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Gold

goldZum Golde drängt, am Golde hängt doch alles.
For gold contend, On gold depend All things.

J. W. Goethe, Faust I

The element gold has many personalities, of which the image of a noble but soft, yellow metal would first across one's mind. The recently discovered nanoparticles and nanowires containing gold are a natural extension of this aspect, as are the uses of gold in electronics and decoration. Thought to be noble, gold actually has a rich chemistry. Fascinating in its complexity for academic chemists, this chemistry has potential applications in materials science, medicine and, recently, in both heterogeneous and homogeneous catalysis. Some fresh promises are related to the optical properties of certain gold compounds or to the possibility of forming new nanostructures based on gold. The unique properties of gold are strongly influenced by relativistic effects.

[1] P. Pyykkö, Theoretical Chemistry of Gold
Angew. Chem. 2004, 116, 4512–4557; Angew. Chem. Int. Ed. 2004, 43, 4412–4456

[2] A. S. K. Hashmi, The Catalysis Gold Rush: New Claims
Angew. Chem. 2005, 117, 7150; Angew. Chem. Int. Ed. 2005, 44, 6990

[3] G. Schmid, B. Corain, Nanoparticulated Gold: Syntheses, Structures, Electronics, and Reactivities
Eur. J. Inorg. Chem. 2003, 3081

Recent Articles

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Biosynthesized Gold Nanoclusters and Iron Complexes as Scaffolds for Multimodal Cancer Bioimaging

Biosynthesized Gold Nanoclusters and Iron Complexes as Scaffolds for Multimodal Cancer Bioimaging

The Au-Fe ions (AuCl4 ions (i.e., HAuCl4) and Fe2+ ions (i.e., FeCl2)) can be converted to Au NCs and iron complexes in the presence of glutathione (GSH). Since the tumor microenvironment is richer in GSH compared with normal cells or tissues, this is encouraging for the use of Au-Fe ions for target cancer multimodal bioimaging.

[Full Paper]
Chunqiu Zhao, Tianyu Du, Fawad ur Rehman, Lanmei Lai, Xiaoli Liu, Xuerui Jiang, Xiaoqi Li, Yun Chen, Hang Zhang, Yi Sun, Shouhua Luo, Hui Jiang, Matthias Selke, Xuemei Wang
Small, September 27, 2016, DOI: 10.1002/smll.201602526. Read article

Theoretical Study of the Adsorption Mechanism of Cystine on Au(110) in Aqueous Solution

Theoretical Study of the Adsorption Mechanism of Cystine on Au(110) in Aqueous Solution

The adsorption of cystine, a cysteine dimer, on the Au(110) slab in water solution is investigated using ReaxFF molecular dynamics simulations. All the steps of the mechanism, namely physisorption, disulfide bond breaking, chemisorption, formation of staples, and reformation of the disulfide bridge in a crowded environment are identified and characterized in detail.

[Full Paper]
Susanna Monti, Vincenzo Carravetta, Hans Ågren
Small, September 27, 2016, DOI: 10.1002/smll.201602275. Read article

Breaching the Hyaluronan Barrier with PH20-Fc Facilitates Intratumoral Permeation and Enhances Antitumor Efficiency: A Comparative Investigation of Typical Therapeutic Agents in Different Nanoscales

Breaching the Hyaluronan Barrier with PH20‐Fc Facilitates Intratumoral Permeation and Enhances Antitumor Efficiency: A Comparative Investigation of Typical Therapeutic Agents in Different Nanoscales

Intratumoral delivery of typical therapeutic agents (doxorubicin, trastuzumab, and pegylated gold nanorods) can be significantly enhanced by degrading tumor microenvironment component hyaluronan with long-acting hyaluronidase PH20-Fc. Meanwhile, the performance of PH20-Fc varies among these three therapeutic agents due to ther different nanoscales, and Tmab benefits most in penetration and accumulation.

