaissance in the way radiopharmaceuticals for molecular imaging are synthesized, however, a paradigm shift is desperately

Berberine-INF55 hybrids are a promising class of antibacterials that combine berberine and the NorA multidrug resistance pump inhibitor INF55 (5-nitro-2-phenylindole) together in one molecule via a chemically stable linkage. Previous studies demonstrated the potential of these compounds for countering efflux-mediated antibacterial drug resistance but they didn't establish whether the compounds function

Rapid growth of complexity and unprecedented molecular architectures are realized via the excited-state intramolecular proton transfer (ESIPT) in o-acylamidobenzaldehydes and ketones followed by [4+2] or [4+4] cycloadditions with subsequent postphotochemical modifications. The approach is congruent with Diversity-Oriented Synthesis: photoprecursors are synthesized in a modular fashion allowing for

The most abundant proteins in vertebrates - the collagen family proteins - play structural and biological roles in the body. The predominant member, type I collagen, provides tissues and organs with structure and connectivity. This protein has several unique post-translational modifications that take place intra- and extra-cellularly. With growing evidence of the relevance of such post-translational

A rhodamine based boronic acid linearly responds to increasing 5-aminoimidazole-4-carboxamide riboside (AICAr) concentrations in human urine. This method is thus an advance in detecting adenylosuccinate lyase (ADSL) deficiency as AICAr is a model riboside for the ADSL substrates succinyladenosine (S-Ado) and succinylaminoimidazolecarboxamide riboside (SAICAr). ADSL deficiency is a rare but devastating

N-heterocyclic carbenes (NHCs) promote the addition of 1,1-bis(phenylsulfonyl)ethylene to the α-position of α,β-unsaturated aldehydes. The proposed reaction pathway for this Rauhut-Currier-type reaction includes an unusual conjugate addition of an NHC to a bis-vinyl sulfone.

The thiazolidinedione, compound 1, has previously shown pan-inhibition of the phosphoinositide 3-kinase (PI3K) class I isoforms. We hypothesized the derivatization of the thiazolidinedione core of compound 1 could introduce isoform selectivity. We report the synthesis, characterization, and inhibitory activity of a novel series of 4-iminothiazolidin-2-ones for inhibition of the class I PI3K isoforms

A powerful combination of chemically specific Raman excitation and deep tissue ultrasound imaging holds the promise to attain spatially resolved distribution of chemical compounds inside the scattering medium. In this report, an attempt is made to evaluate the recent achievements and possible challenges with an eye on potential clinical applications.

Robust water oxidation catalysts using earth abundant metals are required as part of an overall scheme to convert sunlight into fuels. Here, we report the immobilization of [[Formula: see text]O(5)(terpy)(4)(H(2)O)(2)](ClO(4))(6) (terpy = 2,2';6',2″-terpyridine), [Mn(4)O(6)(tacn)(4)](ClO(4))(4) (tacn = 1,4,7-triazacyclononane), and manganese dioxide nanoparticles in Nafion on fluorine-doped tin oxide

Thin films of 1,3-diethylbenzimidazol-2-ylidene (BIEt) were fabricated from THF solution on solid gold substrates and characterised by high-resolution X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy. The surface-analytical data are in accord with the formation of self-assembled monolayers of BIEt molecules exhibiting an approximately vertical orientation on the substrate

Raman vibrational spectroscopic imaging was performed on retinal rod cells isolated from bullfrogs (Rana catesbeiana). The Raman spectra enable determination of the lipid and protein rich rod outer segment (ROS) from the nucleus and inner segment of the cell. Peak fitting analysis of spectra obtained from individual rod photoreceptor cells show characteristic vibrational modes that can be associated

5'-(2-Phosphoryl-1,4-dioxobutane) (DOB) is a lesion produced in DNA via a variety of damaging agents. The DOB lesion spontaneously generates cis- and trans-but-2-en-1,4-dial (1) via β-elimination. Cis- and trans-but-2-en-1,4-dial forms exocyclic adducts with nucleosides. We used chemically synthesized DNA containing tritiated DOB incorporated at defined sites to examine the reactivity of cis- and trans-but-2-en-1

A templated macrocyclization reaction was used to permanently encapsulate a highly fluorescent hydroxy-substituted squaraine dye inside a tetralactam macrocycle. The free squaraine dye is quite rigid due to internal hydrogen bonding and its photophysical properties hardly change upon encapsulation. A combination of X-ray and NMR data show that the surrounding tetralactam macrocycle adopts an unusually

The luminescence properties of lanthanoid ions can be dramatically enhanced by coupling them to antenna ligands that absorb light in the UV/visible and then efficiently transfer the energy to the lanthanoid center. The synthesis and the complexation of Ln(III) cations (Ln=Eu; Gd) for a ligand based on four 1-hydroxy-2-pyridinone (1,2-HOPO) chelators appended to a ligand backbone derived by linking