Metal-free Counterparts Research Articles

A first-principles investigation on the structural, stability and mechanical properties of novel Ag, Au and Cu-graphdiyne magnetic semiconducting monolayers

Most recently, silver-metalated graphdiyne (GDY) nanomembranes have been fabricated using the wet-chemistry approach, with highly efficient response for light-driven decomposition of antibiotics (ACS Appl. Nano Mater. 2023, 6, 7395). Inspired by this exciting advance, herein for the first time we theoretically explore the key physical properties of the single-layer M-(N)GDY (M=Cu, Ag, Au) monolayers. Spin-polarized density functional theory (DFT) results reveal that metalated GDY monolayers favor a high-spin ground state, presenting a magnetic moment of 3 µB/unitcell. The sheets are characterized as small band gap magnetic semiconductors, ranging between 0.112 and 0.960 eV, in which only one spin contributes to the band gap. Ab-initio molecular dynamics results confirm the remarkable thermal stability of the constructed graphdiyne nanomembranes at 1000 K. The dynamical stability and mechanical properties at the ground state are furthermore investigated using machine learning interatomic potentials. The ultimate tensile strengths of the metalated graphdiyne lattices are found to be decent, over 6 GPa close to the ground state, but a few folds lower than the native metal-free counterparts. The presented first-principles results confirm remarkable thermal, dynamical and mechanical stability, and appealing electronic characteristics of the metalated graphdiyne nanosheets, attractive to design advanced light-weight energy storage/conversion and spintronic nanosystems.

Organomercury oligonucleotide conjugates as artificial ribonucleases

Two oligonucleotide conjugates sharing the same sequence but incorporating a different 5′-terminal organometallic moiety were synthesized, by either direct mercuration in solution or oximation with an organomercury aldehyde on solid support. The potential of these conjugates to serve as new type of artificial ribonucleases was tested with a complementary 2´-O-methyl-RNA target sequence featuring a single cleavable RNA phosphodiester linkage. Both organomercury oligonucleotides greatly outperformed their metal-free counterparts as well as the previously reported small molecule organomercury RNA cleaving agent in catalytic activity, providing an important proof-of-concept. Compared to state-of-the-art metal-dependent artificial ribonucleases, however, the observed activity was modest.

Tuning of electrochromic properties of electrogenerated polythiophenes through Ru(II) complex tethering and backbone derivatization

Herein, we present electrochromic properties of polythiophenes (PEDOT-Ru, PProDOT-Ru, PSNS-Ru) which were synthesized through electrochemical polymerization of thiophene derivatives tethered to [Ru(bpy)2pytri]2+ complexes via alkyl chain. The unconjugated spacer hinders the effective electronic interaction between the metal center and polymer backbone provided explicitly different multichromic and ambipolar nature to polythiophenes from their metal free counterparts (PEDOT, PProDOT and PSNS). The cathodic behavior of all polymers was mainly dominated by the redox and optical properties of the tethered Ru complex whereas their anodic behavior depended on properties of both the conjugated backbone and the Ru complex. Modification of conjugated backbone from SNS, ProDOT to EDOT led to a distinct variation of band gap from 2.44 eV, 1.94 eV to 1.84 eV and provided a wide span of colors at neutral state (yellow, orange, green, respectively) which are all evidently different from their metal free counterparts. PEDOT based metallopolymer reached as high as 46.24% optical contrast and 2.52 s switching time. The coloration efficiency of SNS, ProDOT and EDOT based polymers were calculated as 69.42, 298.70, 365.22 cm2/C, respectively. The polymers displayed distinct colors from various hues of red, green and blue legs of RGB color-space upon sequential anodic and cathodic polarization indicating the rewarding effect of tethering of Ru(II) complex and backbone derivatization in refinement of electrochromic properties of polythiophenes.

Ligand field molecular dynamics simulation of Pt(II)-phenanthroline binding to N-terminal fragment of amyloid-β peptide.

We report microsecond timescale molecular dynamics simulation of the complex formed between Pt(II)-phenanthroline and the 16 N-terminal residues of the Aβ peptide that is implicated in the onset of Alzheimer’s disease, along with equivalent simulations of the metal-free peptide. Simulations from a variety of starting points reach equilibrium within 100 ns, as judged by root mean square deviation and radius of gyration. Platinum-bound peptides deviate rather more from starting points, and adopt structures with larger radius of gyration, than their metal-free counterparts. Residues bound directly to Pt show smaller fluctuation, but others actually move more in the Pt-bound peptide. Hydrogen bonding within the peptide is disrupted by binding of Pt, whereas the presence of salt-bridges are enhanced.

