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The understanding on the growth mechanism of complex gold nanostructures both experimentally and theoretically can guide their design and fabrication toward various applications. In this work, we report a cysteine-directed overgrowth of penta-twinned nanorod seeds into jagged gold bipyramids with discontinuous stepped {hhk} facets. By monitoring the growth process, we find that {hhk} facets with large k/h values (∼7) are formed first at two ends of the nanorods, followed by the protrusion of the middle section exposing {hhk} facets with smaller indices (k/h ∼ 2–3). Molecular dynamics simulations indicate that the strong adsorption of cysteine molecules on {110} facets is likely responsible for the formation of stepped {hhk} facets, and the stronger adsorption of cysteine molecules on {hhk} facets with smaller k/h compared to that on {hhk} facets with larger k/h is a possible cause of the discontinuity of {hhk} facets at the middle of gold bipyramids. The obtained jagged gold bipyramids display large field enhancement under illumination due to their sharp nanostructures, demonstrating their application potentials in surface-enhanced spectroscopy and catalysis. [ABSTRACT FROM AUTHOR]

Traditional hydrogen bonds are well-known to exhibit directionality and saturation. By contrast, gold involved hydrogen bonds (GHBs) have been extensively studied but remain lack of in-depth understanding towards the intrinsic nature and saturation property. This work exemplifies three series of complexes: [L–Au–L]−⋯(HF)n (L = H, CH3, (CH3)3; n = 1–8) containing GHBs to dig into the intrinsic nature with the aid of multiple theoretical analysis methods, finding that the formation of GHB is highly subject to orbital interactions along with steric hindrance. Moreover, the saturation level of GHBs largely depends on the ligand attached to the gold center, since different ligands typically possess varying electron-giving ability and steric volume. This work confirms the coexistence of as many as 6 GHBs for one Au atom and thoroughly studies the saturation level of GHBs, which will provide new insights into GHBs and facilitate future synthesis of more complicated gold complexes. [ABSTRACT FROM AUTHOR]

We study the prospects of using quantum Monte Carlo techniques (QMC) to optimize the electronic wavefunctions and atomic geometries of gold compounds. Complex gold nanoclusters are widely studied for diverse biochemical applications, but the dynamic correlation and relativistic effects in gold set the bar high for reliable, predictive simulation methods. Here we study selected ground state properties of few-atom gold clusters by using density functional theory (DFT) and various implementations of the variational Monte Carlo (VMC) and diffusion Monte Carlo. We show that the QMC methods mitigate the exchange-correlation (XC) approximation made in the DFT approach: the average QMC results are more accurate and significantly more consistent than corresponding DFT results based on different XC functionals. Furthermore, we use demonstrate structural optimization of selected thiolated gold clusters with between 1 and 3 gold atoms using VMC forces. The optimization workflow is demonstrably consistent, robust, and its computational cost scales with nb, where b < 3 and n is the system size. We discuss the implications of these results while laying out steps for further developments. [ABSTRACT FROM AUTHOR]

We report that complexes formed between gold nanorods (AuNRs) and metal-mediated DNA exhibit plasmonic circular dichroism (CD) signals up to ∼400 times stronger than the molecular CD signal of DNA. This substantial enhancement enables the detection of metal ions, offering a promising approach to analytical applications in chiral biochemistry. [ABSTRACT FROM AUTHOR]

A series of heterobimetallic complexes Au/M (M = RhIII, IrIII) were prepared on the basis of two ditopic ligands: a monophosphane ligand L1H and a triphosphane ligand L2H. The complexes were fully characterised, including single-crystal X-ray diffraction studies. Catalytic activity of cationic L1/AuI/IrIII and L2/AuI/IrIII bis(trifluoromethane)sulfonimide was analysed through their capacity to induce allenyl ether rearrangement and cycloisomerisation of N-propargyl benzamide. While cationic L1/AuI/IrIII showed some ability to induce allenyl ether rearrangement, no conversion was observed for cationic L2/AuI/IrIII. Similarly, N-propargyl benzamide could undergo cycloisomerisation in the presence of cationic L1/AuI/IrIII, whereas cationic L2/AuI/IrIII was again inactive. These findings highlight how crucial the surroundings of the metal centre are to the catalytic activity. Catalytic activity is only possible when Au has a free coordination site; the gold complex becomes inactive when the tridentate ligand is present. [ABSTRACT FROM AUTHOR]

Electron distribution and bonding in extended structures based on square planar gold complexes, traditionally classified as gold (III), have been addressed through solid‐state DFT calculations. The band structure analysis, taken as a diagnostic tool, highlighted that, when the metal is associated with chalcogen atoms, the gold centers are more electron rich than the classic accepted description. This is in agreement with the Inverted Ligand Field (ILF) theory that predicts a metal center d10 configuration with two electrons vacancy on the orbital combinations of the ligands for sulfur, selenium and tellurium cases. A covalent bond is featured in oxygen compounds, a borderline situation between the ILF and the classical Ligand Field description. In conclusion, the gold atom in chalcogenide square planar complexes should be considered electron richer than commonly thought applying the traditional rules for calculating the oxidation state. [ABSTRACT FROM AUTHOR]

Controlled formation of mixed-metal bimetallics was achieved via two derivatised 1,10-phenanthroline ligands bearing an imino- or amino-phosphine appendage at the 5-position. Selective coordination of the phen group to the [Re(CO)3Cl] core was achieved enabling precise construction of bimetallic complexes with a second rhenium centre or with gold. The mixed Ru/Au complex was similarly obtained with the imino-phosphine but access to the heterobimetallic iridium systems required prior formation of the P-bound gold complexes subsequent to the introduction of the [Ir(Ppy)2]+ fragment. The Re/Pd, Re/Pt, Ir/Pd and Ir/Pt compounds were prepared from the combination of κ-N′′,P-Pd(Pt)Cl2 and the appropriate rhenium or iridium precursors. Spectroscopic and theoretical analyses have been employed to investigate the structural and electronic impact of the second metal. [ABSTRACT FROM AUTHOR]

Silver nanowires-embedded polydimethylsiloxane (AgNWs/PDMS) electrodes are promising components for various soft electronics, but face energy mismatch with organic semiconductors. Attempts at galvanic replacement, involving spontaneous gold (Au) formation on the electrodes, often result in non-uniform and particulate Au coatings, compromising device performance and stability. In this study, we introduce a novel approach for achieving a uniform and complete Au coating on AgNWs/PDMS electrodes by adding NaCl to the Au complex solution. This addition slows down the galvanic replacement process and prevents precipitation, enabling a uniform and complete Au coating on the AgNWs surface. Such coating significantly reduces contact resistance (RC), thereby enhancing the electrical characteristics of p-type organic transistors. Furthermore, the development of high-performance, fully soft organic transistors was achieved incorporating an organic semiconductor-elastomer blend. Additionally, reliable, mechanically stable soft glucose sensor was developed, taking advantage of the complete Au coating, which protects against oxidation during the glucose sensing process. [ABSTRACT FROM AUTHOR]