[Full Paper]
Shan Liu, Wei Wei, Bo Xie, Hua Yue, Dezhi Ni, Yali Bao, Guanghui Ma, Zhiguo G. Su
Adv. Healthcare Mater., September 27, 2016, DOI: 10.1002/adhm.201600528. Read article

Functionalization of Planet–Satellite Nanostructures Revealed by Nanoscopic Localization of Distinct Macromolecular Species

Functionalization of Planet–Satellite Nanostructures Revealed by Nanoscopic Localization of Distinct Macromolecular Species

The functionalization of hybrid polymer/gold planet–satellite nanostructures with functional polymer is achieved by introducing linear reversible addition–fragmentation chain transfer polymers of 4-(chloromethyl)benzyl acrylate. Insights into the fine structural details of the polymeric part of these nanostructures are obtained via scanning transmission electron microscopy and spectrum imaging.

[Communication]
Christian Rossner, Vladimir Roddatis, Sergei Lopatin, Philipp Vana
Macromol. Rapid Commun., September 26, 2016, DOI: 10.1002/marc.201600480. Read article

Hierarchically Templated Synthesis of Hollow Nanoporous Gold Rods and TiO2-Coated Gold Rods

Gold nanomaterials have shown promising applications in catalysis and sensing. Among current research and development of gold catalysts, exploration of new forms is one of the major priority. Using bacteria as the supporting template and polystyrene spheres as the pore-generation template, a hierarchical template synthesis strategy was developed in the present study to synthesize hollow nanoporous gold rods. The pore size can be easily adjusted using PSS with different diameters as the template (The pore size is about 160 nm and 70 nm respectively when using 200nm and 110nm PSS as the template). Moreover, with the simple sol-gel method, TiO2 can be coated on such nanoporous gold rods with different contents. The results showed the thermal stability and catalytic activity of the nanoporous gold rods were improved dramatically with moderate TiO2 coating. Using reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride as the model reaction, excellent catalytic properties (reaction rate constant k=0.246 min-1) of prepared TiO2-coated gold rods catalysts were confirmed.

[Full Paper]
Lei Gao, Chennan Liang, Huihui Li, Zhexue Lu
ChemNanoMat, September 26, 2016, DOI: 10.1002/cnma.201600244. Read article

Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N‐Heterocyclic Carbene Complexes

Golden combination: The iodination of terminal alkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst was achieved in good to excellent yields under mild reaction conditions. The resulting 1-iodoalkynes were used as organic building blocks for the synthesis of trisubstituted (Z)-fluoroalkenes in two sequential steps: The selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex.

[Full Paper]
Alberto Gómez-Herrera, Fady Nahra, Marcel Brill, Steven P. Nolan, Catherine S. J. Cazin
ChemCatChem, September 26, 2016, DOI: 10.1002/cctc.201600868. Read article

High Performance, Multiplexed Lung Cancer Biomarker Detection on a Plasmonic Gold Chip

High Performance, Multiplexed Lung Cancer Biomarker Detection on a Plasmonic Gold Chip

Plasmonic gold (pGOLD) chip-based diagnosis of lung cancer is performed using multiplexed near-infrared detection of biomarkers in the serum samples of patients. Multiplexed microarray analysis of biomarkers in 10 μL of human serum on a pGOLD chip leads to markedly improved limit-of-quantification, limit-of-detection, reproducibility, and higher diagnostic sensitivity and specificity compared to traditional biochips and Luminex technology currently in use in hospitals.

[Full Paper]
Bin Liu, Yaling Li, Hao Wan, Lin Wang, Wei Xu, Shoujun Zhu, Yongye Liang, Bo Zhang, Jiatao Lou, Hongjie Dai, Kun Qian
Adv. Funct. Mater., September 26, 2016, DOI: 10.1002/adfm.201603547. Read article

Fabrication and Application of Isotopically Labelled Gold Arrays for Multiplexed Peptide Analysis

Fabrication and Application of Isotopically Labelled Gold Arrays for Multiplexed Peptide Analysis

Solid gold: A new array-based technology for the simultaneous capture, chemical labelling and mass spectrometric analysis of peptides is presented. This new solid-phase array platform has the advantages of minimal sample manipulation and is suitable for multiple analyses of single protein digests on a single MALDI target plate.

