Adsorption and Distribution of Triplex-Hybridizing Bioconjugated Gold Nanoclusters Inside Spermatozoa- A Study Using Confocal Microscopy and Fluorescence Lifetime Imaging.

The study of the interactions between biofunctionalized gold nanoclusters (Au NCs) and spermatozoa is highly relevant to evaluate the potential of Au NCs as imaging probes and transfection agents in reproductive biology. In this work, confocal laser scanning microscopy (CLSM) was used to investigate the distribution of Au NCs bioconjugated with peptide (nuclear localisation sequence, NLS) and oligonucleotide (locked nucleic acid, LNA) ligands in bovine spermatozoa. Fluorescence lifetime imaging (FLIM) was employed to detect changes in the NC's chemical environment.

The multivariate interaction between Au and TiO colloids: the role of surface potential, concentration, and defects.

The established DLVO theory explains colloidal stability by the electrostatic repulsion between electrical double layers. While the routinely measured zeta potential can estimate the charges of double layers, it is only an average surface property which might deviate from the local environment. Moreover, other factors such as the ionic strength and the presence of defects should also be considered.

Tailoring Pore Size and Catalytic Activity in Cobalt Iron Layered Double Hydroxides and Spinels by Microemulsion-Assisted pH-Controlled Co-Precipitation.

Cobalt iron containing layered double hydroxides (LDHs) and spinels are promising catalysts for the electrochemical oxygen evolution reaction (OER). Towards development of better performing catalysts, the precise tuning of mesostructural features such as pore size is desirable, but often hard to achieve. Herein, a computer-controlled microemulsion-assisted co-precipitation (MACP) method at constant pH is established and compared to conventional co-precipitation.

Non-Majorana modes in diluted spin chains proximitized to a superconductor.

Spin chains proximitized with superconducting condensates have emerged as one of the most promising platforms for the realization of Majorana modes. Here, we craft diluted spin chains atom by atom following a seminal theoretical proposal suggesting indirect coupling mechanisms as a viable route to trigger topological superconductivity. Starting from single adatoms hosting deep Shiba states, we use the highly anisotropic Fermi surface of the substrate to create spin chains characterized by different magnetic configurations along distinct crystallographic directions.

Mechanical Stability of Nano-Coatings on Clinically Applicable Electrodes, Generated by Electrophoretic Deposition.

The mechanical stability of implant coatings is crucial for medical approval and transfer to clinical applications. Here, electrophoretic deposition (EPD) is a versatile coating technique, previously shown to cause significant post-surgery impedance reduction of brain stimulation platinum electrodes. However, the mechanical stability of the resulting coating has been rarely systematically investigated.

Influence of Gold/Silver Ratio in Ablative Nanoparticles on Their Interaction with Aptamers and Functionality of the Obtained Conjugates.

Nano-bio-conjugates, featuring noble metal gold-silver alloy nanoparticles, represent a versatile tool in diagnostics and therapeutics due to their plasmonic and antimicrobial properties tunable by the particle's gold molar fraction. However, little is known about how the binding of thiolated biomolecules to noble metal nanoparticles is influenced by the fraction of gold and silver atoms on the nanoparticle's surface and to which extend this would affect the functionality of the conjugated biomolecules. In this work, we generated gold-silver alloy nanoparticles with average diameters of 7-8 nm using the modern, surfactant-free laser ablation in liquids (LAL) synthesis approach.

The Roles of Composition and Mesostructure of Cobalt-Based Spinel Catalysts in Oxygen Evolution Reactions.

By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co O , MgCo O , Co FeO , Co AlO and CoFe O . The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H O decomposition.

Impact of Ligands on Structural and Optical Properties of Ag Nanoclusters.

A ligand exchange strategy has been employed to understand the role of ligands on the structural and optical properties of atomically precise 29 atom silver nanoclusters (NCs). By ligand optimization, ∼44-fold quantum yield (QY) enhancement of Ag(BDT)(DHLA) NCs ( = 1-6) was achieved, where BDT and DHLA refer to 1,3-benzene-dithiol and dihydrolipoic acid, respectively. High-resolution mass spectrometry was used to monitor ligand exchange, and structures of the different NCs were obtained through density functional theory (DFT).

Active Ga-catalysts for the ring opening homo- and copolymerization of cyclic esters, and copolymerization of epoxide and anhydrides.