Trace hydrogen in helium atmosphere white dwarfs as a possible signature of water accretion

A handful of white dwarfs with helium-dominated atmospheres contain exceptionally large masses of hydrogen in their convection zones, with the metal-polluted white dwarf GD 16 being one of the earliest recognised examples. We report the discovery of a similar star: the white dwarf coincidentally named GD 17. We obtained medium-resolution spectroscopy of both GD 16 and GD 17 and calculated abundances and accretion rates of photospheric H, Mg, Ca, Ti, Fe and Ni. The metal abundance ratios indicate that the two stars recently accreted debris which is Mg-poor compared to the composition of bulk Earth. However, unlike the metal pollutants, H never diffuses out of the atmosphere of white dwarfs and we propose that the exceptionally high atmospheric H content of GD 16 and GD 17 ($2.2\times 10^{24}$g and $2.9\times 10^{24}$g respectively) could result from previous accretion of water bearing planetesimals. Comparing the detection of trace H and metal pollution among 729 helium atmosphere white dwarfs, we find that the presence of H is nearly twice as common in metal-polluted white dwarfs compared to their metal-free counterparts. This highly significant correlation indicates that, over the cooling age of the white dwarfs, at least some fraction of the H detected in many He atmospheres (including GD 16 and GD 17) is accreted alongside metal pollutants, where the most plausible source is water. In this scenario, water must be common in systems with rocky planetesimals.

Through-Space Shielding Effects of Metal-Complexed Phenyl Rings.

Several naphthalene compounds containing a methyl group in a 1,8-relationship to a metal-complexed phenyl ring bearing various substituents have been synthesized. The through-space shielding effects of the phenyl ring, as a function of substituent and complexing metal species, were monitored by observing the 1H NMR signal of the methyl group located in the shielding zone of the ring. In all cases, the methyl signal was slightly more downfield in the complexes than in the uncomplexed analogues. A comparison of available crystal structures, however, shows that the phenyl ring is slightly closer to the naphthyl methyl group in the complexes than in their metal-free counterparts. X-ray structures and DFT calculations also reveal a slight elongation in the average length of the carbon-carbon bonds of the phenyl ring upon complexation. The effect of substituents on the signal of the naphthyl methyl group is small but discernible in the uncomplexed derivatives, and consistent with our previous report. A similar trend is absent in the corresponding metal complexes, as exemplified by the chromium series, and the effect of the metal appears to be more dominant than that of the substituents. These observations were found to be in line with NMR shift calculations.

Enhanced oxygen reduction reaction activity of iron-containing nitrogen-doped carbon nanotubes for alkaline direct methanol fuel cell application

Abstract Non-precious metal catalysts for electrochemical oxygen reduction reaction are synthesised by pyrolysis of multi-walled carbon nanotubes in the presence of nitrogen and iron precursors. For the physico-chemical characterisation of the catalysts transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction are used. The electrocatalytic activity of the catalysts for oxygen reduction is studied in 0.1 M KOH solution using the rotating disk electrode method. The Fe-containing nitrogen-doped carbon nanotubes exhibit an enhanced electrocatalytic performance as compared to metal-free counterparts and their electrocatalytic activity is comparable to that of commercial Pt/C catalyst. Alkaline direct methanol fuel cell tests also show performance close to Pt/C. Thus, these materials can be considered as promising cathode catalysts for application in alkaline fuel cells.

