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1.
Chemistry ; 26(34): 7711-7719, 2020 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-32298506

RESUMO

Catenation is common for the light main-group elements whereas it is rare for the heavy elements. Herein, we report the first example of a neutral molecule containing a Bi4 chain. It is prepared in a one-step reaction between bismuth trichloride and bis(diisopropylphosphino)amine in methanol suspension. The same reaction carried out in dichloromethane gives quite different products. All products have been characterized spectroscopically and using single-crystal X-ray analysis.

2.
Faraday Discuss ; 2020 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-32108185

RESUMO

H2 has been identified as one of the potential energy vectors that can provide a sustainable energy supply when produced through solar-driven water-splitting reaction. Si is the second most abundant element in the Earth's crust and can absorb a significant fraction of the solar spectrum while presenting little toxicity risk, making it an attractive material for photocatalytic H2 production. Hydrogen-terminated mesoporous Si (mp-Si) nanoparticles can be utilized to effectively drive the hydrogen evolution reaction using UV-to-visible light. In this work, the response of the photocatalytic activity of mp-Si nanoparticles to a series of HF acid treatments was investigated. A two-step magnesiothermic reduction method was used to prepare crystalline mp-Si nanoparticles with a specific surface area of 573 m2 g-1. The HF etching process was optimized as a function of the amount of acid added and the reaction time. The reaction time did not influence the H2 evolution rate substantially. However, the amount of HF used did have a significant effect on the photocatalytic activity. In the presence of ≥1.0 mL HF acid per 0.010 g of Si, morphological damage was observed using electron microscopy. N2 adsorption measurements indicated that the pore size and surface area were also altered. Solution-phase 19F{1H} NMR studies indicated the formation of SiF5- and SiF62- when larger volumes of HF were used. Both factors, morphological damage and the presence of byproducts in the pores, likely result in a lowering of the photocatalytic H2 evolution rate. Under the optimized HF treatment conditions (0.5 mL of HF per 0.010 g of Si), a H2 evolution rate of 1398 ± 30 µmol g-1 h-1 was observed.

3.
Magn Reson Chem ; 2020 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-31945203

RESUMO

In the present work, our aim is to decipher the cationic ordering in the octahedral and tetrahedral sheets of two Al-rich synthetic materials, namely, phlogopites of nominal composition K(Mg3-x Alx )[Al1+x Si3-x O10 ](OH)y F2-y and lepidolites in the system trilithionite-polylithionite with composition K (Lix Al3-x )[Al4-2x Si2x O10 ](OH)y F2-y , by directly probing the aluminium distribution through 27 Al and 17 O magic-angle spinning, multiple-quantum magic-angle spinning, and 27 Al-27 Al double-quantum single-quantum nuclear magnetic resonance (NMR) experiments. Notably, 27 Al-27 Al double-quantum single-quantum magic-angle spinning NMR spectra, recorded at 9.34 and/or 20.00 T, show the spatial proximity or avoidance of the Al species inside or between the sheets. In both studied minerals, the ensemble of NMR data suggests a preference for [4] Al in the tetrahedral sheet to occupy position close to the [6] Al of the octahedral sheets.

4.
Chemistry ; 25(71): 16414-16424, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31574185

RESUMO

The use of pincer ligands to access non-VSEPR geometries at main-group centers is an emerging strategy for eliciting new stoichiometric and catalytic reactivity. As part of this effort, several different tridentate trianionic substituents have to date been employed at a range of different central elements, providing a patchwork dataset that precludes rigorous structure-function correlation. An analysis of periodic trends in structure (solid, solution, and computation), bonding, and reactivity based on systematic variation of the central element (P, As, Sb, or Bi) with retention of a single tridentate triamide substituent is reported herein. In this homologous series, the central element can adopt either a bent or planar geometry. The tendency to adopt planar geometries increases descending the group with the phosphorus triamide (1) and its arsenic congener (2) exhibiting bent conformations, and the antimony (3) and bismuth (4) analogues exhibiting a predominantly planar structure in solution. This trend has been rationalized using an energy decomposition analysis. A rare phase-dependent dynamic covalent dimerization was observed for 3 and the associated thermodynamic parameters were established quantitatively. Planar geometries were found to engender lower LUMO energies and smaller band gaps than bent ones, resulting in different reactivity patterns. These results provide a benchmark dataset to guide further research in this rapidly emerging area.

5.
Angew Chem Int Ed Engl ; 58(23): 7850-7855, 2019 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-30945403

RESUMO

Reaction of a tethered triamine ligand with Bi(NMe2 )3 gives a Bi triamide, for which a BiI electronic structure is shown to be most appropriate. The T-shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi-N and P-N bond polarities. Although considerable BiI character is indicated for the title Bi triamide, it exhibits reactivity similar to BiIII electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N-oxide or W(CO)5 . The product of the former shows evidence of coordination-induced oxidation state change at bismuth.