A series of gallium complexes L12Ga4Me8 (1), L22Ga4Me8 (2), and L32Ga4Me8 (3) was synthesized by reaction of GaMe3 with Schiff base ligands L1-3H2 (L1H2 = 2,4-di-tert-butyl-6-{[(3-hydroxypropyl)imino]methyl}phenol; L2H2 = 2,4-dichloro-6-{[(3-hydroxypropyl)imino]methyl}phenol; L3H2 = 4-tert-butyl-2-{[(3-hydroxypropyl)imino]methyl}phenol) and characterized by 1H, 13C NMR, IR spectroscopy, elemental analysis and single crystal X-ray analysis (1, 2), proving their tetranuclear structure in the solid state. Complexes 1-3 showed good catalytic activity in the ring opening homopolymerization (ROP) and ring opening copolymerization (ROcoP) of lactide (LA) and ε-caprolactone (ε-CL) in the presence of benzyl alcohol (BnOH) in toluene at 100 °C, yielding polymers with the expected average molecular weights (Mn) and narrow molecular weight distributions (MWD), as well as a high isoselectivity for the ROP of rac-lactide (rac-LA), yielding isotactic-enriched PLAs with Pm values up to 0.78.

Stepwise Bi-Bi Bond Formation: From a Bi-centered Radical to Bi Butterfly and Bi Cuneane-Type Clusters.

In contrast to their lighter homologues (P, As, Sb), the synthesis of polybismuthane clusters is still restricted to classical solid-state approaches. We herein report on systematic reduction reactions of different bismuth precursors with Ga(I) and Mg(I) complexes. This study not only yielded the first metal-coordinated tetrabismuthane ([{L(Cl)Ga}-μ,η-Bi] , L = HC[C(Me)N(2,6--PrCH)]) and realgar-type bismuth cluster ([(LMg)(μ,η-Bi)] , L = HC[C(Me)N(2,4,6-MeCH)]) in addition to the bismuth-centered radical [LGa(Cl)]Bi and dibismuthene [L(Cl)GaBi] , but clearly demonstrates the crucial role of the substituents and the oxidation state of the bismuth precursor as well as the specific reduction potential of the main group metal reductants on the product formation.

Syntheses, structures and catalytic activity of tetranuclear Mg complexes in the ROP of cyclic esters under industrially relevant conditions.

Four tetranuclear magnesium complexes were synthesized and fully characterized. They are excellent catalysts for the ring-opening polymerization (ROP) of bulk racemic-lactide (rac-LA) and ε-caprolactone (ε-CL) even with low catalyst loading under industrially relevant conditions without additional co-initiators, yielding polymers with high molecular weight (Mn) and moderately controlled molecular weight distribution (MWD). The polymerization activity depends on the steric and electronic properties of the imino(phenolate) ligands.

Synthesis and structures of gallaarsenes LGaAsGa(X)L featuring a Ga-As double bond.

Three equivalents of LGa {L = HC[C(Me)N(2,6-i-PrCH)]} react with AsX (X = Cl, Br) by insertion into two As-X bonds, followed by the elimination of LGaX and formation of LGaAsGa(Cl)L (1) and LGaAsGa(Br)L (2). According to single crystal X-ray analysis, 1 and 2 each exhibit one Ga-As single bond and one Ga-As double bond. The π-bonding contribution (9.

Correction: Determining the role of redox-active materials during laser-induced water decomposition.

Correction for 'Determining the role of redox-active materials during laser-induced water decomposition' by Mark-Robert Kalus et al., Phys. Chem.

Heterolepic -Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide.

Zinc phenoxide complexes LZnOAr - (L=MeNCHNC(Me)CHC(Me)O) and LZnOAr - (L=MeNCHNC(Me)CHC(Me)O) with donor-functionalized -ketoiminate ligands (L) and OAr substituents (Ar=Ph , ; 2,6-Me-CH , ; 3,5-Me-CH , ; 4-Bu-CH , ) with tuneable electronic and steric properties were synthesized and characterized. - adopt binuclear structures in the solid state except for , while they are monomeric in CDCl solution. - are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CHCl at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight ( ) and moderately controlled molecular weight distribution (MWDs).

Synergism between Specific Halide Anions and pH Effects during Nanosecond Laser Fragmentation of Ligand-Free Gold Nanoparticles.

Gold nanoclusters (AuNCs) with diameters smaller than 3 nm are an emerging field of research because they possess interesting optical properties, such as photoluminescence. However, to date, it is still difficult to distinguish whether these properties originate from the cores of the nanoparticles or from the adsorbates on their surfaces. Hence, there is a high demand for ligand-free, ultra-small particles because they make it possible to study ligand and core effects separately.

Solvent-induced ion separation of a beryllium scorpionate complex.

Spontaneous ion separation of the scorpionate beryllium complex, TpBeI 1 (Tp = 1-trispyrazolylborate), occurs upon treatment with THF, yielding [TpBe(thf)]I 2, which was characterized by heteronuclear NMR spectroscopy (1H, 9Be, 13C) and structurally characterized by single crystal X-ray diffraction. 2 represents a rare example of a structurally characterized monocationic beryllium complex, and to the best of our knowledge, the synthesis of 2 by a solvent-induced ion separation has previously only been observed in the reactions of beryllium dihalides with strong Lewis bases.