[Communication]
Roberto Castangia, Siân R. Hudson, Helen K. Robinson, Sabine L. Flitsch, Jane Thomas-Oates, Anne Routledge
ChemBioChem, September 21, 2016, DOI: 10.1002/cbic.201600347. Read article

Au-Decorated Cracked Carbon Tube Arrays as Binder-Free Catalytic Cathode Enabling Guided Li2O2 Inner Growth for High-Performance Li-O2 Batteries

Au‐Decorated Cracked Carbon Tube Arrays as Binder‐Free Catalytic Cathode Enabling Guided Li2O2 Inner Growth for High‐Performance Li‐O2 Batteries

Ni-supported carbon submicron tube arrays with Au decorated on the inner walls (Au@CST) catalyze conformal growth of thin-layered Li2O2 on the inner walls, leading to a high capacity and long cycle life of Li-O2 cells. The Li-O2 cell with an Au@CST array cathode maintains a stable cycling of 112 times under 400 mA g–1 at 500 mAh g–1.

[Full Paper]
Fangfang Tu, Junping Hu, Jian Xie, Gaoshao Cao, Shichao Zhang, Shengyuan A. Yang, Xinbing Zhao, Hui Ying Yang
Adv. Funct. Mater., September 16, 2016, DOI: 10.1002/adfm.201603088. Read article

Bimetallic and Plasmonic Ag–Au on TiO2 for Solar Water Splitting: An Active Nanocomposite for Entire Visible-Light-Region Absorption

Bimetallic and Plasmonic Ag–Au on TiO2 for Solar Water Splitting: An Active Nanocomposite for Entire Visible‐Light‐Region Absorption

Silver lining to water splitting: Light absorption to the wide wavelength range within the visible-light-region is demonstrated with a combination of two different plasmonic metals Ag+Au on TiO2. H2 generation from water splitting or photocurrent generation on Ag on Au-TiO2 increases at least twice that of Ag or Au alone on TiO2.

[Full Paper]
Kshirodra K. Patra, Chinnakonda S. Gopinath
ChemCatChem, September 15, 2016, DOI: 10.1002/cctc.201600937. Read article

Gold-Catalyzed Synthesis of Quinolines from Propargyl Silyl Ethers and Anthranils through the Umpolung of a Gold Carbene Carbon

Gold‐Catalyzed Synthesis of Quinolines from Propargyl Silyl Ethers and Anthranils through the Umpolung of a Gold Carbene Carbon

All together now: A gold-catalyzed cascade annulation of propargylic silyl ethers with anthranils proceeds through a sequential ring opening/1,2-H-shift/protodeauration/Mukaiyama aldol cyclization. This method offers regiospecific and modular access to 2-aminoquinolines and other quinoline derivatives under mild conditions and with a broad functional-group tolerance.

[Communication]
Hongming Jin, Bin Tian, Xinlong Song, Jin Xie, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Angew. Chem. Int. Ed., September 15, 2016, DOI: 10.1002/anie.201606043. Read article

Gold–Organic Hybrids: On-Surface Synthesis and Perspectives

Gold–Organic Hybrids: On‐Surface Synthesis and Perspectives

Gold–organic hybrids with various aryl[BOND]Au bonding geometries can be prepared on gold substrates through on-surface dehalogenation of molecular precursors with multiple halogen substituents. Recent progress made in the synthesis, large-scale alignment and scanning tunneling spectroscopy of gold–organic hybrids is highlighted.

[Research News]
Haiming Zhang, Lifeng Chi
Adv. Mater., September 15, 2016, DOI: 10.1002/adma.201602131. Read article

Reaction and Mechanistic Studies of Heterogeneous Hydroamination over Support-Stabilized Gold Nanoparticles

Reaction and Mechanistic Studies of Heterogeneous Hydroamination over Support‐Stabilized Gold Nanoparticles

Au hydroamination catalyst: The in situ synthesis of gold nanoparticles in the surface cavity of mesoporous nitrogen-rich carbon (MCN) allowed them to be utilized efficiently as a catalyst in the hydroamination of phenylacetylene with aniline, with more than 98 % selectivity towards the Markovnikov addition product. The mechanistic pathway has been studied with DFT-based calculations, which predict the stabilization of tetranuclear Au clusters over the MCN support.

