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1.
J Phys Chem B ; 124(17): 3568-3582, 2020 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-32259444

RESUMO

The speciation of calcium carbonate in water is important to the geochemistry of the world's oceans and has ignited significant debate regarding the mechanism by which nucleation occurs. Here, it is vital to be able to quantify the thermodynamics of ion pairing versus higher order association processes in order to distinguish between possible pathways. Given that it is experimentally challenging to quantify such species, here we determine the thermodynamics for ion pairing and multiple binding of calcium carbonate species using bias-enhanced molecular dynamics. In order to examine the uncertainties underlying these results, we derived a new polarizable force field for both calcium carbonate and bicarbonate in water based on the AMOEBA model to compare against our earlier rigid ion model, both of which are further benchmarked against ab initio molecular dynamics for the ion pair. Both force fields consistently indicate that the association of calcium carbonate ion pairs to form larger species is stable, though with an equilibrium constant that is lower than for ion pairing itself.

2.
Nat Commun ; 10(1): 2318, 2019 05 24.
Artigo em Inglês | MEDLINE | ID: mdl-31127116

RESUMO

Since Pasteur first successfully separated right-handed and left-handed tartrate crystals in 1848, the understanding of how homochirality is achieved from enantiomeric mixtures has long been incomplete. Here, we report on a chirality dominance effect where organized, three-dimensional homochiral suprastructures of the biomineral calcium carbonate (vaterite) can be induced from a mixed nonracemic amino acid system. Right-handed (counterclockwise) homochiral vaterite helicoids are induced when the amino acid L-Asp is in the majority, whereas left-handed (clockwise) homochiral morphology is induced when D-Asp is in the majority. Unexpectedly, the Asp that incorporates into the homochiral vaterite helicoids maintains the same enantiomer ratio as that of the initial growth solution, thus showing chirality transfer without chirality amplification. Changes in the degree of chirality of the vaterite helicoids are postulated to result from the extent of majority enantiomer assembly on the mineral surface. These mechanistic insights potentially have major implications for high-level advanced materials synthesis.


Assuntos
Asparagina/metabolismo , Carbonato de Cálcio/química , Conformação Molecular , Asparagina/química , Carbonato de Cálcio/metabolismo , Estereoisomerismo
3.
Phys Rev E ; 99(3-1): 030102, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30999486

RESUMO

Equilibrium and nonequilibrium molecular dynamics (MD) are used to investigate the thermal conductivity of binary hard-sphere fluids. It is found that the thermal conductivity of a mixture can not only lie outside the series and parallel bounds set by their pure component values, but can lie beyond even the pure component fluid values. The MD simulations verify that revised Enskog theory can accurately predict nonequilibrium thermal conductivities at low densities and this theory is applied to explore the model parameter space. Only certain mass and size ratios are found to exhibit conductivity enhancements above the parallel bounds and dehancement below the series bounds. The anomalous dehancement is experimentally accessible in helium-hydrogen gas mixtures and a review of the literature confirms the existence of mixture thermal conductivity below the series bound and even below the pure fluid values, in accordance with the predictions of revised Enskog theory. The results reported here may reignite the debate in the nanofluid literature on the possible existence of anomalous thermal conductivities outside the series and parallel bounds as this Rapid Communication demonstrates they are a fundamental feature of even simple fluids.

4.
Phys Rev Lett ; 120(11): 116101, 2018 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-29601750

RESUMO

It seems natural to assume that defects at mineral surfaces critically influence interfacial processes such as the dissolution and growth of minerals in water. The experimental verification of this claim, however, is challenging and requires real-space methods with utmost spatial resolution, such as atomic force microscopy (AFM). While defects at mineral-water interfaces have been resolved in 2D AFM images before, the perturbation of the surrounding hydration structure has not yet been analyzed experimentally. In this Letter, we demonstrate that point defects on the most stable and naturally abundant calcite (10.4) surface can be resolved using high-resolution 3D AFM-even within the fifth hydration layer. Our analysis of the hydration structure surrounding the point defect shows a perturbation of the hydration with a lateral extent of approximately one unit cell. These experimental results are corroborated by molecular dynamics simulations.