The 3-phenoxybenzoic acid (3-PBA) residues in environment are posing a significant challenge to our daily lives. To establish a more sensitive and rapid detection method, anti-3-PBA nanobodies (Nbs) were immobilized onto magnetosomes (bacterial magnetic nanoparticles, termed as BMPs), forming a robust BMP-Nb complex. The 3-PBA derivative was labeled with horseradish peroxidase (HRP) and further associated with gold nanoparticles (AuNPs) to create a highly sensitive probe (3-PBA-HRP-AuNP). An innovative immunoassay that combined BMP-Nb complex with 3-PBA-HRP-AuNP was developed for determinaton of 3-PBA. This method enabled the determination of 3-PBA with a half-maximum signal inhibition concentration (IC50) of 1.03 ng/mL, which was more sensitive than that of using 3-PBA-HRP as tracer with an IC50 of 2.18 ng/mL. The reliability of the assay was evidenced by the quantitative recovery of 3-PBA from water and soil samples ranging from 76.85 to 95.64%. The 3-PBA residues determined by this assay in actual water samples were between < LOD and 2.54 ng/mL and were between < LOD and 11.25 ng/g (dw) in real soils, respectively, which agreed well with those of liquid chromatography mass spectrometry (LC–MS). Collectively, the BMP-Nb and 3-PBA-HRP-AuNP-based immunoassay provides a powerful tool for the precise detection of 3-PBA residues in environment matrices, reinforcing our capacity to monitor and mitigate potential ecological and health impacts associated with this prevalent pollutant. [ABSTRACT FROM AUTHOR]

Worldwide, rheumatoid arthritis is a major cause of morbidity and mortality. In recent years, the domain of inorganic medicinal chemistry has shown more interest in metal-based drugs owing to their beneficial pharmacological activities. Since then, many useful anti-cancer metalbased drugs have been introduced. However, less attention has been paid to improving inflammatory drugs based on metal complexes. The objective of this review is to recapitulate previously published studies that concentrated on metal-based drugs used for the treatment of arthritis. It is anticipated that the current compilation of earlier studies will be helpful for the researcher to find the data and areas for future studies. The literature survey was done without any time limit using the help of various electronic databases, including ScienceDirect, SpringerLink, Web of Science, PubMed, and the Cochrane Library. Articles published in the English language are used for the current review. Only 20 studies were found to be pertinent to the present review. Metal complexes of non-steroidal anti-inflammatory drugs have been the subject of extensive research. To date, metal complexes of drugs such as aspirin, ibuprofen, anthranilic acid, methotrexate, indomethacin, and aceclofenac have been studied and evaluated for their possible antiarthritic activity. Gold metal complexes showed better efficacy and have been used in clinical practice as well. Due to their advantageous therapeutic properties, metals and their complexes are becoming more and more important today. To find new treatments for diseases, it is suggested that the mechanism of action and potential toxicity of metal complexes must be assessed. [ABSTRACT FROM AUTHOR]

Three cationic Gold(I)‐NHC complexes with potential anticancer properties were studied using DFT with B3LYP functional in combination with two basis sets, LanL2DZ and SDD. Obtained equilibrium geometries and computed IR spectra were found in excellent agreement with previously reported x‐ray structures and experimental IR spectral data. NBO population analysis showed gold(I) has a charge deficiency of 0.26–0.30 e. All three complex cations are polar, with dipole moment values ranging from 6.8 to 7.4 Debye. Regardless of some structural differences in their co‐ligands, all three complex cations have remarkably similar HOMO‐LUMO energy gaps, with values ranging from 5.2 to 5.4 eV, confirming they are chemically stable and that they share an almost identical stability. Long‐range intramolecular interactions Au ⋅⋅⋅H−X (X=N or C) in all three cationic complexes were identified. Both basis sets employed in this study were found equally effective in producing reliable results. [ABSTRACT FROM AUTHOR]

During our studies of the oxidation of gold(I) complexes of tri­alkyl­phosphane chalcogenides, general formula R¹R²R³PEAuX, (R = tert-butyl or isopropyl, E = S or Se, X = Cl or Br) with PhICl2 or elemental bromine, we have isolated a set of seven mixed-valence by-products, the bis­(tri­alkyl­phosphane chalcogenido)gold(I) tetra­halogenidoaurates(III) [(R¹R²R³PE)2Au]+[AuX4]−. These corres­pond to the addition of one halogen atom per gold atom of the AuI precursor. Com­pound 1, bis­(triiso­propyl­phosphane sulfide)­gold(I) tetra­chlorido­aur­ate(III), [Au(C9H21PS)2][AuCl4] or [(iPr3PS)2Au][AuCl4], crystallizes in space group P21/n with Z = 4; the gold(I) atoms of the two cations lie on twofold rotation axes, and the gold(III) atoms of the two anions lie on inversion centres. Compound 2, bis­(tert-butyl­diiso­propyl­phosphane sulfide)­gold(I) tetra­chlorido­aurate(III), [Au(C10H23PS)2][AuCl4] or [(tBuiPr2PS)2Au][AuCl4], crystallizes in space group P1 with Z = 4; the asymmetric unit contains two cations and two anions with no imposed symmetry. A least-squares fit of the two cations gave an r.m.s. deviation of 0.19 Å. Compound 3, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­chlorido­aurate(III), [Au(C12H27PS)2][AuCl4] or [(tBu3PS)2Au][AuCl4], crystallizes in space group P1 with Z = 1; both gold atoms lie on inversion centres. Compound 4a, bis­(tert-butyl­diiso­propyl­phosphane sulfide)­gold(I) tetra­bromi­doaurate(III), [Au(C10H23PS)2][AuBr4] or [(tBuiPr2PS)2Au][AuBr4], crystallizes in space group P21/c with Z = 4; the cation lies on a general position, whereas the gold(III) atoms of the two anions lie on inversion centres. Compound 4b, bis­(tert-butyl­diiso­propyl­phosphane selenide)gold(I) tetra­bromido­aurate(III), [Au(C10H23PSe)2][AuBr4] or [(tBuiPr2PSe)2Au][AuBr4], is isotypic with 4a. Compound 5a, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­bromido­aurate(III), [Au(C12H27PS)2][AuBr4] or [(tBu3PS)2Au][AuBr4], is isotypic with compound 4a. Compound 5a, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­bromido­aurate(III), [Au(C12H27PS)2][AuBr4] or [(tBu3PS)2Au][AuBr4], crystallizes in space group P1 with Z = 1; both gold atoms lie on inversion centres. Compound 5b, bis­(tri-tert-butyl­phosphane selenide)gold(I) tetra­bromido­aurate(III), [Au(C12H27PSe)2][AuBr4] or [(tBu3PSe)2Au][AuBr4], is isotypic with 5a. All AuI atoms are linearly coordinated and all AuIII atoms exhibit a square-planar coordination environment. The ligands at the AuI atoms are anti­periplanar to each other across the S⋯S vectors. There are several short intra­molecular H⋯Au and H⋯E contacts. Average bond lengths (Å) are: P—S = 2.0322, P—Se = 2.1933, S—Au = 2.2915, and Se—Au = 2.4037. The complex three-dimensional packing of 1 involves two short C—Hmethine⋯Cl contacts (and some slightly longer contacts). For 2, four C—Hmethine⋯Cl inter­actions combine to produce zigzag chains of residues parallel to the c axis. Additionally, an S⋯Cl contact is observed that might qualify as a ‘chalcogen bond’. The packing of 3 is three-dimensional, but can be broken down into two layer structures, each involving an S⋯Cl and an H⋯Cl contact. For the bromido derivatives 4a/b and 5a/b, loose associations of the anions form part of the packing patterns. For all four compounds, these combine with an E⋯Br contact to form layers parallel to the ab plane. [ABSTRACT FROM AUTHOR]