6.
Adv Mater ; 31(5): e1806993, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30516861

RESUMO

In quantum materials, macroscopic behavior is governed in nontrivial ways by quantum phenomena. This is usually achieved by exquisite control over atomic positions in crystalline solids. Here, it is demonstrated that the use of disordered glassy materials provides unique opportunities to tailor quantum material properties. By borrowing ideas from single-molecule spectroscopy, single delocalized π-electron dye systems are isolated in relatively rigid ultrasmall (<10 nm diameter) amorphous silica nanoparticles. It is demonstrated that chemically tuning the local amorphous silica environment around the dye over a range of compositions enables exquisite control over dye quantum behavior, leading to efficient probes for photodynamic therapy (PDT) and stochastic optical reconstruction microscopy (STORM). The results suggest that efficient fine-tuning of light-induced quantum behavior mediated via effects like spin-orbit coupling can be effectively achieved by systematically varying averaged local environments in glassy amorphous materials as opposed to tailoring well-defined neighboring atomic lattice positions in crystalline solids. The resulting nanoprobes exhibit features proven to enable clinical translation.

7.
Nanoscale ; 10(26): 12337-12348, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-29780989

RESUMO

We report enhanced protonic and ionic dynamics in an imidazole/protic ionic liquid mixture confined within the nanopores of silica particles. The ionic liquid is 1-octylimidazolium bis(trifluoromethanesulfonyl)imide ([HC8Im][TFSI]), while the silica particles are microsized and characterized by internal well connected nanopores. We demonstrate that the addition of imidazole is crucial to promote a proton motion decoupled from molecular diffusion, which occurs due to the establishment of new N-HN hydrogen bonds and fast proton exchange events in the ionic domains, as evidenced by both infrared and 1H NMR spectroscopy. An additional reason for the decoupled motion of protons is the nanosegregated structure adopted by the liquid imidazole/[HC8Im][TFSI] mixture, with segregated polar and non-polar nano-domains, as clearly shown by WAXS data. This arrangement, promoted by the length of the octyl group and thus by significant chain-chain interactions, reduces the mobility of molecules (Dmol) more than that of protons (DH), which is manifested by DH/Dmol ratios greater than three. Once included into the nanopores of hydrophobic silica microparticles, the nanostructure of the liquid mixture is preserved with slightly larger ionic domains, but effects on the non-polar ones are unclear. This results in a further enhancement of proton motion with localised paths of conduction. These findings demonstrate significant progress in the design of proton conducting materials via tailor-made molecular structures as well as by smart exploitation of confinement effects. Compared to other imidazole-based proton conducting materials that are crystalline up to 90 °C or above, the gel materials that we propose are useful for applications at room temperature, and can thus find applications in e.g. intermediate temperature proton exchange fuel cells.

8.
Angew Chem Int Ed Engl ; 57(3): 749-754, 2018 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-29152832

RESUMO

An extended π-system containing two [3]cumulene fragments separated by a p-carboquinoid and stabilized by two capping N-heterocyclic carbenes (NHCs) has been prepared. Mono- and bis(imidazolidinium ethynyl) cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4-bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis-1,4-([3]cumulene)-p-carboquinoid as a result of the π-accepting properties of the capping NHCs.

9.
Inorg Chem ; 57(2): 892-898, 2018 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-29286238

RESUMO

The local environments around tellurium atoms in a series of tellurium oxide crystals were probed by 125Te solid-state NMR spectroscopy. Crystals with distinct TeOn units (n from 3 to 6), including Na2TeO3, α-TeO2 and γ-TeO2, Te2O(PO4)2, K3LaTe2O9, BaZnTe2O7, and CsYTe3O8 were studied. The latter four were synthesized through a solid-state process. X-ray diffraction was used to confirm the successful syntheses. The 125Te chemical shift was found to exhibit a strong linear correlation with the Te coordination number. The 125Te chemical-shift components (δ11, δ22, and δ33) of the TeO4 units were further correlated to the O-Te-O-bond angles. With the aid of 125Te NMR, it is likely that these relations can be used to estimate the coordination states of Te atoms in unknown Te crystals and glasses.