5.
J Phys Chem B ; 122(4): 1471-1483, 2018 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-29231729

RESUMO

A new force field has been derived for the aqueous calcium phosphate system that aims to reproduce the key thermodynamic properties of the system, including free energies of hydration of the ions and the solubility of the solid mineral phases. Interactions of three phosphate anions (PO43-, HPO42-, and H2PO4-) with water were calibrated through comparison with the results obtained from ab initio molecular dynamics using both GGA and hybrid density functional theory with dispersion corrections. In the solid state, the force field has been evaluated by benchmarking against experiment and other existing models and is shown to reproduce the structural and mechanical properties well, despite the primary focus being on thermodynamics. To validate the force field, the thermodynamics of ion pairing for calcium phosphate species in water has been computed and shown to be in excellent agreement with experimental data.

6.
Chemistry ; 23(62): 15666-15679, 2017 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-28782852

RESUMO

A family of five neutral cyclometalated iridium(III) tetrazolato complexes and their methylated cationic analogues have been synthesised and characterised. The complexes are distinguished by variations of the substituents or degree of π conjugation on either the phenylpyridine or tetrazolato ligands. The photophysical properties of these species have been evaluated in organic and aqueous media, revealing predominantly a solvatochromic emission originating from mixed metal-to-ligand and ligand-to-ligand charge transfer excited states of triplet multiplicity. These emissions are characterised by typically long excited-state lifetimes (∼hundreds of ns), and quantum yields around 5-10 % in aqueous media. Methylation of the complexes caused a systematic red-shift of the emission profiles. The behaviour and the effects of the different complexes were then examined in cells. The neutral species localised mostly in the endoplasmic reticulum and lipid droplets, whereas the majority of the cationic complexes localised in the mitochondria. The amount of complexes found within cells does not depend on lipophilicity, which potentially suggests diverse uptake mechanisms. Methylated analogues were found to be more cytotoxic compared to the neutral species, a behaviour that might to be linked to a combination of uptake and intracellular localisation.


Assuntos
Complexos de Coordenação/química , Irídio/química , Tetrazóis/química , Animais , Cátions/química , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/metabolismo , Complexos de Coordenação/toxicidade , Cristalografia por Raios X , Retículo Endoplasmático/química , Retículo Endoplasmático/metabolismo , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/química , Corantes Fluorescentes/metabolismo , Ligantes , Luz , Microscopia de Fluorescência , Conformação Molecular , Fotólise/efeitos da radiação , Piridinas/química , Ratos
7.
Angew Chem Int Ed Engl ; 56(29): 8464-8467, 2017 07 10.
Artigo em Inglês | MEDLINE | ID: mdl-28407395

RESUMO

Determining a complete atomic-level picture of how minerals grow from aqueous solution remains a challenge as macroscopic rates can be a convolution of many reactions. For the case of calcite (CaCO3 ) in water, computer simulations have been used to map the complex thermodynamic landscape leading to growth of the two distinct steps, acute and obtuse, on the basal surface. The carbonate ion is found to preferentially adsorb at the upper edge of acute steps while Ca2+ only adsorbs after CO32- . In contrast to the conventional picture, ion pairs prefer to bind at the upper edge of the step with only one ion, at most, coordinated to the step and lower terrace. Migration of the first carbonate ion to a growth site is found to be rate-limiting for kink nucleation, with this process having a lower activation energy on the obtuse step.