The basis of most neurological syndromes is the accumulation of free radical molecules. Quercetin is a polyphenolic bioflavonoid molecule and it has a very strong antioxidant effect by maintaining oxidative balance. There are many difficulties in the clinical use of quercetin due to its hydrophobic structure, low solubility, instability, poor oral bioavailability, and limited tissue-barrier penetration. Its synergistic use in complex with gold nanoparticles (AuNPs) could overcome these problems. AuNPs have recently emerged as an attractive candidate for delivery applications of various biomolecules and drugs. The aim of this study was to synthesize two different sized gold nanoparticles (AuNP 20 and AuNP 50) modified with polyethyleneimine (PEI) and quercetin, evaluate their potential neuroprotective effects on the in vitro oxidative stress model using DRG primary sensory neurons. It was shown that the antioxidant and anti-apoptotic ability of the bioflavonoid was preserved after exposure to the designed quercetin modified AuNPs. The PEI surface coating increased the stability and biocompatibility of the AuNPs in both sizes. It also potentially enables additional surface functionalization. This study indicates that designed nanoparticles (AuNP-Q-PEI) with different sizes could be a useful potential platform for the treatment of neurodegenerative syndromes or cancer diseases. Quercetin/PEI modified and two different sized (AuNP 20 and AuNP 50) gold nanoparticles were successfully synthesized. Designed nanoplatform (AuNPs-Q-PEI) increased stability and biocompatibility. After nanomaterial exposure in the oxidative stress model of the DRG sensory neurons, the level of ROS and apoptosis was significantly reduced. [Display omitted] • Quercetin/PEI modified and two different sized (AuNP 20 and AuNP 50) gold nanoparticles were successfully synthesized. • The antioxidant property of the bioflavonoid was preserved after exposure to designed Q-coated AuNPs in the DRG neurons. • The PEI surface coating increased the stability and biocompatibility of the AuNPs in both sizes. • The designed gold nanoconjugates could be a useful potential nanoplatform for the treatment of neurodegenerative syndromes. [ABSTRACT FROM AUTHOR]

A family of luminescent pyrenyl‐(NHC)‐M−Cl coinage metal complexes has been prepared and fully characterized (NHC=N‐heterocyclic carbene). Two classes of complexes are described: (M=Cu (1 a), Ag (2 a), Au (3 a) where pyrenyl‐(NHC)=1‐pyrenyl‐3‐methyl‐Imidazolin‐2‐ylidene and M=Cu (1 b), Ag (2 b), Au (3 b) with pyrenyl‐(NHC)=1‐pyrenyl‐3‐naphthyl‐Imidazolin‐2‐ylidene. The molecular structures of the six complexes were confirmed by single crystal X‐ray diffraction studies. All complexes were found to be emissive both in solution and solid state. The use of the chromophoric‐(NHC) ligand endows to these complexes emissive properties in solution in the blue region (376–397 nm). The presence of the naphthyl‐substituent in the 1 b–3 b series enhances the quantum yields relative to the methyl‐series 1 a–3 a. In particular, the carbene gold complexes were the most emissive and displayed the highest quantum yields. [ABSTRACT FROM AUTHOR]

Gold(III) complexes containing trifluoromethyl ligands are efficient catalysts in the hydration of alkynes, operating at low catalyst loadings, without additives, using environmentally friendly solvents and at mild conditions (60 °C). Hydration of terminal and internal alkynes provides the corresponding ketones in quantitative yields without special precautions as dry solvents or inert atmospheres. Remarkably, hydration of asymmetric internal alkynes proceeds with moderate to notable regioselectivities, providing mixtures of the two possible isomers with ratios up to 90 : 10. [ABSTRACT FROM AUTHOR]

Another class of gold(I) redox‐switchable catalysts, incorporating ferrocenyl phosphane‐imines, enriches the existing library of gold(I) complexes. Our catalyst proves efficacy in gold(I)‐catalyzed cyclizations of furans and benzamides, exhibiting reversible "on‐off" switching. Furthermore, we explored the unconventional role of "Magic Blue", commonly used as an oxidizing agent in various organic transformations, as a potential activator of the Au−Cl bond, initiating conventional gold(I) catalysis. [ABSTRACT FROM AUTHOR]

Singlet oxygen production and its reactivity have significant implications in fields ranging from polymer science to photodynamic therapy. Extensive research has focused on the development of organic-based materials and heavy metal complexes, including Ru(II), Rh(III), Ir(III) and Pt(II). However, metal complexes containing Au(I) have been scarcely explored and warrant further investigation. This review provides a comprehensive analysis of reported compounds, classified based on the ligands coordinated to the gold(I) centre. Additionally, future directions in photosensitizer development and singlet oxygen applications are discussed. [ABSTRACT FROM AUTHOR]

ABSTRACT Canine mammary gland tumour (CMT) is the most common spontaneous tumour in intact female dogs and often exhibits metastases. Auranofin (AF) is a gold complex used for treating rheumatism. The excellent anti‐tumour ability of AF has been demonstrated in various types of human and canine tumours. In this study, five CMT cell lines (CIPp, CMT‐7364, CHMp, CIPm and CTBp) and three CMT primary cells (G7894, L1883 and L6783) were used to explore the anti‐tumour effect of AF on CMT. Two CMT cell lines (CIPp and CMT‐7364) were used to search the underlying mechanism of the effect of AF on CMT. The results showed that AF inhibited the growth, migration, invasion, and colony formation abilities of CMT cells. Additionally, the growth of CMT in a 3D cell culture model was effectively suppressed by AF. Furthermore, AF induced cell apoptosis of CMT cells via the PI3K/AKT pathway. In conclusion, AF effectively induces CMT apoptosis by regulating the PI3K/AKT pathway, indicating that AF should be explored as a potential CMT treatment in future studies. [ABSTRACT FROM AUTHOR]