[Full Paper]
Manideepa Sengupta, Arijit Bag, Subhasis Das, Astha Shukla, L. N. Sivakumar Konathala, C. A. Naidu, Ankur Bordoloi
ChemCatChem, September 14, 2016, DOI: 10.1002/cctc.201600762. Read article

Copper-Modified Gold Nanoparticles as Highly Selective Catalysts for Glycerol Electro-Oxidation in Alkaline Solution

Copper‐Modified Gold Nanoparticles as Highly Selective Catalysts for Glycerol Electro‐Oxidation in Alkaline Solution

C3 selectivity is important: The C3 selectivity of carbon-supported Au nanoparticles for glycerol electro-oxidation is significantly enhanced by the interaction of Au with electrodeposited Cu species. Notably, the C3 selectivity of supported Au nanoparticles doubles after 90 min of Cu electrodeposition at +0.015 V.

[Full Paper]
Larissa Thia, Mingshi Xie, Zhaolin Liu, Xiaoming Ge, Yizhong Lu, Wenmei Eileen Fong, Xin Wang
ChemCatChem, September 14, 2016, DOI: 10.1002/cctc.201600725. Read article

Split-GFP: SERS Enhancers in Plasmonic Nanocluster Probes

Split‐GFP: SERS Enhancers in Plasmonic Nanocluster Probes

Split-green fluorescence protein (sGFP) fragments are used as molecular glue to assemble plasmonic gold nanoparticles into surface-enhanced Raman scattering (SERS) nanoprobes with controlled hot spot geometry. Numerical modeling of a variety of nanocluster sizes and shapes indicate that near-infrared SERS enhancement of the GFP chromophore within hot spots can be achieved with factors of 108–109 that are sufficiently large for single molecule SERS detection.

[Full Paper]
Taerin Chung, Tugba Koker, Fabien Pinaud
Small, September 08, 2016, DOI: 10.1002/smll.201601631. Read article

The Conversion of Methanol into Higher Hydrocarbons Catalyzed by Gold

The Conversion of Methanol into Higher Hydrocarbons Catalyzed by Gold

Golden combination: Gold/zinc oxide catalysts are active in the conversion of methanol to higher hydrocarbons under mild conditions. Conversions exceed 97 % and a selectivity of approximately 44 % hydrocarbons and 56 % dimethyl ether under the selected reaction conditions can be achieved.

[Full Paper]
Sam Gabriel, Michael S. Scurrell
ChemCatChem, August 31, 2016, DOI: 10.1002/cctc.201600727. Read article

D6h-Au42 Isomer: A Golden Aromatic Toroid Involving Superatomic π-Orbitals that Follow the Hückel (4n+2)π rule

D6h‐Au42 Isomer: A Golden Aromatic Toroid Involving Superatomic π‐Orbitals that Follow the Hückel (4n+2)π rule

Taking it to the next level: A Au42 isomer shows similarity to cyclic aromatic molecules with a superatomic π-electron system.

[Article]
Alvaro Muñoz-Castro
ChemPhysChem, August 30, 2016, DOI: 10.1002/cphc.201600864. Read article

A Simple and Highly Stable Porous Gold-based Electrochemical Sensor for Bisphenol A Detection

A Simple and Highly Stable Porous Gold‐based Electrochemical Sensor for Bisphenol A Detection

[Full Paper]
Rodtichoti Wannapob, Panote Thavarungkul, Supaporn Dawan, Apon Numnuam, Warakorn Limbut, Proespichaya Kanatharana
Electroanalysis, August 25, 2016, DOI: 10.1002/elan.201600371. Read article

