Detection of chemical and biological agents plays a fundamental role in biomedical, forensic and environmental sciences1–4 as well as in anti bioterrorism applications.5–7 The development of highly sensitive, cost effective, miniature sensors is therefore in high demand which requires advanced technology coupled with fundamental knowledge in chemistry, biology and material sciences.8–13

In general, sensors feature two functional components: a recognition element to provide selective/specific binding with the target analytes and a transducer component for signaling the binding event. An efficient sensor relies heavily on these two essential components for the recognition process in terms of response time, signal to noise (S/N) ratio, selectivity and limits of detection (LOD).14,15 Therefore, designing sensors with higher efficacy depends on the development of novel materials to improve both the recognition and transduction processes. Nanomaterials feature unique physicochemical properties that can be of great utility in creating new recognition and transduction processes for chemical and biological sensors15–27 as well as improving the S/N ratio by miniaturization of the sensor elements.28

Gold nanoparticles (AuNPs) possess distinct physical and chemical attributes that make them excellent scaffolds for the fabrication of novel chemical and biological sensors (Figure 1).29–36 First, AuNPs can be synthesized in a straightforward manner and can be made highly stable. Second, they possess unique optoelectronic properties. Third, they provide high surface-to-volume ratio with excellent biocompatibility using appropriate ligands.30 Fourth, these properties of AuNPs can be readily tuned varying their size, shape and the surrounding chemical environment. For example, the binding event between recognition element and the analyte can alter physicochemical properties of transducer AuNPs, such as plasmon resonance absorption, conductivity, redox behavior, etc. that in turn can generate a detectable response signal. Finally, AuNPs offer a suitable platform for multi-functionalization with a wide range of organic or biological ligands for the selective binding and detection of small molecules and biological targets.30–32,36 Each of these attributes of AuNPs has allowed researchers to develop novel sensing strategies with improved sensitivity, stability and selectivity. In the last decade of research, the advent of AuNP as a sensory element provided us a broad spectrum of innovative approaches for the detection of metal ions, small molecules, proteins, nucleic acids, malignant cells, etc. in a rapid and efficient manner.37



Figure 1

Physical properties of AuNPs and schematic illustration of an AuNP-based detection system.



In this current review, we have highlighted the several synthetic routes and properties of AuNPs that make them excellent probes for different sensing strategies. Furthermore, we will discuss various sensing strategies and major advances in the last two decades of research utilizing AuNPs in the detection of variety of target analytes including metal ions, organic molecules, proteins, nucleic acids, and microorganisms.

/pdf/gold-nanoparticles-in-chemical-and-biological-sensing-5e2qojkdzn.pdf

Gold nanoparticles in chemical and biological sensing.

/pdf/aryl-aryl-bond-formation-one-century-after-the-discovery-of-1jdyxlkwix.pdf

Aryl-aryl bond formation one century after the discovery of the Ullmann reaction.

The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of β-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Differently from passive Brownian particles, active particles, also known as self-propelled Brownian particles or microswimmers and nanoswimmers, are capable of taking up energy from their environment and converting it into directed motion. Because of this constant flow of energy, their behavior can be explained and understood only within the framework of nonequilibrium physics. In the biological realm, many cells perform directed motion, for example, as a way to browse for nutrients or to avoid toxins. Inspired by these motile microorganisms, researchers have been developing artificial particles that feature similar swimming behaviors based on different mechanisms. These man-made micromachines and nanomachines hold a great potential as autonomous agents for health care, sustainability, and security applications. With a focus on the basic physical features of the interactions of self-propelled Brownian particles with a crowded and complex environment, this comprehensive review will provide a guided tour through its basic principles, the development of artificial self-propelling microparticles and nanoparticles, and their application to the study of nonequilibrium phenomena, as well as the open challenges that the field is currently facing.