8.
Phys Rev Lett ; 117(22): 226101, 2016 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-27925727

RESUMO

While the atomic force microscope (AFM) is able to image mineral surfaces in solution with atomic resolution, so far, it has been a matter of debate whether imaging point defects is also possible under these conditions. The difficulties stem from the limited knowledge of what types of defects may be stable in the presence of an AFM tip, as well as from the complicated imaging mechanism involving interactions between hydration layers over the surface and around the tip apex. Here, we present atomistic molecular dynamics and free energy calculations of the AFM imaging of vacancies and ionic substitutions in the calcite (101[over ¯]4) surface in water, using a new silica AFM tip model. Our results indicate that both calcium and carbonate vacancies, as well as a magnesium substitution, could be resolved in an AFM experiment, albeit with different imaging mechanisms.

9.
J Am Chem Soc ; 138(40): 13396-13401, 2016 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-27618560

RESUMO

Safranine O, a synthetic dye, was found to inhibit growth of ice at millimolar concentrations with an activity comparable to that of highly evolved antifreeze glycoproteins. Safranine inhibits growth of ice crystals along the crystallographic a-axis, resulting in bipyramidal needles extended along the <0001> directions as well as and plane-specific thermal hysteresis (TH) activity. The interaction of safranine with ice is reversible, distinct from the previously reported behavior of antifreeze proteins. Spectroscopy and molecular dynamics indicate that safranine forms aggregates in aqueous solution at micromolar concentrations. Metadynamics simulations and aggregation theory suggested that as many as 30 safranine molecules were preorganized in stacks at the concentrations where ice growth inhibition was observed. The simulations and single-crystal X-ray structure of safranine revealed regularly spaced amino and methyl substituents in the aggregates, akin to the ice-binding site of antifreeze proteins. Collectively, these observations suggest an unusual link between supramolecular assemblies of small molecules and functional proteins.


Assuntos
Gelo , Proteínas Anticongelantes/metabolismo , Modelos Moleculares , Conformação Molecular , Temperatura
10.
J Phys Chem Lett ; 7(16): 3112-7, 2016 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-27478906

RESUMO

Spiral hillocks on n-alkane crystal surfaces were observed immediately after Frank recognized the importance of screw dislocations for crystal growth, yet their structures and energies in molecular crystals remain ill-defined. To illustrate the structural chemistry of screw dislocations that are responsible for plasticity in organic crystals and upon which the organic electronics and pharmaceutical industries depend, molecular dynamics was used to examine heterochiral dislocation pairs with Burgers vectors along [001] in n-hexane, n-octane, and n-decane crystals. The cores were anisotropic and elongated in the (110) slip plane, with significant local changes in molecular position, orientation, conformation, and energy. This detailed atomic level picture produced a distribution of strain consistent with linear elastic theory, giving confidence in the simulations. Dislocations with doubled Burgers vectors split into pairs with elementary displacements. These results suggest a pathway to understanding the mechanical properties and failure associated with elastic and plastic deformation in soft crystals.