A Novel Solid-state Electrochemiluminescent Enantioselective Sensor for Ascorbic Acid and Isoascorbic Acid

A Novel Solid‐state Electrochemiluminescent Enantioselective Sensor for Ascorbic Acid and Isoascorbic Acid

[Full Paper]
Shu Zhu, Xia Lin, Qinghong Wang, Qiao Xia, Peiyao Ran, Yingzi Fu
Electroanalysis, August 25, 2016, DOI: 10.1002/elan.201600329. Read article

From the Superatom Model to a Diverse Array of Super-Elements: A Systematic Study of Dopant Influence on the Electronic Structure of Thiolate-Protected Gold Clusters

From the Superatom Model to a Diverse Array of Super‐Elements: A Systematic Study of Dopant Influence on the Electronic Structure of Thiolate‐Protected Gold Clusters

The effects of microdoping: The tunability of doped thiolate-protected gold clusters is systematically investigated by means of density functional theory. The superatomic model is evaluated for its applicability, by comparing structural distortion and electronic inhomogeneity for Pd-, Pt-, Cu- and Ag-doped clusters.

[Article]
Julia Schacht, Nicola Gaston
ChemPhysChem, August 19, 2016, DOI: 10.1002/cphc.201600684. Read article

A Simple Flow Amperometric Electrochemical Biosensor Based on Chitosan Scaffolds and Gold Nanowires Modified on a Glassy Carbon Electrode for Detection of Glutamate in Food Products

A Simple Flow Amperometric Electrochemical Biosensor Based on Chitosan Scaffolds and Gold Nanowires Modified on a Glassy Carbon Electrode for Detection of Glutamate in Food Products

[Full Paper]
Jiraporn Kitikul, Sakchai Satienperakul, Anchana Preechaworapun, Pusit Pookmanee, Tanin Tangkuaram
Electroanalysis, August 12, 2016, DOI: 10.1002/elan.201600263. Read article

Selective Detection of Dopamine in the Presence of Ascorbic and Uric Acids through its Covalent Immobilization on Gold Mercaptopropionic Acid Self-assembled Monolayer

Selective Detection of Dopamine in the Presence of Ascorbic and Uric Acids through its Covalent Immobilization on Gold Mercaptopropionic Acid Self‐assembled Monolayer

[Full Paper]
Reza Karimi Shervedani, Sonia Bahrani, Marzieh Samiei Foroushani, Fariborz Momenbeik
Electroanalysis, August 12, 2016, DOI: 10.1002/elan.201600220. Read article

Effects of Functionalized Electrodes and Gold Nanoparticle Carrier Signal Amplification on an Electrochemical DNA Sensing Strategy

Effects of Functionalized Electrodes and Gold Nanoparticle Carrier Signal Amplification on an Electrochemical DNA Sensing Strategy

Which effect is stronger? A DNA sensing strategy to analyze the effects on the electrochemical response of electrode functionalization and signal amplification is described (see figure). Four kinds of electrodes and a methyl blue labeled DNA signal probe with or without the gold nanoparticle (nanoAu) carrier amplification strategy are discussed.

[Article]
Yi Zhang, Chen Qian, Guang Ming Zeng, Lin Tang, Chang Zhang, Yuan Zhu, Chong Ling Feng, Yuan Yuan Liu
ChemElectroChem, August 11, 2016, DOI: 10.1002/celc.201600362. Read article

Controlled Synthesis of Carbon-Supported Gold Clusters for Rational Catalyst Design

Controlled Synthesis of Carbon‐Supported Gold Clusters for Rational Catalyst Design

The development of metal-cluster catalysts requires a rational design principle as well as atomically precise synthetic methods. A method to precisely and independently control the size, composition, and surface modification of heterogeneous gold clusters by calcination of the ligand-protected Au clusters on carbon supports is discussed using benzyl alcohol oxidation as a test reaction.