10.
J Biomed Mater Res B Appl Biomater ; 105(4): 764-777, 2017 05.
Artigo em Inglês | MEDLINE | ID: mdl-26748481

RESUMO

In this study, nine phosphate-based glass formulations from the system P2 O5 -CaO-Na2 O-MgO-B2 O3 were prepared with P2 O5 content fixed as 40, 45 and 50 mol%, where Na2 O was replaced by 5 and 10 mol% B2 O3 and MgO and CaO were fixed to 24 and 16 mol%, respectively. The effect of B2 O3 addition on the viscosity-temperature behaviour, fragility index and structure of the glasses was investigated. The composition of the glasses was confirmed by ICP-AES. The viscosity-temperature behaviour of the glasses were measured using beam-bending and parallel -plate viscometers. The viscosity of the glasses investigated was found to shift to higher temperature with increasing B2 O3 content. The kinetic fragility parameter, m and F1/2 , estimated from the viscosity curve were found to decease with increasing B2 O3 content. The structural analysis was achieved by a combination of Fourier transform infrared spectroscopy and solid state nuclear magnetic resonance. 31 P solid-state magic-angle-spinning nuclear magnetic resonance (MAS-NMR) showed that the local structure of the glasses changes with increasing B2 O3 content. As B2 O3 was added to the glass systems, the phosphate connectivity increases as the as the Q1 units transforms into Q2 units. The 11 B NMR results confirmed the presence of tetrahedral boron (BO4 ) units for all the compositions investigated. Structural analysis indicates an increasing level of cross-linking with increasing B2 O3 content. Evidence of the presence of P-O-B bonds was also observed from the FTIR and 31 P NMR analysis. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 764-777, 2017.


Assuntos
Compostos de Boro/química , Cerâmica/química , Cerâmica/síntese química , Temperatura Alta , Fosfatos/química , Viscosidade
11.
J Mater Sci Mater Med ; 27(7): 117, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-27255688

RESUMO

A 2-Step sinter/anneal treatment has been reported previously for forming porous CPP as biodegradable bone substitutes [9]. During the 2-Step annealing treatment, the heat treatment used strongly affected the rate of CPP degradation in vitro. In the present study, x-ray diffraction and (31)P solid state nuclear magnetic resonance were used to determine the phases that formed using different heat treating processes. The effect of in vitro degradation (in PBS at 37 °C, pH 7.1 or 4.5) was also studied. During CPP preparation, ß-CPP and γ-CPP were identified in powders formed from a calcium monobasic monohydrate precursor after an initial calcining treatment (10 h at 500 °C). Melting of this CPP powder (at 1100 °C), quenching and grinding formed amorphous CPP powders. Annealing powders at 585 °C (Step-1) resulted in rapid sintering to form amorphous porous CPP. Continued annealing to 650 °C resulted in crystallization to form a multi-phase structure of ß-CPP primarily plus lesser amounts of α-CPP, calcium ultra-phosphates and retained amorphous CPP. Annealing above 720 °C and up to 950 °C transformed this to ß-CPP phase. In vitro degradation of the 585 °C (Step-1 only) and 650 °C Step-2 annealed multi-phase samples occurred significantly faster than the ß-CPP samples formed by Step-2 annealing at or above 720 °C. This faster degradation was attributable to preferential degradation of thermodynamically less stable phases that formed in samples annealed at 650 °C (i.e. α-phase, ultra-phosphate and amorphous CPP). Degradation in lower pH solutions significantly increased degradation rates of the 585 and 650 °C annealed samples but had no significant effect on the ß-CPP samples.


Assuntos
Substitutos Ósseos/química , Fosfatos de Cálcio/química , Materiais Biocompatíveis/química , Cimentos para Ossos/química , Osso e Ossos/fisiologia , Humanos , Concentração de Íons de Hidrogênio , Espectroscopia de Ressonância Magnética , Microscopia Eletrônica de Varredura , Isótopos de Fósforo/química , Polifosfatos/química , Porosidade , Pós , Temperatura , Termodinâmica , Difração de Raios X
12.
J Biomater Appl ; 30(10): 1445-59, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-26675751

RESUMO

A host of research opportunities with innumerable clinical applications are open to biomedical glasses if one considers their potential as therapeutic inorganic ion delivery systems. Generally, applications have been limited to repair and regeneration of hard tissues while compositions are largely constrained to the original bioactive glass developed in the 1960s. However, in oncology applications the therapeutic paradigm shifts from repair to targeted destruction. With this in mind, the composition-structure-property-function relationships of vanadium-containing zinc-silicate glasses (0.51SiO2-0.29Na2O-(0.20-X)ZnO-XV2O5, 0 ≤ X ≤ 0.09) were characterized in order to determine their potential as therapeutic inorganic ion delivery systems. Increased V2O5mole fraction resulted in a linear decrease in density and glass transition temperature (Tg).(29)Si MAS NMR peak maxima shifted upfield while(51)V MAS NMR peak maxima were independent of V2O5content and overlapped well with the spectra NaVO3 Increased V2O5mole fraction caused ion release to increase. When human liver cancer cells, HepG2, were exposed to these ions they demonstrated a concentration-dependent cytotoxic response, mediated by apoptosis. This work demonstrates that the zinc-silicate system studied herein is capable of delivering therapeutic inorganic ions at concentrations that induce apoptotic cell death and provide a simple means to control therapeutic inorganic ion delivery.