11.
Dalton Trans ; 45(32): 12884-96, 2016 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-27477005

RESUMO

The bis-tetrazolate dianion [1,2 BTB](2-), which is the deprotonated form of 1,2 bis-(1H-tetrazol-5-yl)benzene [1,2-H2BTB], is for the first time exploited as an ancillary N^N ligand for negatively charged [Ir(C^N)2(N^N)](-)-type complexes, where C^N is represented by cyclometalated 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (F2ppy). The new Ir(iii) complexes [Ir(ppy)2(1,2 BTB)]- and [Ir(F2ppy)2(1,2 BTB)]- have been fully characterised and the analysis of the X-ray structure of [Ir(ppy)2(1,2 BTB)]- confirmed the coordination of the [1,2 BTB](2-) dianion in a bis chelated fashion through the N-atoms adjacent to each of the tetrazolic carbons. Both of the new anionic Ir(iii) complexes displayed phosphorescence in the visible region, with intense sky-blue (λmax = 460-490 nm) or aqua (λmax = 490-520 nm) emissions originating from [Ir(F2ppy)2(1,2 BTB)]- and [Ir(ppy)2(1,2 BTB)]-, respectively. In comparison with our very recent examples of anionic Ir(iii)tetrazolate cyclometalates, the new Ir(iii) tris chelate complexes [Ir(F2ppy)2(1,2 BTB)]- and [Ir(ppy)2(1,2 BTB)]-, display an improved robustness, allowing the study of their reactivity toward the addition of electrophiles such as H(+) and CH3(+). In all cases, the electrophilic attacks occurred at the coordinated tetrazolate rings, involving the reversible - by a protonation deprotonation mechanism - or permanent - upon addition of a methyl moiety - switching of their global net charge from negative to positive and, in particular, the concomitant variation of their photoluminescence output. The combination of the anionic complexes [Ir(F2ppy)2(1,2 BTB)]- or [Ir(ppy)2(1,2 BTB)]- with a deep red emitting (λmax = 686 nm) cationic Ir(iii) tetrazole complex such as [IrTPYZ-Me]+, where TPYZ-Me is 2-(2-methyl-2H-tetrazol-5-yl)pyrazine, gave rise to two fully Ir(iii)-based soft salts capable of displaying additive and O2-sensitive emission colours, with an almost pure white light obtained by the appropriate choice of the ionic components.

12.
Chemphyschem ; 17(21): 3535-3541, 2016 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-27540706

RESUMO

The understanding of the molecular mechanisms underlying the early stages of crystallisation is still incomplete. In the case of calcium carbonate, experimental and computational evidence suggests that phase separation relies on so-called pre-nucleation clusters (PNCs). A thorough thermodynamic analysis of the enthalpic and entropic contributions to the overall free energy of PNC formation derived from three independent methods demonstrates that solute clustering is driven by entropy. This can be quantitatively rationalised by the release of water molecules from ion hydration layers, explaining why ion association is not limited to simple ion pairing. The key role of water release in this process suggests that PNC formation should be a common phenomenon in aqueous solutions.

13.
J Am Chem Soc ; 138(14): 4881-9, 2016 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-26986837

RESUMO

Structures of the α and ß phases of resorcinol, a major commodity chemical in the pharmaceutical, agrichemical, and polymer industries, were the first polymorphic pair of molecular crystals solved by X-ray analysis. It was recently stated that "no additional phases can be found under atmospheric conditions" (Druzbicki, K. et al. J. Phys. Chem. B 2015, 119, 1681). Herein is described the growth and structure of a new ambient pressure phase, ε, through a combination of optical and X-ray crystallography and by computational crystal structure prediction algorithms. α-Resorcinol has long been a model for mechanistic crystal growth studies from both solution and vapor because prisms extended along the polar axis grow much faster in one direction than in the opposite direction. Research has focused on identifying the absolute sense of the fast direction-the so-called "resorcinol riddle"-with the aim of identifying how solvent controls crystal growth. Here, the growth velocity dissymmetry in the melt is analyzed for the ß phase. The ε phase only grows from the melt, concomitant with the ß phase, as polycrystalline, radially growing spherulites. If the radii are polar, then the sense of the polar axis is an essential feature of the form. Here, this determination is made for spherulites of ß resorcinol (ε, point symmetry 222, does not have a polar axis) with additives that stereoselectively modify growth velocities. Both ß and ε have the additional feature that individual radial lamellae may adopt helicoidal morphologies. We correlate the appearance of twisting in ß and ε with the symmetry of twist-inducing additives.