[Personal Account]
Seiji Yamazoe, Tatchamapan Yoskamtorn, Shinjiro Takano, Sudarat Yadnum, Jumras Limtrakul, Tatsuya Tsukuda
The Chemical Record, August 04, 2016, DOI: 10.1002/tcr.201600074. Read article

Tuning Gold Nanoparticle Aggregation through the Inhibition of Acid Phosphatase Bioactivity: A Plasmonic Sensor for Light-Up Visual Detection of Arsenate (AsV)

Tuning Gold Nanoparticle Aggregation through the Inhibition of Acid Phosphatase Bioactivity: A Plasmonic Sensor for Light‐Up Visual Detection of Arsenate (AsV)

Good AsV gold: The first colorimetric sensor specifically for arsenate makes use of gold nanoparticles. The sensing rationale relies on the selective inhibition of acid phosphatase bioactivity by arsenate, leading to the reversal of solution color from blue to red.

[Communication]
Jia Zhang, Chuan-Ling Zhang, Shu-Hong Yu
ChemPlusChem, August 03, 2016, DOI: 10.1002/cplu.201600355. Read article

When Inert Becomes Active: A Fascinating Route for Catalyst Design

When Inert Becomes Active: A Fascinating Route for Catalyst Design

The nanoscale functionalization of catalytically inactive or completely inert materials via their size, structure, morphology, and support material represents a novel route to catalytically active systems. In particular, functionalization of hexagonal boron nitride led to its activity in a number of catalytic reactions involving oxygen activation, oxidation by molecular oxygen, and the oxygen reduction reaction.

[Personal Account]
Andrey Lyalin, Min Gao, Tetsuya Taketsugu
The Chemical Record, July 29, 2016, DOI: 10.1002/tcr.201600035. Read article

Deubiquitinases as Anticancer Targets of Gold Complexes

Deubiquitinases as Anticancer Targets of Gold Complexes

[Review]
Taotao Zou, Jing-Jing Zhang, Bei Cao, Ka-Chung Tong, Chun-Nam Lok, Chi-Ming Che
Isr. J. Chem., July 28, 2016, DOI: 10.1002/ijch.201600044. Read article

Preparation of Triazole Gold(III) Complex as an Effective Catalyst for the Synthesis of E-α-Haloenones

Preparation of Triazole Gold(III) Complex as an Effective Catalyst for the Synthesis of E-α-Haloenones

[Communication]
Yongchun Yang, Wenkang Hu, Xiaohan Ye, Dawei Wang, Xiaodong Shi
Adv. Synth. Catal., July 12, 2016, DOI: 10.1002/adsc.201600243. Read article.

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Au nanocluster catalysts exhibit remarkable catalytic activities for several reactions. The emphasis here is on our research into the development of preparation methods, their characterization, theoretical calculations, and application in catalysis. We share our insight into the interplay between them.

[Personal Account]
Tamao Ishida, Hiroaki Koga, Mitsutaka Okumura, Masatake Haruta
The Chemical Record, June 27, 2016, DOI: 10.1002/tcr.201600046. Read article

Dopamine-Directed In-Situ and One-Step Synthesis of Au@Ag Core–Shell Nanoparticles Immobilized to a Metal–Organic Framework for Synergistic Catalysis

Dopamine‐Directed In‐Situ and One‐Step Synthesis of Au@Ag Core–Shell Nanoparticles Immobilized to a Metal–Organic Framework for Synergistic Catalysis

There′s a synergy: Bimetallic core–shell Au@Ag NPs were immobilized in MOFs via one-step synthetic route at room temperature by using dopamine (DA) as a moderate reductant to reduce the bimetallic precursors step-by-step spontaneously. The as-formed Au@Ag/MOF composites show a striking synergistic effect for heterogeneous catalysis.