Lung cancer is a leading cause of cancer-related death worldwide that needs updated therapies to contrast both the serious side effects and the occurrence of drug resistance. A panel of non-small cell lung cancer (NSCLC) cells were herein employed as cancer models. Eight structurally related gold(I) and gold(III) complexes with NHC and halides or triphenylphosphane ligands were investigated as lung cancer cell growth inhibitors. As expected, gold compounds with PPh3 were found to be more cytotoxic than homoleptic [(NHC)2-Au(I)]X or heteroleptic NHC-Au(I)X or NHC-Au(III)X3 complexes. Mixed ligand gold(I) compounds exhibiting the linear NHC-AuPPh3 (compound 7) or the trigonal NHC-Au(Cl)PPh3 (compound 8) arrangements at the central metal were found to be the best lung cancer cytotoxic compounds. Analysis of the TrxR residual activity of the treated cells revealed that these compounds efficiently inhibit the most accredited molecular target for gold compounds, the TrxR, with compound 8 reaching more than 80% activity reduction in lung cells. Some of the current cancer lung therapy protocols consist of specific lung cancer cell cytotoxic agents combined with antifolate drugs; interestingly, the herein gold compounds are both TrxR and antifolate inhibitors. The human DHFR was inhibited with IC50 ranging between 10–21 µM, depending on substrate concentrations, proceeding by a likely allosteric mechanism only for compound 8. [ABSTRACT FROM AUTHOR]

A microfine-grained complex refractory gold ore in Henan has a grade of 1.2 g/t, but the recovery rate by beneficiation is low. To improve the recovery rate and economic benefits, a process mineralogy study was conducted on the flotation tailings. The study revealed that the gold-bearing minerals in the tailings are primarily pyrite, followed by silicate minerals such as quartz and feldspar. The pyrite particles are mostly smaller than 0.038 mm, typically occurring as fine particles intergrown with gangue minerals or encapsulated within them, with occasional monomeric occurrences. The monomer liberation degree is only 4. 60%, indicating that increasing the grinding fineness could further recover the gold from the tailings. Open-circuit and closed-circuit tests showed that when the grinding fineness was increased to 0.074 mm accounting for about 85%, and the flotation reagent regime was optimized and adjusted, the recovery rate increased to 85.86%, leading to significant economic benefits. [ABSTRACT FROM AUTHOR]

In this work, we have prepared and characterized some gold compounds wearing a N-heterocyclic carbene (NHC) ligand as well as alkynyl derivatives with different substituents. The study of their electrochemical behavior reveals that these complexes show an irreversible wave at potentials ranging between −2.79 and −2.91 V, referenced to the ferrocenium/ferrocene pair. DFT calculations indicate that the reduction occurs mainly on the aryl−C≡C fragment. The cyclic voltammetry experiments under CO2 atmosphere show an increase in the faradaic current of the reduction wave compared to the experiments under argon atmosphere, indicating a possible catalytic activity towards the carbon dioxide reduction reaction (CO2RR). [ABSTRACT FROM AUTHOR]

Two‐coordinate Au(I) complexes with a donor‐metal‐acceptor (D‐M‐A) structure have shown rich luminescent properties. However, charge‐neutral dinuclear donor‐metal‐acceptor type Au(I) complexes featuring aurophilic interactions have been seldom explored. Herein, we describe the structures and photoluminescence properties of two dinuclear Au(I) complexes, namely DiAu‐Ph and DiAu‐Me. Single crystal X‐ray structural analysis of DiAu‐Ph reveals a short intramolecular Au‐Au distance of 3.224 Å. In dilute solution and doped films, excitation wavelength dependent multiple phosphorescence phenomena were observed for these dinuclear complexes. Theoretical calculations reveal that the aurophilic interaction causes increased contribution of the Au d orbital to the highest occupied molecular orbitals. Thus, the gap between singlet and triplet excited states (ΔEST) is enlarged, which disables the thermally activated delayed fluorescence (TADF). Moreover, the large energy separation (0.45–0.52 eV) and the different orbital configurations between the various excited states result in an inefficient internal conversion, accounting for their multiple phosphorescence properties. [ABSTRACT FROM AUTHOR]

Interactions between gold‐based materials and dioxygen (O2) have motivated researchers to understand reaction mechanisms for O2 activation by homo‐ and heterogeneous gold catalysts. In this work, gold(I) porphyrin dinuclear complexes were synthesized with a saddle‐distorted porphyrin ligand. The gold(I) porphyrin complexes showed unprecedented O2 activation in the presence of protic solvents to form gold(III) tetradentate porphyrin complexes. Mechanistic insights into the O2 activation by the gold(I) center were elucidated by spectroscopic measurements and theoretical calculations, revealing that dissociation of halides on the gold(I) center by alcohol solvents and hydrogen bonding of an N−H proton in the distorted porphyrin with dioxygen played important roles in establishing the unique reactivities of gold(I) complexes. [ABSTRACT FROM AUTHOR]

Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing to their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, a series of ferrocenyl diphosphines functionalized with no, one or two ylide moieties and their corresponding bimetallic gold complexes were prepared. The complexes feature an anti‐conformation of the two phosphine moieties, guaranteeing the presence of two independent metal centers. Comparative studies of the complexes in the hydroamination and hydrohydrazination of alkynes revealed a significant increase in catalytic activity for each newly introduced ylide group. The di‐YPhos ligands were revealed to be the most active precatalysts, functioning effectively even at 0.1 or 0.2 mol % catalyst loading. This catalytic efficiency was demonstrated for a series of alkynes, amines and hydrazines. [ABSTRACT FROM AUTHOR]

Tetradentate meso‐octaalkylcalix[4]pyrroles are well‐established ligands in d‐ and f‐block chemistry. In contrast to the related porphyrins, the sp3‐hybridized meso‐carbon atoms linking the four pyrrole units result in highly divers coordination modes. We previously reported on the combination of this ligand system with Sn(II) centers yielding tetracoordinated stannate(II) anions which could be employed as electron‐rich, strong σ‐donor ligands in transition metal chemistry. With this work we are extending the coordination chemistry of meso‐octaethylcalix[4]pyrrolato stannate(II) [1]2− onto gold(I). Synthesis of mono‐ and dinuclear gold complexes reveal a new dynamic binding mode involving μ2‐bridging coordination of a pyrrole nitrogen atom to both Sn and Au. Single‐crystal X‐ray diffraction and variable temperature NMR spectroscopy combined with quantum mechanical computations and bond analysis tools shed light on the involved intermediates. [ABSTRACT FROM AUTHOR]