14.
Dalton Trans ; 44(47): 20636-47, 2015 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-26563409

RESUMO

Three new complexes of formulation fac-[Re(CO)3(diim)L], where diim is either 1,10-phenanthroline or 1,10-phenanthroline functionalised at position 5 by a thioalkyl chain, and L is either a chloro or aryltetrazolato ancillary ligand, were synthesised and photophysically characterised. The complexes exhibit phosphorescent emission with maxima around 600 nm, originating from triplet metal-to-ligand charge transfer states with partially mixed ligand-to-ligand charge transfer character. The emission is relatively long-lived, within the 200-400 ns range, and with quantum yields of 2-4%. The complexes were trialed as cellular markers in live HeLa cells, along with two previously reported rhenium tetrazolato complexes bound to unsubstituted 1,10-phenanthroline. All five complexes exhibit good cellular uptake and non-specific perinuclear localisation. Upon excitation at 405 nm, the emission from the rhenium complexes could be clearly distinguished from autofluorescence, as demonstrated by spectral detection within the live cells. Four of the complexes did not appear to be toxic, however prolonged excitation could result in membrane blebbing. No major sign of photobleaching was detected upon multiple imaging on the same cell sample.


Assuntos
Complexos de Coordenação/química , Fenantrolinas/química , Rênio/química , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/farmacologia , Células HeLa , Humanos , Ligantes , Fenantrolinas/farmacologia , Rênio/farmacologia
15.
Inorg Chem ; 53(7): 3629-41, 2014 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-24665819

RESUMO

A family of tricarbonyl Re(I) complexes of the formulation fac-[Re(CO)3(NHC)L] has been synthesized and characterized, both spectroscopically and structurally. The NHC ligand represents a bidentate N-heterocyclic carbene species where the central imidazole ring is substituted at the N3 atom by a butyl, a phenyl, or a mesityl group and substituted at the N1 atom by a pyridyl, a pyrimidyl, or a quinoxyl group. On the other hand, the ancillary L ligand alternates between chloro and bromo. For the majority of the complexes, the photophysical properties suggest emission from the lowest triplet metal-to-ligand charge transfer states, which are found partially mixed with triplet ligand-to-ligand charge transfer character. The nature and relative energy of the emitting states appear to be mainly influenced by the identity of the substituent on the N3 atom of the imidazole ring; thus, the pyridyl complexes have blue-shifted emission in comparison to the more electron deficient pyrimidyl complexes. The quinoxyl complexes show an unexpected blue-shifted emission, possibly occurring from ligand-centered excited states. No significant variations were found upon changing the substituent on the imidazole N3 atom and/or the ancillary ligand. The photochemical properties of the complexes have also been investigated, with only the complexes bound to the pyridyl-substituted NHC ligands showing photoinduced CO dissociation upon excitation at 370 nm, as demonstrated by the change in the IR and NMR spectra as well as a red shift in the emission profile after photolysis. Temperature-dependent photochemical experiments show that CO dissociation occurs at temperatures as low as 233 K, suggesting that the Re-C bond cleaves from excited states of metal-to-ligand charge transfer nature rather than thermally activated ligand field excited states. A photochemical mechanism that takes into account the reactivity of the complexes bound to the pyridyl-NHC ligand as well as the stability of those bound to the pyrimidyl- and quinoxyl-NHC ligands is proposed.

16.
Inorg Chem ; 53(1): 229-43, 2014 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-24354312

RESUMO

One of the distinct features of metal-tetrazolate complexes is the possibility of performing electrophilic additions onto the imine-type nitrogens of the coordinated five-membered ring. These reactions, in particular, provide a useful tool for varying the main structural and electronic properties of the starting tetrazolate complexes. In this paper, we demonstrate how the use of a simple protonation-deprotonation protocol enables us to reversibly change, to a significant extent, the light-emission output and performance of a series of Re(I)-tetrazolate-based phosphors of the general formulation fac-[Re(N(∧)N)(CO)3L], where N(∧)N denotes diimine-type ligands such as 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) and L represents a series of different 5-aryl tetrazolates. Indeed, upon addition of triflic acid to these neutral Re(I) complexes, a consistent blue shift (Δλmax ca. 50 nm) of the emission maximum is observed and the protonated species also display increased quantum yield values (4-13 times greater than the starting compounds) and longer decay lifetimes. This alteration can be reversed to the initial condition by further treating the protonated Re(I) complex with a base such as triethylamine. Interestingly, the reversible modulation of luminescent features by the same protonation-deprotonation mechanism appears as a quite general characteristic of photoactive metal tetrazolate complexes, even for compounds in which the 2-pyridyl tetrazolate ligands coordinate the metal center with a bidentate mode, such as the corresponding Ir(III) cyclometalates [Ir(C(∧)N)2L] and the Ru(II) polypyridyl derivatives [Ru(bpy)2L](+). In these cases, the protonation of the starting materials leads to red-shifted and more intense emissions for the Ir(III) complexes, while almost complete quenching is observed in the case of the Ru(II) analogues.