Simultaneous Rayleigh/Mie and Raman/Fluorescence Characterization of Molecularly Functionalized Colloids by Correlative Single-Particle Real-Time Imaging in Suspension.

Many applications of nano- and microparticles require molecular functionalization. Assessing the heterogeneity of a colloidal sample in terms of its molecular functionalization is highly desirable but not accessible by conventional ensemble experiments. Retrieving this information necessitates single-particle experiments which simultaneously detect both functionalized and nonfunctionalized particles via two separate imaging channels.

Site-Specific SERS Assay for Survivin Protein Dimer: From Ensemble Experiments to Correlative Single-Particle Imaging.

An assay for Survivin, a small dimeric protein which functions as modulator of apoptosis and cell division and serves as a promising diagnostic biomarker for different types of cancer, is presented. The assay is based on switching on surface-enhanced Raman scattering (SERS) upon incubation of the Survivin protein dimer with Raman reporter-labeled gold nanoparticles (AuNP). Site-specificity is achieved by complexation of nickel-chelated N-nitrilo-triacetic acid (Ni-NTA) anchors on the particle surface by multiple histidines (His -tag) attached to each C-terminus of the centrosymmetric protein dimer.

Optical and electron microscopy study of laser-based intracellular molecule delivery using peptide-conjugated photodispersible gold nanoparticle agglomerates.

Background: Cell-penetrating peptides (CPPs) can act as carriers for therapeutic molecules such as drugs and genetic constructs for medical applications. The triggered release of the molecule into the cytoplasm can be crucial to its effective delivery. Hence, we implemented and characterized laser interaction with defined gold nanoparticle agglomerates conjugated to CPPs which enables efficient endosomal rupture and intracellular release of molecules transported.

Surface plasmon coupled chemiluminescence during adsorption of oxygen on magnesium surfaces.

The dissociative adsorption of oxygen molecules on magnesium surfaces represents a non-adiabatic reaction exhibiting exoelectron emission, chemicurrent generation, and weak chemiluminescence. Using thin film Mg/Ag/p-Si(111) Schottky diodes with 1 nm Mg on a 10-60 nm thick Ag layer as 2π-photodetectors, the chemiluminescence is internally detected with a much larger efficiency than external methods. The chemically induced photoyield shows a maximum for a Ag film thickness of 45 nm.

Inclusion of supported gold nanoparticles into their semiconductor support.

Supported particles are easily accessible as standard materials used in heterogeneous catalysis and photocatalysis. This article addresses our exemplary studies on the integration of supported nanoparticles into their solid support, namely gold nanoparticles into zinc oxide sub-micrometer spheres, by energy controlled pulsed laser melting in a free liquid jet. This one-step, continuous flow-through processing route reverses the educt's structure, converting the ligand-free surface adsorbate into a spherical subsurface solid inclusion within its former support.

Monophasic ligand-free alloy nanoparticle synthesis determinants during pulsed laser ablation of bulk alloy and consolidated microparticles in water.

Chemical syntheses of homogenous solid solution alloy nanoparticles of noble metals require high temperature above 100 °C. Beside this, aqueous co-reduction methods lead to phase separation. In contrast, pulsed laser ablation in liquid (PLAL) allows synthesis of alloy nanoparticles with totally homogeneous ultrastructure in aqueous media at room temperature without reducing agents or organic ligands.

Effects of silver nitrate and silver nanoparticles on a planktonic community: general trends after short-term exposure.

Among metal pollutants silver ions are one of the most toxic forms, and have thus been assigned to the highest toxicity class. Its toxicity to a wide range of microorganisms combined with its low toxicity to humans lead to the development of a wealth of silver-based products in many bactericidal applications accounting to more than 1000 nano-technology-based consumer products. Accordingly, silver is a widely distributed metal in the environment originating from its different forms of application as metal, salt and nanoparticle.

In situ non-DLVO stabilization of surfactant-free, plasmonic gold nanoparticles: effect of Hofmeister's anions.

Specific ion effects ranking in the Hofmeister sequence are ubiquitous in biochemical, industrial, and atmospheric processes. In this experimental study specific ion effects inexplicable by the classical DLVO theory have been investigated at curved water-metal interfaces of gold nanoparticles synthesized by a laser ablation process in liquid in the absence of any organic stabilizers. Notably, ion-specific differences in colloidal stability occurred in the Hückel regime at extraordinarily low salinities below 50 μM, and indications of a direct influence of ion-specific effects on the nanoparticle formation process are found.