Gold catalysis has emerged as a groundbreaking field in synthetic chemistry, revolutionizing numerous organic transformations. Despite the significant achieved advancements, the mechanistic understanding behind many gold‐catalyzed reactions remains elusive. This Concept article covers the so‐called "self‐activating" Au(I) complexes, sorting out their pivotal role in gold catalysis. We comment on how Au(I) complexes can undergo self‐activation, triggering diverse catalytic transformations without the need for external additives. The most important examples reported so far that underlie the catalytic activity of these species are discussed. This intrinsic reactivity represents a paradigm shift in gold catalysis, offering new avenues for the design of efficient and sustainable catalytic systems. Furthermore, we explore the factors influencing the stability, reactivity, and selectivity of these Au(I) complexes, providing insights into their synthetic utility and potential applications. This area of research not only advances our fundamental understanding of gold catalysis but also paves the way for the development of novel catalytic strategies with broad implications in organic synthesis and the chemical industry. [ABSTRACT FROM AUTHOR]

Cyanide leaching technology was studied for low-grade oxidized gold ores in Guangxi Province. The gold grade of the raw ores was 1.32 g/t. The gold leaching rate was 90.91% under the optimal conditions for the following conventional leaching process: using steel forging as the grinding medium, a grinding fineness of −0.074 mm accounting for 92.53%, a stirring speed of 1500 r/min, a pulp leaching concentration of 28.57%, a pH value of 10.5, a temperature of 25 °C, a leaching time of 24 h, and a potassium cyanide consumption of 4 kg/t. A new type of mixed aid-leaching agent (0.6 kg/t) was used, with a dosage of potassium cyanide of 2 kg/t. All else being equal, the gold leaching rate increased by 2.17% to 93.20% after 18 h of aid leaching compared to that of conventional leaching for 28 h. Meanwhile, the amount of potassium cyanide used was reduced by 50%. The aid-leaching agents restored the surface activity of passivated gold particles and depressed the adsorption of gold and its complexes by gangue minerals. This approach could shorten the leaching time and increase the gold leaching rate. [ABSTRACT FROM AUTHOR]

Simple Summary: Aquaporins (AQPs) have emerged as potential predictors of response to cancer therapy and as targets for increasing sensitivity to treatment. However, systemic therapeutic inhibition using pan-AQP or AQP-specific inhibitors has not been characterized for efficacy in treating breast cancer or as a component of combination treatment. We evaluated AQP inhibition using established AQP inhibitors in cytotoxicity and pharmacologic assays. This study identified AQPs as a targetable vulnerability in breast cancer. AQP inhibitors can increase therapeutic efficacy, both as single agents and in a combination therapy strategy, in treating breast cancer progression and metastasis. These results provide significant insights that support the future development of improved AQP inhibitors. AQPs contribute to breast cancer progression and metastasis. We previously found that genetic inhibition of Aqp7 reduces primary tumor burden and metastasis in breast cancer. In this study, we utilized two AQP inhibitors, Auphen and Z433927330, to evaluate the efficacy of therapeutic inhibition of AQPs in breast cancer treatment. The inhibitors were evaluated in breast cancer for both cytotoxicity and metabolic stability assays across both murine and human breast cancer cell lines. Both AQP inhibitors also affected the expression of other AQP transcripts and proteins, which demonstrates compensatory regulation between AQP family members. As a single agent, Auphen treatment in vivo extended overall survival but did not impact primary or metastatic tumor burden. However, Auphen treatment made cells more responsive to chemotherapy (doxorubicin) or endocrine treatment (tamoxifen, fulvestrant). In fact, treatment with Tamoxifen reduced overall AQP7 protein expression. RNA-seq of breast cancer cells treated with Auphen identified mitochondrial metabolism genes as impacted by Auphen and may contribute to reducing mammary tumor progression, lung metastasis, and increased therapeutic efficacy of endocrine therapy in breast cancer. Interestingly, we found that Auphen and tamoxifen cooperate to reduce breast cancer cell viability, which suggests that Auphen treatment makes the cells more susceptible to Tamoxifen. Together, this study highlights AQPs as therapeutic vulnerabilities of breast cancer metastasis that are promising and should be exploited. However, the pharmacologic results suggest additional chemical refinements and optimization of AQP inhibition are needed to make these AQP inhibitors appropriate to use for therapeutic benefit in overcoming endocrine therapy resistance. [ABSTRACT FROM AUTHOR]

The goal of this study is to synthesize, determine the structure, and examine the antimicrobial properties of novel Cu(II) and Au(III) complexes of 2,4-dithiouracil and its derivatives. These complexes were obtained by mixing aqueous solutions of the corresponding metal salts with the ligand dissolved in DMSO and aqueous NaOH, using a metal-to-ligand ratio of 1:4:2. The structures of the new compounds were analyzed by melting point determination, microwave plasma atomic emission spectrometry (MP-AES) for Cu and Au, inductively coupled plasma optical emission spectrometry (ICP-OES) for S, attenuated total reflection (ATR), solution and solid-state NMR, and Raman spectroscopy. The data for 2,4-dithiouracil obtained from the 1H NMR, 13C NMR, distortionless enhancement by polarization transfer spectrum (DEPT-135), proton–proton homonuclear correlation spectrum (1H-1H COSY), long-range 1H-13C heteronuclear multiple bond correlation experiment (HMBC), and heteronuclear single quantum coherence spectra (HSQC) aided the interpretation of the NMR data for the gold and copper complexes. Furthermore, the antimicrobial effect of the free ligands and their complexes was assessed against Gram-positive and Gram-negative bacteria, as well as yeasts. [ABSTRACT FROM AUTHOR]

We disclose a novel series of N-heterocyclic carbene (NHC) gold complexes with varied steric and electronic properties, bearing fluorinated alkoxide anions. Early reactivity studies involving these synthons, lead to the synthesis of various complexes of relevance to gold chemistry and catalysis. [ABSTRACT FROM AUTHOR]

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This study utilized water-soluble fluorescein isothiocyanate (FITC) to cover graphene loaded gold nanoparticle composites, and the fluorescence of the probe molecule FITC was quenched. Then, by adding cyanide to the system, the strong complexation of cyanide ions (CN-) with gold nanoparticles formed a stable complex Au (CN)3-x, gradually restoring the fluorescence of the probe molecules, thereby achieving rapid detection of cyanide. The pH value of the experimental solution, reaction time, and interfering ions were optimized. The experimental results indicated that the FITC-Au NPs fluorescence probe had a minimum detection limit of 0.036 μmol/L for CN- in the presence of an H2O2 environment. There was a good linear relationship within the 0.05-80 μmol/L concentration range. The high stability and selectivity of FITC-Au NPs probes were utilized to achieve rapid detection of CN- in complex samples. This simple, fast, and economical fluorescence sensing system shows great practical potential in the detection of anions in actual samples. [ABSTRACT FROM AUTHOR]