[Communication]
Pengcheng Huang, Wenjie Ma, Ping Yu, Lanqun Mao
Chem. Asian J., June 02, 2016, DOI: 10.1002/asia.201600469. Read article

Synthesis and Catalytic Activity of Gold Nanoparticles Supported on Dendrimeric Nanocellulose Hybrids

Synthesis and Catalytic Activity of Gold Nanoparticles Supported on Dendrimeric Nanocellulose Hybrids

Alkynyl-dendrons of the PAMAM family were covalently attached to azide-linked cellulose nanocrystals using click chemistry and then used as templates for the preparation of stable and monodispersed gold nanoparticles in aqueous media. The new materials were evaluated as catalysts for the reduction of 4-nitrophenyl and displayed enhanced activity relative to other supported AuNPs.

[Full Paper]
Ana Herreros-López, Caroline Hadad, Luis Yate, Ali A. Alshatwi, Nicola Vicentini, Tommaso Carofiglio, Maurizio Prato
Eur. J. Org. Chem., April 27, 2016, DOI: 10.1002/ejoc.201600148. Read article.

Synthesis of Gold(I) Derivatives Bearing Alkylated 1,3,5-Triaza-7-phosphaadamantane as Selective Anticancer Metallodrugs

Synthesis of Gold(I) Derivatives Bearing Alkylated 1,3,5-Triaza-7-phosphaadamantane as Selective Anticancer Metallodrugs

The preparation of new water-soluble mono- and bis-phosphanes derived from 1,3,5-triaza-7-phosphaadamantane (PTA) is described. Antiproliferative effects against colon cancer cell lines and low cytotoxicity towards differentiated cells (non-carcinogenic) have been observed for some of the gold complexes formed with these phosphanes.

[Full Paper]
Elena Atrián-Blasco, Sonia Gascón, M. Jesús Rodríguez-Yoldi, Mariano Laguna, Elena Cerrada
Eur. J. Inorg. Chem., April 24, 2016, DOI: 10.1002/ejic.201600177. Read article.

Isolable Ethylene Complexes of Copper(I), Silver(I), and Gold(I) Supported by Fluorinated Scorpionates [HB{3-(CF3),5-(CH3)Pz}3] and [HB{3-(CF3),5-(Ph)Pz}3]

Isolable Ethylene Complexes of Copper(I), Silver(I), and Gold(I) Supported by Fluorinated Scorpionates [HB{3-(CF3),5-(CH3)Pz}3]– and [HB{3-(CF3),5-(Ph)Pz}3]–

Partially fluorinated scorpionate [HB{3-(CF3),5-(CH3)Pz}3] allows the stabilization of molecules with gold(I), silver(I) and copper(I) ethylene adducts. Related adducts supported by [HB{3-(CF3),5-(CH3)Pz}3] are also included for comparisons. Notable differences exist in scorpionate modes of coordination and ethylene carbon chemical shift values.

[Communication]
Shawn G. Ridlen, Jiang Wu, Naveen V. Kulkarni, H. V. Rasika Dias
Eur. J. Inorg. Chem., February 9, 2016, DOI: 10.1002/ejic.201501365. Read article.

Detailed Investigation of the Structural, Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano-Triggered Single-Crystal-to-Single-Crystal Phase Transitions

Detailed Investigation of the Structural, Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano-Triggered Single-Crystal-to-Single-Crystal Phase Transitions

Mechano-induced phase transitions: A detailed investigation of two intriguing gold(I) complexes that show mechano-triggered single-crystal-to-single-crystal (SCSC) phase transitions is described, which includes face index experiments, thermal analyses, and conductivity measurements (see figure). Various hitherto unknown insights into the mechano-responsive molecular crystals have been reported.

[Full Paper]
Tomohiro Seki, Kenta Sakurada, Mai Muromoto, Shu Seki, Hajime Ito
Chem. Eur. J., January 11, 2016, DOI: 10.1002/chem.201503721. Read article.

Co-Adsorption of O2 and CO on Au2: Infrared Photodissociation Spectroscopy and Theoretical Study of [Au2O2(CO)n] (n=2–6)

Co-Adsorption of O2 and CO on Au2−: Infrared Photodissociation Spectroscopy and Theoretical Study of [Au2O2(CO)n]− (n=2–6)

Co-adsorption: The [Au2O2(CO)n] (n=2–6) complexes were prepared through a laser vaporization supersonic ion source and were studied by using infrared photodissociation spectroscopy (see figure). All complexes were characterized to have a core structure involving one CO and one O2 molecule co-adsorbed on Au2 with the other CO molecules physically tagged around.