Assuntos
Apoptose/efeitos dos fármacos , Materiais Biocompatíveis/química , Sistemas de Liberação de Medicamentos , Vidro/química , Íons/administração & dosagem , Neoplasias Hepáticas/tratamento farmacológico , Silicatos/química , Compostos de Vanádio/química , Células Hep G2 , Humanos , Íons/farmacologia , Fígado/efeitos dos fármacos , Fígado/patologia , Neoplasias Hepáticas/patologia , Teste de Materiais , Zinco/química
13.
Nano Lett ; 16(1): 651-5, 2016 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-26669906

RESUMO

Stimuli-responsive materials have attracted great interest in catalysis, sensing, and drug delivery applications and are typically constituted by soft components. We present a one-pot synthetic method for a type of inorganic silica-based shape change material that is responsive to water vapor exposure. After the wetting treatment, the cross-sectional shape of aminated mesoporous silica nanoparticles (MSNs) with hexagonal pore lattice changed from hexagonal to six-angle-star, accompanied by the loss of periodic mesostructural order. Nitrogen sorption measurements suggested that the wetting treatment induced a shrinkage of mesopores resulting in a broad size distribution and decreased mesopore volume. Solid-state (29)Si nuclear magnetic resonance (NMR) spectroscopy of samples after wetting treatment displayed a higher degree of silica condensation, indicating that the shape change was associated with the formation of more siloxane bonds within the silica matrix. On the basis of material characterization results, a mechanism for the observed anisotropic shrinkage is suggested based on a buckling deformation induced by capillary forces in the presence of a threshold amount of water vapor available beyond a humidity of about 50%. The work presented here may open a path toward novel stimuli-responsive materials based on inorganic components.


Assuntos
Sistemas de Liberação de Medicamentos , Nanopartículas/química , Dióxido de Silício/química , Humanos , Umidade , Espectroscopia de Ressonância Magnética , Porosidade
14.
J Biomed Mater Res A ; 103(7): 2344-54, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-25366812

RESUMO

We have synthesized TiO2 doped strontium borate glasses, 70B2O3-(30-x)SrO-xTiO2 and 70B2 O3 -20SrO(10-x)Na2 O-xTiO2 . The composition dependence of glass structure, density, thermal properties, durability, and cytotoxicity of degradation products was studied. Digesting the glass in mineral acid and detecting the concentrations of various ions using an ICP provided the actual compositions that were 5-8% deviated from the theoretical values. The structure was investigated by means of (11)B magic angle spinning (MAS) NMR spectroscopy. DSC analyses provided the thermal properties and the degradation rates were measured by measuring the weight loss of glass disc-samples in phosphate buffered saline at 37°C in vitro. Finally, the MTT assay was used to analyze the cytotoxicity of the degradation products. The structural analysis revealed that replacing TiO2 for SrO or Na2 O increased the BO3/BO4 ratio suggesting the network-forming role of TiO2 . Thermal properties, density, and degradation rates also followed the structural changes. Varying SrO content predominantly controlled the degradation rates, which in turn controlled the ion release kinetics. A reasonable control (2-25% mass loss in 21 days) over mass loss was achieved in current study. Even though, very high concentrations (up to 5500 ppm B, and 1200 ppm Sr) of ions were released from the ternary glass compositions that saturated the degradation media in 7 days, the degradation products from ternary glass system was found noncytotoxic. However, quaternary glasses demonstrated negative affect on cell viability due to very high (7000 ppm) Na ion concentration. All the glasses investigated in current study are deemed fast degrading with further control over degradation rates, release kinetics desirable.