Trisilacyclohexanes and bissilylmethanes with acetylene units attached to silicon sites have been converted into tri‐ and di‐nuclear gold(I)phosphane complexes and characterized by NMR spectroscopy and X‐ray diffraction. The bissilylmethane‐based gold complexes were used as a test system to work out the synthetic routes before transferring them to the trisilacyclohexane scaffolds, because the latter are more difficult to access. The occurrence of aurophilic interactions (short Au ⋅ ⋅ ⋅ Au contacts) depends on the steric bulk of the phosphorus‐bonded alkyl and aryl groups. DFT studies show that dispersion effects play an important role in the ability to form intramolecular Au ⋅ ⋅ ⋅ Au interactions. QTAIM analyses show that a subtle change of the steric bulk of the phosphane groups alters the relative strength of the dispersion and aurophilic interactions. The combination of DFT studies and X‐ray diffraction experiments shows that the conformation of the trisilacyclohexane backbone is also phase dependent. [ABSTRACT FROM AUTHOR]

Aquaporin‐3 (AQP3) is a membrane channel with dual aquaglyceroporin/peroxiporin activity, facilitating the diffusion of water, glycerol and H2O2 across cell membranes. AQP3 shows aberrant expression in melanoma and its role in cell adhesion, migration and proliferation is well described. Gold compounds were shown to modulate AQP3 activity with reduced associated toxicity, making them promising molecules for cancer therapy. In this study, we validated the phenotype resulting from AQP3‐silencing of two melanoma cell lines, MNT‐1 and A375, which resulted in decreased H2O2 permeability. Subsequently, the AQP3 inhibitory effect of a new series of organogold compounds derived from Auphen, a potent AQP3 inhibitor, was first evaluated in red blood cells (RBCs) that highly express AQP3, and then in HEK‐293T cells with AQP3 overexpression to ascertain the compounds' specificity. The first screening in RBCs unveiled two organogold compounds as promising blockers of AQP3 permeability. Moderate reduction of glycerol permeability but drastic inhibition of H2O2 permeability was detected for some of the gold derivatives in both AQP3‐overexpressing cells and human melanoma cell lines. Additionally, all compounds were effective in impairing cell adhesion, proliferation and migration, although in a cell type‐dependent manner. In conclusion, our data show that AQP3 peroxiporin activity is crucial for melanoma progression and highlight organogold compounds as promising AQP3 inhibitors with implications in melanoma cell adhesion, proliferation and migration, unveiling their potential as anticancer drugs against AQP3‐overexpressing tumours. Key points: AQP3 affects cellular redox balance.Gold compounds inhibit AQP3 permeability in melanoma cells.AQP3 is involved in cell adhesion, proliferation and migration of melanoma.Blockage of AQP3 peroxiporin activity impairs melanoma cell migration.Gold compounds are potential anticancer drug leads for AQP3‐overexpressing cancers. [ABSTRACT FROM AUTHOR]

[Display omitted] Transition metal complexes of copper subgroup metals are actively studied objects for temperature sensors. Their luminescence arising from the 3ILCT, 3MLCT or 3CC excited states is characterized by emission in all ranges of visible spectra and high quantum yields. Due to the ability of the complexes to emit in a dual band mode, these complexes are attractive for the temperature sensing in the ratiometric mode. Dual emission of complexes is usually susceptible of the irregular changes in intensity of two emission bands during the temperature changes. This is an important and necessary property for the utilization of phosphors as ratiometric thermometers. The structures and emission properties of gold(i) and copper(i) complexes are considered with the aim to demonstrate the possibility to apply such complexes as ratiometric molecular luminescent thermometers for the remote control of the object's temperature. [ABSTRACT FROM AUTHOR]

Overexpression of the epidermal growth factor receptor (EGFR, erbB1) has been observed in a wide range of solid tumors and has frequently been associated with poor prognosis. As a result, EGFR inhibition has become an attractive anticancer drug design strategy, and a large number of small molecular inhibitors have been developed. Despite the widespread clinical use of EGFR tyrosine kinase inhibitors (TKIs), their drug resistance, inadequate accumulation in tumors, and severe side effects have spurred the search for better antitumor drugs. Metal complexes have attracted much attention because of their different mechanisms compared with EGFR‐TKIs. Therefore, the combination of metals and inhibitors is a promising anticancer strategy. For example, Ru and Pt centers are introduced to design complexes with double or multiple targets, while Au complexes are combined with inhibitors to overcome drug resistance. Co complexes are designed as prodrugs with weak side effects and enhanced targeting by the hypoxia activation strategy, and other metals such as Rh and Fe enhance the anticancer effect of the complexes. In addition, the introduction of Ga center is beneficial to the development of nuclear imaging tracers. In this paper, metal EGFR‐TKI complexes in the last 15 years are reviewed, their mechanisms are briefly introduced, and their advantages are summarized. [ABSTRACT FROM AUTHOR]

Two N-alkyloxy-N′-phenylimidazolium proligands and the corresponding platinum(II) cyclometalated N-alkyloxyimidazol-2-ylidene complexes with β-diketonate auxiliary ligands, [(CNOHC^C*)Pt(L∩L)] (L∩L = acetyacetonate (acac) or 1,3-bis(2,4,6-trimethylphenyl)-propane-1,3-dionato (mesacac)) were synthesized and fully characterized. In addition, a Au(I) monocarbene complex was synthesized, isolated and characterized. Solid-state structures of two cyclometalated platinum(II) NOHC complexes and the Au(I) NOHC complex were obtained providing structural proof. [ABSTRACT FROM AUTHOR]

Developing candidate materials which possess the ability of both selective detection and efficient capture of precious metal gold is highly desirable for environment and economy. However, most of reported materials only focus on single function, which seriously restricts their practical application as probes or adsorbents. Herein, a two dimensional (2D) acridine‐based covalent organic framework (TpDa‐COF) is prepared via the linkage of imine bonds for gold detection and adsorption. The synthesized COF can achieve both fluorescence and colorimetric dual sensing for Au3+ in a low concentration range (0.1–1.5 ppm) with the limit of detection (LOD) of 0.036 ppm. Impressively, the selectivity of TpDa‐COF for the detection of Au3+ is admirable (Fe3+, Fe2+ and Cu2+ for negligible influence on its fluorescence). In addition, TpDa‐COF exhibits ultrahigh adsorption capacity of 982.5 mg ⋅ g−1 for gold at pH=4, which is attributed the synergistic effect of both selective coordination and reductive process of Au(III) to Au(0). Meanwhile, both positive entropy change (ΔS=76.07 J ⋅ mol−1 ⋅ K−1) and high distribution coefficient (Kd=12484.8 mL ⋅ g−1) confirm the good affinity between TpDa‐COF framework and gold. This work gives us a new insight to prepare COF with pyridine nitrogen sites for gold detection and adsorption. [ABSTRACT FROM AUTHOR]

This work explores the combination of sterically crowded low‐valent germanium compounds bearing one or two terphenyl (C6H3‐2,6‐Ar2) substituents with gold fragments, the latter stabilized by crowded phosphines also containing a terphenyl moiety. The steric protection of these motifs has allowed to examine a series of unusual gold‐germylene compounds featuring small hydride and methyl substituents at the germanium site. A gold‐germylene dicationic structure is also reported. The bonding in this series is investigated by computational means, providing understanding for the two‐way transfer of electrons from germanium to gold and vice versa. [ABSTRACT FROM AUTHOR]