Effects of Multidentate Metal Interactions on the Structure of Collisionally Activated Proteins: Insights from Ion Mobility Spectrometry and Molecular Dynamics Simulations

Much remains to be learned about the way in which bound metal ions modulate the response of electrosprayed proteins and protein complexes to collisional excitation. Nonspecific metal adducts can affect the extent of collision-induced unfolding (CIU) and collision-induced dissociation (CID). Here, we examine how Na(+) and Ca(2+) adducts alter the CIU response of monomeric proteins under native electrospray conditions. Both of these metals are commonly encountered in biological samples. Measured collision cross sections are largely independent of metal adduction as long as in-source excitation is minimized. In contrast, under CIU conditions, the metal-adducted proteins are markedly more compact than their metal-free counterparts. This phenomenon is particularly pronounced for Ca(2+) binding, but Na(+) adducts have significant effects as well. Molecular dynamics simulations reproduce the experimentally observed trends. The simulations show that structural expansion of the collisionally unfolded proteins is limited by multidentate metal contacts that restrict the conformational freedom of the polypeptide chains. Multidentate interactions with carboxylates and other electron-rich moieties are to be anticipated for divalent metals such as Ca(2+). It is surprising that Na(+) also engages in multidentate ligation. Electrostatic mapping reveals that the propensity of both Na(+) and Ca(2+) to interact with multiple electron-rich groups is caused by ineffective charge shielding during ion pairing. Despite their compactness, the CIU structures of metalated proteins do not retain native-like elements. Instead, CIU generates inside-out conformations where previously surface-exposed hydrophilic side chains get buried along with most of the metal ions. Our findings caution that the observation of compact conformers after collisional excitation does not imply the survival of solution-like structural features. We also discuss possible implications of adduct-mediated effects for CIU fingerprinting studies.

Significant Enhancement of Water Splitting Activity of N-Carbon Electrocatalyst by Trace Level Co Doping.

Replacement of precious metal electrocatalysts with highly active and cost efficient alternatives for complete water splitting at low voltage has attracted a growing attention in recent years. Here, this study reports a carbon-based composite co-doped with nitrogen and trace amount of metallic cobalt (1 at%) as a bifunctional electrocatalyst for water splitting at low overpotential and high current density. An excellent electrochemical activity of the newly developed electrocatalyst originates from its graphitic nanostructure and highly active Co-Nx sites. In the case of carefully optimized sample of this electrocatalyst, 10 mA cm(-2) current density can be achieved for two half reactions in alkaline solutions-hydrogen evolution reaction and oxygen evolution reaction-at low overpotentials of 220 and 350 mV, respectively, which are smaller than those previously reported for nonprecious metal and metal-free counterparts. Based on the spectroscopic and electrochemical investigations, the newly identified Co-Nx sites in the carbon framework are responsible for high electrocatalytic activity of the Co,N-doped carbon. This study indicates that a trace level of the introduced Co into N-doped carbon can significantly enhance its electrocatalytic activity toward water splitting.

How Metals Can Help Multiphotochromism: An Ab Initio Study

Dimers of dithienylethenes containing a metallic center in their bridging unit often exhibit a full and stepwise photochromism, and their photoactivity typically surpasses the majority of their metal-free counterparts that are often plagued by the impossibility to switch all units. In this work, we investigate five different photochromic dimers with a relativistic spin–orbit time-dependent density functional theory (SO-TD-DFT) approach and explore the possible sources of this enhanced photoactivity. In particular the potential intersystem crossing (ISC) from an intense singlet state in the UV region to a triplet state presenting the necessary topology to trigger the ring closing of the switch is unravelled in several cases. The efficiency of this crossing is found to be dependent on both the nature of the metallic center and the structure of the dithienylethene ligand but, in general, improves the probability for the second ring closing starting from the partially switched dimer. This work provides the fi...

ChemInform Abstract: Organocatalytic Strategies for Enantioselective Metal‐Free Reductions

AbstractReview: 107 refs.

Organocatalytic strategies for enantioselective metal-free reductions

One of the most important chemical transformations is the reduction of multiple bonds, carbon–carbon as well as carbon–heteroatom double bonds, since it leads very often to the generation of new stereocenters in the molecule. The replacement of metal-based catalysts with equally efficient metal-free counterparts is very appealing in view of possible future applications of non toxic, low cost, and environmentally friendly promoters on an industrial scale. This perspective will focus specially, but not exclusively, on the enantioselective reduction of the carbon nitrogen double bond; despite the historical need for and continued interest in chiral amines, their synthesis remains challenging. Three metal-free catalytic methodologies available for the reduction of carbon–nitrogen double bond will be discussed: i) binaphthol-derived phosphoric acids catalyzed reductions, with dihydropyridine-based compound as the reducing agent; ii) trichlorosilane mediated reductions, in the presence of catalytic amounts of chiral Lewis bases; iii) metal-free hydrogenation of imines through FLP (Frustrated Lewis Pair) methodology, that involves the use of a combination of a strong Lewis acid with a variety of sterically encumbered Lewis bases, for examples phosphines or tertiary amines, to activate hydrogen at ambient conditions. Special attention will be devoted to the most recent applications of the last five years.