17.
Methods Enzymol ; 532: 3-23, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-24188760

RESUMO

The existence of an accurate force field (FF) model that reproduces the free-energy landscape is a key prerequisite for the simulation of biomineralization. Here, the stages in the development of such a model are discussed including the quality of the water model, the thermodynamics of polymorphism, and the free energies of solvation for the relevant species. The reliability of FFs can then be benchmarked against quantities such as the free energy of ion pairing in solution, the solubility product, and the structure of the mineral-water interface.


Assuntos
Carbonato de Cálcio/metabolismo , Modelos Biológicos , Carbonato de Cálcio/química , Cristalização , Simulação de Dinâmica Molecular , Método de Monte Carlo , Transição de Fase , Solubilidade , Soluções , Solventes/química , Propriedades de Superfície , Termodinâmica , Água/química
18.
Science ; 341(6148): 885-9, 2013 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-23970697

RESUMO

Recent experimental observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. This study uses molecular dynamics simulations to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. Our results predict formation of a dense liquid phase through liquid-liquid separation within the concentration range in which clusters are observed. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liquid-liquid binodal enables a diverse set of experimental observations to be reconciled within the context of established phase-separation mechanisms.

19.
Dalton Trans ; 42(39): 14100-14, 2013 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-23939232

RESUMO

The photophysical and photochemical properties of the new tricarbonyl rhenium(I) complexes bound to N-heterocyclic carbene ligands (NHC), fac-[Re(CO)3(N^C)X] (N^C = 1-phenyl-3-(2-pyridyl)imidazole or 1-quinolinyl-3-(2-pyridyl)imidazole; X = Cl or Br), are reported. The photophysics of these complexes highlight phosphorescent emission from triplet metal-to-ligand ((3)MLCT) excited states, typical of tricarbonyl rhenium(I) complexes, with the pyridyl-bound species displaying a ten-fold shorter excited state lifetime. On the other hand, these pyridyl-bound species display solvent-dependent photochemical CO dissociation following what appear to be two different mechanisms, with a key step being the formation of cationic tricarbonyl solvato-complexes, being themselves photochemically active. The photochemical mechanisms are illustrated with a combination of NMR, IR, UV-Vis, emission and X-ray structural characterization techniques, clearly demonstrating that the presence of the NHC ligand is responsible for the previously unobserved photochemical behavior in other photoactive tricarbonyl rhenium(I) species. The complexes bound to the quinolinyl-NHC ligand (which possess a lower-energy (3)MLCT) are photostable, suggesting that the photoreactive excited state is not any longer thermally accessible. The photochemistry of the pyridyl complexes was investigated in acetonitrile solutions and also in the presence of triethylphosphite, showing a competing and bifurcated photoreactivity promoted by the trans effect of both the NHC and phosphite ligands.

20.
Dalton Trans ; 42(23): 8188-91, 2013 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-23661108

RESUMO

The reaction of 2-pyridyltetrazolate with [Re(CO)5X] (X = Cl, Br) yielded the formation of an unexpected cyclic metallacalix[3]arene, as revealed by X-ray structural studies, characterised by aqua emission and reversible three-electron oxidation.

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