Reaction of (P)AuOTf [P=P(t‐Bu)2o‐biphenyl] with indenyl‐ or 3‐methylindenyl lithium led to isolation of gold η1‐indenyl complexes (P)Au(η1‐inden‐1‐yl) (1 a) and (P)Au(η1‐3‐methylinden‐1‐yl) (1 b), respectively, in >65 % yield. Whereas complex 1 b is static, complex 1 a undergoes facile, degenerate 1,3‐migration of gold about the indenyl ligand (ΔG≠153K=9.1±1.1 kcal/mol). Treatment of complexes 1 a and 1 b with (P)AuNTf2 led to formation of the corresponding cationic bis(gold) indenyl complexes trans‐[(P)Au]2(η1,η1‐inden‐1,3‐yl) (2 a) and trans‐[(P)Au]2(η1,η2‐3‐methylinden‐1‐yl) (2 b), respectively, which were characterized spectroscopically and modeled computationally. Despite the absence of aurophilic stabilization in complexes 2 a and 2 b, the binding affinity of mono(gold) complex 1 a toward exogenous (P)Au+ exceed that of free indene by ~350‐fold and similarly the binding affinity of 1 b toward exogenous (P)Au+ exceed that of 3‐methylindene by ~50‐fold. The energy barrier for protodeauration of bis(gold) indenyl complex 2 a with HOAc was ≥8 kcal/mol higher than for protodeauration of mono(gold) complex 1 a. [ABSTRACT FROM AUTHOR]

Objective: A new series of pyrazole-3-carbaldehyde derivatives from new hydrazones by using the Vilsmeier–Haack reaction were synthesized. Pyrazoles have the characteristic qualities of the aromatic system, which are generally quite evident in their structures having insecticide, herbicide, and healthful significance as anti-inflammatory properties and antipyretic medication actions. Pyrazole compounds have a wide spectrum of bioactivity as reported in the literature, which encourages synthesis and testing of the antimicrobial activity for synthesis compounds. Methods: P-acetamido-phenol, and 2-mercaptobenzoimidazole, which used as a starting materials for synthesis pyrazole-3-carbaldehyde derivatives. The biological activity of some prepared compounds was also tested against two G-positive bacteria and two G-negative bacteria, in addition to C. albinos fungi. A molecular modeling study of some prepared compounds showed good binding strength with the target protein. Results and Discussion: Compound N-(4-((5-(4′-(4-formyl-1-phenyl-1H-pyrazole-3-carbonyl)-[1,1′-biphenyl]4-yl)-1,3,4-oxadiazol-2-yl)methoxy) phenyl)acetamide passes a good activity against Staphylococcus aurous; the compound 3-(4′-(5-(((1H-benzo[d]imidazol-2-yl)thio)methyl)-1,3,4-oxadiazol-2-yl)-[1,1′-biphenyl]-4-carbonyl)1-phenyl-1H-pyrazole-4-carbaldehyde passes good active with C. albinos. Molecular modeling was studied for the compounds prepared with human corona virus NL63, compound N-(4-((5-(4′-(4-formyl-1-phenyl-1H-pyrazole-3carbonyl)-[1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)methoxy)phenyl)acetamide has best docking score –181.9 kcal/mol, while compound 3-(4′-(5-(((1H-benzo[d]imidazol-2-yl)thio)methyl)-1,3,4-oxadiazol-2-yl)[1,1′-biphenyl]-4-carbonyl)-1-(4-nitroph enyl)-1H-pyrazole-4-carbaldehyde has best hydrogen-bonding with –10 kcal/mol. In general, the binding by hydrogen bonding and steric interference was high, which leads to the conclusion that the prepared compounds have an effect on the Corona virus. Conclusions: The prepared compounds have biological activity and have good binding force with the Corona virus protein NL63, thus disrupting its work, and ccording to the toxicity assessment, the synthesized compounds belong to the third class (III). [ABSTRACT FROM AUTHOR]

The following new compounds of gold(III) with 1,1-dimethylbiguanide (NH2C(=NH)NHC(=NH)N(CH3)2) are prepared and studied by XRD: [Au(dmbgH)Cl2]Cl.0.5H2O, [Au(dmbgH)Cl2]ClO4.H2O, [Au(dmbgH) Cl2]ClO4, [Au(dmbg)Cl2][Au(dmbgH)Cl2]Cl.H2O (dmbgH = 1,1-dimethylbiguanide, dmbg = deprotonated 1,1-dimethylbiguanide). [ABSTRACT FROM AUTHOR]

Gold precipitation in hydrothermal systems is traditionally attributed to supersaturation of gold due to decreasing gold complex stability triggered by changes in physicochemical conditions of the ore fluid. However, ultrahigh-grade gold veins in orogenic (shear zone related) gold deposits can contain kilograms per tonne of gold or more, in marked contrast to the typically very low gold concentrations (tens of parts per billion) in fluid. The gold mineral assemblage is commonly restricted to native gold and/or Au-(Ag)-tellurides and occurs in micro-fractures of sheared quartz veins. Textural and compositional characterization of such assemblages, coupled with hydrothermal diamond anvil cell experiments and heating-freezing experiments, provides evidence for an alternative ultrahigh-grade gold enrichment mechanism via growth of polymetallic melt droplets induced by quartz fracturing. We propose that polymetallic melt droplets of Au-Ag-Te-Bi-rich composition form through adsorption-reduction of metal complexes on fractured quartz surfaces, where surface silanol groups and hydrogen serve as reductants. The melt droplets subsequently grow by catalyzing reduction of metal complexes and absorbing metals from fluids percolating in the fractured quartz network. The mobile and reactive polymetallic melt droplets can repeatedly react with the fluid on protracted quartz fracturing and efficiently continue to scavenge gold from multiple pulses of gold-undersaturated ore fluids. [ABSTRACT FROM AUTHOR]

We report here a formal insertion of a metal carbene complex in a single carbon‐carbon bond. This behavior occurs with the participation of an α‐imino gold carbene complex, generated from benzofused triazapentalenes or, in a one‐pot procedure, from their 1‐propargyl‐1H‐benzotriazole precursors, and gold‐catalytically activated ynamides. As the result, 3H‐indole derivatives were obtained, with formation of a quaternary center. A computational analysis carried out on the reaction mechanism indicates that the bulkiness of the gold ligand plays a key role forcing a conformation, which includes aromatic interactions, that favors the approximation of the carbenic carbon to the reactive site. In addition, a negative crossover experiment rules out a cationic arene migration pathway. [ABSTRACT FROM AUTHOR]