Zinc Is Externalized Rather than Released during Synaptic Transmission

The synaptic vesicles of some glutamatergic terminals contain a high concentration of zinc that serves functions that remain obscure. In this publication we have used the membrane permeant zinc fluophore, ZnAF-2 to determine if zinc is released during the course of synaptic transmission. Stimulation of the slices with either high potassium or electrically, leads to an increase in fluorescence that long outlasts the stimulus and remains elevated for many minutes. We demonstrate that this response is inconsistent with the free release of zinc but is with the presentation of zinc coordinated to macromolecules within the exocytosed vesicles to the extracellular space; a process we term 'externalization'. Our data suggests a novel mechanism of synaptic transmission at zinc-rich glutamatergic terminals that distinguishes them from their metal free counterparts.

Compositional and Electrochemical Characterization of Noble Metal−Diamondlike Carbon Nanocomposite Thin Films

A detailed characterization of platinum- and gold-diamondlike carbon (DLC) nanocomposite films deposited onto silicon substrates is presented. A modified pulsed laser deposition (PLD) technique was used to incorporate noble metal nanoclusters into hydrogen-free DLC films. Several analytical techniques, including transmission electron microscopy, atomic force microscopy, Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and nanoindentation testing, were used to investigate these thin films in an effort to determine their physical and electrochemical properties. Rutherford backscattering spectroscopy indicated that the gold- and platinum-DLC films contain metal concentrations between three and 36 atomic percent. Cross-sectional transmission electron microscopy revealed that metal is present as arrays of noble metal islands embedded within the DLC matrix, while atomic force microscopy provided evidence of target splashing. In addition, due to the inclusion of metal, metal-DLC thin films exhibited greater conductivity than their metal-free counterparts. The electrochemical properties were studied using quasi-reversible redox couples and correlated to the metal concentration. Finally, the influence of the layer's composition on the electron-transfer kinetics and the achievable working potential window is discussed. The results discussed herein suggest that metal-DLC thin films grown by pulsed laser deposition present a promising alternative electrode material for electrochemistry.

Metal–matrix interface in reinforced glass ionomers

Objective: In reinforced materials, interfacial bonding is critical for efficient transfer of stress from the matrix to the reinforcement. The goal of this study was to characterize the physical and chemical nature of this interface in three metal-reinforced glass ionomers. Two of them were commercial, ESPE-Ketac Silver (KS) and GC-Miracle Mix (MM), and the third, EX, was experimental. Methods: The techniques of scanning electron microscopy (SEM) and infrared spectroscopy (IR) were used to accomplish the stated goal. SEM analysis utilized polished sections of set cylindrical specimens of each material prepared from their respective powder and liquid components. The glass and the liquid in EX were the same as in MM. The reinforcing agent in EX, 50% by weight, was an Ag-base spherical alloy similar in composition to that in MM. For EX, the alloy was oxidized to promote its bonding to the matrix. The specimens for IR study were prepared as follows. The metallic powders of each material were mixed with the corresponding liquid in excess, stored at 37°C for 1 h, washed with warm water (60°C), filtered and dried. The untreated metallic powders served as controls for IR analysis. Results: SEM revealed a distinct halo shaped internal reaction layer surrounding each alloy particle in EX. A similar layer was not seen in MM and KS. The alloy–matrix interface was continuous and gap-free in EX. In contrast, gaps separating matrix from respective reinforcements were conspicuous features in MM and KS. The IR spectrum of the liquid treated EX alloy powder showed absorbency bands characteristic of unreacted carboxyl groups and carboxylate salts. These bands were absent in the IR spectra of all other powders—treated and untreated. Significance: The absence of interfacial bonding in MM and KS demonstrated in this study provides a reason why these two materials, in spite of metal addition, have not proved to be any stronger or more durable than their metal-free counterparts. A means of creating interfacial bonding presented here could be useful in the design of improved reinforced glass ionomer materials.