Assuntos
Materiais Biocompatíveis , Boratos/química , Vidro , Estrôncio/química , Difração de Raios X
15.
J Biomater Appl ; 29(9): 1203-17, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25391445

RESUMO

Non-classical ionomer glasses like those based on zinc-boron-germanium glasses are of special interest in a variety of medical applications owning to their unique combination of properties and potential therapeutic efficacy. These features may be of particular benefit with respect to the utilization of glass ionomer cements for minimally invasive dental applications such as the atruamatic restorative treatment, but also for expanded clinical applications in orthopedics and oral-maxillofacial surgery. A unique system of zinc-boron-germanium-based glasses (10 compositions in total) has been designed using a Design of Mixtures methodology. In the first instance, ionomer glasses were examined via differential thermal analysis, X-ray diffraction, and (11)B MAS NMR spectroscopy to establish fundamental composition - structure-property relationships for the unique system. Secondly, cements were synthesized based on each glass and handling characteristics (working time, Wt, and setting time, St) and compression strength were quantified to facilitate the development of both experimental and mathematical composition-structure-property relationships for the new ionomer cements. The novel glass ionomer cements were found to provide Wt, St, and compression strength in the range of 48-132 s, 206-602 s, and 16-36 MPa, respectively, depending on the ZnO/GeO2 mol fraction of the glass phase. A lower ZnO mol fraction in the glass phase provides higher glass transition temperature, higher N4 rate, and in combination with careful modulation of GeO2 mol fraction in the glass phase provides a unique approach to extending the Wt and St of glass ionomer cement without compromising (in fact enhancing) compression strength. The data presented in this work provide valuable information for the formulation of alternative glass ionomer cements for applications within and beyond the dental clinic, especially where conventional approaches to modulating working time and strength exhibit co-dependencies (i.e. the enhancement of one property comes at the expense of the other) and therefore limit development strategies.


Assuntos
Cimentos de Ionômeros de Vidro/química , Fenômenos Biomecânicos , Boro/química , Força Compressiva , Germânio/química , Humanos , Espectroscopia de Ressonância Magnética , Teste de Materiais , Análise de Regressão , Termodinâmica , Difração de Raios X , Zinco/química
16.
Science ; 344(6179): 75-8, 2014 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-24700853

RESUMO

Why does cyanide not react destructively with the proximal iron center at the active site of 1-aminocyclopropane-1-carboxylic acid (ACC) oxidase, an enzyme central to the biosynthesis of ethylene in plants? It has long been postulated that the cyanoformate anion, [NCCO2](-), forms and then decomposes to carbon dioxide and cyanide during this process. We have now isolated and crystallographically characterized this elusive anion as its tetraphenylphosphonium salt. Theoretical calculations show that cyanoformate has a very weak C-C bond and that it is thermodynamically stable only in low dielectric media. Solution stability studies have substantiated the latter result. We propose that cyanoformate shuttles the potentially toxic cyanide away from the low dielectric active site of ACC oxidase before breaking down in the higher dielectric medium of the cell.


Assuntos
Aminoácido Oxirredutases/metabolismo , Formiatos/isolamento & purificação , Nitrilos/isolamento & purificação , Aminoácido Oxirredutases/química , Dióxido de Carbono/química , Domínio Catalítico , Cristalização , Cianetos/química , Etilenos/metabolismo , Formiatos/química , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Nitrilos/química , Termodinâmica , Difração de Raios X
17.
Chem Commun (Camb) ; 48(64): 7922-4, 2012 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-22766842

RESUMO

Reactions of Me(3)P with SnCl(4) in the presence of nAlCl(3) (n = 0, 1, 2) yields a series of P-Sn complexes illustrating new bonding environments for tin.

18.
Chem Commun (Camb) ; 48(59): 7359-61, 2012 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-22717577

RESUMO

Reactions of Me(3)P with alkyl- or arylchlorophosphines yield phosphinophosphonium salts in quantitative yields, demonstrating a Menschutkin P-P methodology that has potentially broad application for element-element bond formation.

19.
Nat Mater ; 11(5): 460-7, 2012 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-22426457

RESUMO

Batteries, fuel cells and solar cells, among many other high-current-density devices, could benefit from the precise meso- to macroscopic structure control afforded by the silica sol-gel process. The porous materials made by silica sol-gel chemistry are typically insulators, however, which has restricted their application. Here we present a simple, yet highly versatile silica sol-gel process built around a multifunctional sol-gel precursor that is derived from the following: amino acids, hydroxy acids or peptides; a silicon alkoxide; and a metal acetate. This approach allows a wide range of biological functionalities and metals--including noble metals--to be combined into a library of sol-gel materials with a high degree of control over composition and structure. We demonstrate that the sol-gel process based on these precursors is compatible with block-copolymer self-assembly, colloidal crystal templating and the Stöber process. As a result of the exceptionally high metal content, these materials can be thermally processed to make porous nanocomposites with metallic percolation networks that have an electrical conductivity of over 1,000 S cm(-1). This improves the electrical conductivity of porous silica sol-gel nanocomposites by three orders of magnitude over existing approaches, opening applications to high-current-density devices.

20.
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