/pdf/active-particles-in-complex-and-crowded-environments-4pyirdi1aj.pdf

Active Particles in Complex and Crowded Environments

A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used has been described as the active catalytic species. However, recent research has begun to shed light on the in situ transformations that many palladium precatalysts undergo during and before the catalytic reaction, and there are now many suggestions in the literature that narrow the scope of types of palladium that may be considered true “catalysts” in these coupling reactions. In this work, for each type of precatalyst, the recent literature is summarized and the type(s) of palladium that are proposed to be truly active are enumerated. All forms of palladium, including discrete soluble palladium complexes, solid-supported metal ligand complexes, supported palladium nano- and macroparticles, soluble palladium nanoparticles, soluble ligand-free palladium, and palladium-exchanged oxides are considered and reviewed here. A considerable focus is placed on solid precatalysts and on evidence for and against catalysis by solid surfaces vs. soluble species when starting with various precatalysts. The review closes with a critical overview of various control experiments or tests that have been used by authors to assess the homogeneity or heterogeneity of catalyst systems.

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review

Treatment of U(BH4)4 with 1 or 3 equiv of Li2(SCS)·1.5Et2O, 1, afforded the actinide carbene complexes U(μ-SCS)3[U(BH4)3]2 (4) and U(μ-SCS)3[Li(Et2O)]2 (6), respectively [SCS = (Ph2P = S)2C]. In THF, complex 4 was transformed into the mononuclear derivative (SCS)U(BH4)2(THF)2 (5). The multiple bond character of the uranium−carbon bond was first revealed by the X-ray crystal structures of the three complexes. The U═C bond in these complexes present a nucleophilic character, as shown by their reaction with a carbonyl derivative. Finally, DFT calculations prove the involvement of both 5f and 6d orbitals in both the σ and the π U−C bonds.

The U=C double bond: synthesis and study of uranium nucleophilic carbene complexes.

New mono- and bis-carbene samarium complexes: synthesis, X-ray crystal structures and reactivity.

A bis(thiophosphinoyl)methanediide palladium complex: coordinated dianion or nucleophilic carbene complex?

The stabilisation of the carbene centre in a complex can be achieved either by the metal moiety or the carbon substituents. The balance between these two stabilising effects determines the nature of the MC bond and therefore the reactivity of the metal complexes. Introducing two vicinal phosphorus groups as substituents of the carbene centre proved to be rewarding, since depending on the coordination number of this atom different electronic properties are observed. Indeed, a σ3-P atom possesses a lone pair that can interact with a carbene centre by destabilising its vacant pπ orbital. On the contrary a σ4-P group presents low lying σ* orbitals which can be involved in delocalising electronic density in the carbene pπ orbital by negative hyperconjugation. Therefore, PCP carbene complexes can exhibit either an electrophilic or nucleophilic reactivity depending on the nature of the phosphorus group and the metal centre. Carbenes complexes of early and late transition metals, but also of lanthanides are discussed in this perspective.

Bis-phosphorus stabilised carbene complexes

The synthesis of polyphosphinine macrocycles, which consist of a 16-membered ring with four phosphorus atoms (P 4 ) and a 12-membered ring with three phosphorus atoms (P 3 ), is described. Their high coordination ability is demonstrated by the quantitative synthesis of the rhodium and iridium cation complexes of the P 4 macrocycle and by quantitative synthesis of the W(CO) 3 complex of the P 3 compound. Unlike the other available macrocyclic ligands bearing oxygen, sulfur, di- or tricoordinate nitrogen, and even tricoordinate phosphorus as ligating atoms, which are all essentially σ donors, these dicoordinate phosphorus-based macrocycles have strong π-acceptor properties. Their use can be envisaged for the stabilization of negative oxidation states of transition metals or in reductive catalysis.

https://science.sciencemag.org/content/sci/280/5369/1587.full.pdf

Pascal Le Floch

Papers

The U=C double bond: synthesis and study of uranium nucleophilic carbene complexes.

New mono- and bis-carbene samarium complexes: synthesis, X-ray crystal structures and reactivity.

A bis(thiophosphinoyl)methanediide palladium complex: coordinated dianion or nucleophilic carbene complex?

Bis-phosphorus stabilised carbene complexes

Silacalix-[n]-phosphaarenes: Macrocyclic Ligands Based on Dicoordinate Phosphorus Centers