In the search for a more effective chemotherapy for the treatment of Chagas' disease, caused by Trypanosoma cruzi parasite, the use of gold compounds may be a promising approach. In this work, four gold(I) compounds [AuCl(HL)], (HL = bioactive 5-nitrofuryl containing thiosemicarbazones) were studied. The compounds were theoretically characterized, showing identical chemical structures with the metal ion located in a linear coordination environment and the thiosemicarbazones acting as monodentate ligands. Cyclic voltammetry and Electron Spin Resonance (ESR) studies demonstrated that the complexes could generate the nitro anion radical (NO2−) by reduction of the nitro moiety. The compounds were evaluated in vitro on the trypomastigote form of T. cruzi and human cells of endothelial morphology. The gold compounds studied showed activity in the micromolar range against T. cruzi. The most active compounds (IC50 of around 10 μM) showed an enhancement of the antiparasitic activity compared with their respective bioactive ligands and moderate selectivity. To get insight into the anti-chagasic mechanism of action, the intracellular free radical production capacity of the gold compounds was assessed by ESR and fluorescence measurements. DMPO (5,5-dimethyl-1-pirroline-N-oxide) spin adducts related to the bioreduction of the complexes and redox cycling processes were characterized. The potential oxidative stress mechanism against T. cruzi was confirmed. [ABSTRACT FROM AUTHOR]

Transition metal complexes, such as the low‐spin bis (phenylterpyridine) (A) and bis (pyridylterpyrazine)iron (II) (B) complexes, provide didactic chromophore species for demonstrating the Raman, resonance Raman, and the surface‐enhanced Raman scattering (SERS) behavior in coordination chemistry, as well as for elucidating the nature of inner‐sphere and outer‐sphere association with plasmonic nanoparticles. Their electrostatically stabilized ion pairs with citrate–gold nanoparticles have been studied in an aqueous solution, from the pronounced changes in the plasmonic band at 540 nm. Complex A, lacking any coordinating site, can only generate outer‐sphere complexes with citrate–gold nanoparticles, but they are stable enough to give a strong SERS response, even at 10−8 M. At 10−6 M, agglomeration accompanies the decrease of the electrostatic repulsion, resulting in a sharp decay of the plasmon resonance band at 540 nm. This is followed by the rise of a plasmon coupling band above 700 nm. However, at 10−4 M, the excess of the complex in the adsorption layer produces a reverse effect, decreasing agglomeration. The observed Raman spectra are essentially similar for the several concentrations employed because the outer‐sphere interaction implies a SERS electromagnetic mechanism. In contrast, complex B exhibits several pyridine and pyrazine N‐atoms available to form inner‐sphere‐associated species. A selective enhancement of the SERS signals is observed at 10−8 M, clearly indicating a chemical mechanism, consistent with a bridging mode. At 10−6 M and above, the agglomeration leads to a plasmon coupling band at 800 nm, while the SERS response indicates a change in the binding modes dictated by the excess of the complexing molecules. [ABSTRACT FROM AUTHOR]

We recently found that polyvinylpyrrolidone (PVP)-protected metal nanoparticles dispersed in water/butanol mixture spontaneously float to the air/water interface and form two-dimensional assemblies due to classical surface excess theory and Rayleigh–Bénard–Marangoni convection induced by butanol evaporation. In this study, we found that by leveraging this principle, a unique structure is formed where hetero gold nanospheres (AuNPs)/gold nanostars (AuNSs) complexes are dispersed within AuNP two-dimensional assemblies, obtained from a mixture of polyvinylpyrrolidone-protected AuNPs and AuNSs that interact electrostatically with the AuNPs. These structures were believed to form as a result of AuNPs/AuNSs complexes formed in the water/butanol mixture floating to the air/water interface and being incorporated into the growth of AuNP two-dimensional assemblies. These structures were obtained by optimizing the amount of mixed AuNSs, with excessive addition resulting in the formation of random three-dimensional network structures. The AuNP assemblies dispersed with AuNPs/AuNSs complexes exhibited significantly higher Raman (surface-enhanced resonance Raman scattering: SERRS) activity compared to simple AuNP assemblies, while the three-dimensional network structure did not show significant SERRS activity enhancement. These results demonstrate the excellent SERRS activity of AuNP two-dimensional assemblies dispersed with hetero AuNPs/AuNSs complexes. [ABSTRACT FROM AUTHOR]

Pyridoxal and pyridoxal 5′-phosphate are aldehyde forms of B6 vitamin that can easily be transformed into each other in the living organism. The presence of a phosphate group, however, provides the related compounds (e.g., hydrazones) with better solubility in water. In addition, the phosphate group may sometimes act as a binding center for metal ions. In particular, a phosphate group can be a strong ligand for a gold(III) ion, which is of interest for researchers for the anti-tumor and antimicrobial potential of gold(III). This paper aims to answer whether the phosphate group is involved in the complex formation between gold(III) and hydrazones derived from pyridoxal 5′-phosphate. The answer is negative, since the comparison of the stability constants determined for the gold(III) complexes with pyridoxal- and pyridoxal 5′-phosphate-derived hydrazones showed a negligible difference. In addition, quantum chemical calculations confirmed that the preferential coordination of two series of phosphorylated and non-phosphorylated hydrazones to gold(III) ion is similar. The preferential protonation modes for the gold(III) complexes were also determined using experimental and calculated data. [ABSTRACT FROM AUTHOR]

One of the recent significant but challenging research studies in computational biology and bioinformatics is to unveil protein complexes from protein-protein interaction networks (PPINs). However, the development of a reliable algorithm to detect more complexes with high quality is still ongoing in many studies. The main contribution of this paper is to improve the effectiveness of the well-known modularity density ( ) model when used as a single objective optimization function in the framework of the canonical evolutionary algorithm (EA). To this end, the design of the EA is modified with a gene ontology-based mutation operator, where the aim is to make a positive collaboration between the modularity density model and the proposed gene ontology-based mutation operator. The performance of the proposed EA to have a high quantity and quality of the detected complexes is assessed on two yeast PPINs and compared with two benchmarking gold complex sets. The reported results reveal the ability of modularity density to be more productive in detecting more complexes with high quality when teamed up with a gene ontology-based mutation operator. [ABSTRACT FROM AUTHOR]

Cancer treatments are advancing to harness the body's immune system against tumours, aiming for lasting effects. This progress involves combining potent chemotherapy drugs with immunogens to kill cancer cells and trigger lasting immunity. Developing new prodrugs that integrate both chemotherapy and immune-boosting elements could significantly improve anticancer outcomes by activating multiple mechanisms to kill cancer cells. While bacterial polysaccharides are typically not used in therapy due to their immune-stimulating properties, we propose a safe application of an extremophilic bacterial polysaccharide, Mauran (MR), modified with the anticancer drug 5-fluorouracil (5FU) to create a novel prodrug. This obtained prodrug, chloracetyl-MR-5FU, is specifically targeted using gold nanocages to CD133+ glioma cells. Test results have shown a high encapsulation efficiency of the drug during the polysaccharide modification process; its anticancer activity was demonstrated in vitro and the release of the prodrug was demonstrated in ex vivo studies. [ABSTRACT FROM AUTHOR]