[Full Paper]
Hao Liu, Xiaopeng Xing, Xuefeng Wang, Hui Qu, Guan-jun Wang, Ming-fei Zhou
Chem. Eur. J., January 8, 2016, DOI: 10.1002/chem.201504384. Read article.

Gold-Catalyzed Tandem Cycloisomerization–Halogenation of Chiral Homopropargyl Sulfonamides

Gold-Catalyzed Tandem Cycloisomerization–Halogenation of Chiral Homopropargyl Sulfonamides

Two new gold-catalyzed tandem cycloisomerization–halogenation reactions of chiral homopropargyl sulfonamides have been developed. Enantioenriched 3,3-diiodopyrrolidin-2-ols and 3-fluoropyrrolidin-2-ols were obtained in moderate-to-good yields with excellent enantio- and diastereocontrol (see scheme; PG=protecting group, DCE=1,2-dichloroethane, NIS=N-iodosuccinimide).

[Full Paper]
Chao Shu, Long Li, Cang-Hai Shen, Peng-Peng Ruan, Chao-Yue Liu, Long-Wu Ye 
Chem. Eur. J., January 8, 2016, DOI: 10.1002/chem.201503891. Read article.

Chemo- and Regioselective Ethynylation of Tryptophan-Containing Peptides and Proteins

Chemo- and Regioselective Ethynylation of Tryptophan-Containing Peptides and Proteins

Alkynes on a gold Tr(i)p! Various peptides and one model protein were functionalized with ethynyl moieties at their tryptophan residues using Waser’s reagent, TIPS-EBX, under gold(I) catalysis (see scheme; TIPS=triisopropylsilyl). The reaction proceeded in a regio- and chemoselective manner leading to C2 substitution at the tryptophan residues only. Subsequently, the terminal alkyne was used to label one of the model peptides with a fluorophore by means of copper-catalyzed click chemistry.

[Communication]
Morten Borre Hansen, František Hubálek, Troels Skrydstrup, Thomas Hoeg-Jensen
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504462. Read article.

Activation and Transformation of Ethane by Au2VO3+ Clusters with Closed-Shell Electronic Structures

Activation and Transformation of Ethane by Au2VO3+ Clusters with Closed-Shell Electronic Structures

The crucial role of gold in the transformation of ethane to ethene and dihydrogen is observed in the reaction between C2H6 and Au2VO3+ clusters with closed-shell electronic structures. The first C-H activation is initiated by gold rather than an oxygen species. The Au-Au dimer formed during the reactions plays important roles in converting ethane into ethene and making dihydrogen energetically more favorable.

[Full Paper]
Ya-Ke Li, Zi-Yu Li, Yan-Xia Zhao, Qing-Yu Liu, Jing-Heng Meng, Sheng-Gui He
Chem. Eur. J., December 17, 2015, DOI: 10.1002/chem.201503676. Read article.

On the Mechanism of the Digold(I)–Hydroxide-Catalysed Hydrophenoxylation of Alkynes

On the Mechanism of the Digold(I)–Hydroxide-Catalysed Hydrophenoxylation of Alkynes

Gold rush! A series of in silico studies, supported by experimental work, have been carried out to further elucidate the mechanistic aspects of the hydrophenoxylation of alkynes. The results suggest that the synergic cooperation of two mono-gold species facilitates this process, although analogous mono-gold species are not capable of mediating this reaction (see figure).

[Full Paper]
Adrián Gómez-Suárez, Yoshihiro Oonishi, Anthony R. Martin, Sai V. C. Vummaleti, David J. Nelson, David B. Cordes, Alexandra M. Z. Slawin, Luigi Cavallo, Steven P. Nolan, Albert Poater
Chem. Eur. J., December 11, 2015, DOI: 10.1002/chem.201503097. Read article.

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