Altering the Surface Characteristics of Coated Silver Surfaces. Soft Donors Allow the Direct Detection of Isolated Porphyrins Using Surface-Enhanced Resonance Raman Spectroscopy

Reglinski, John; Spicer, Mark D.; Ojo, J. Folorunso; McAnally, Gerard; Skorska, A.; Smith, Susan J.; Smith, W. Ewen

doi:10.1021/la034279j

Cited by 6 publications

(11 citation statements)

References 21 publications

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“…Although the chemistry is still to some degree in its infancy, it is also gratifying to see applications beginning to develop. The extensive work on metalloenzyme models has been discussed previously, but in addition applications of the Tm ligands in surface coordination chemistry,146 mass spectrometry,147 as sensors for zinc and thiocyanate in biological and environmental samples148 and in cadmium ion selective membrane sensors149 underlines the potential yet to be tapped. A recent review of strongly donating scorpionate ligands (including Tm and related ligands) has recently been published 150…”

Section: Discussionmentioning

confidence: 99%

Soft Scorpionate Ligands Based on Imidazole‐2‐thione Donors

2009

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Section: Discussionmentioning

confidence: 99%

Soft Scorpionate Ligands Based on Imidazole‐2‐thione Donors

2009

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“…In the former case, the 1353 cm À1 band can be used as the marker band of the free base PPIX, since it lies outside the 1360-1373 cm À1 range in which the n 4 bands of the Fe-PPIX species are located. 13,14,45 Therefore, detection of the spectral form F(II) (attributed to free-base PPIX) at concentrations above 2.5 Â 10 À10 M can be regarded as another advantage of Ag colloid/NaCl/ PPIX systems. A possible explanation of free base PPIX detection in these systems stems from a large promoting effect of NaCl on PPIX aggregate formation.…”

Section: Discussionmentioning

confidence: 99%

Probing strong optical fields in compact aggregates of silver nanoparticles by SERRS of protoporphyrin IX

et al. 2006

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TEM images and measurements of SERRS (surface-enhanced resonance Raman scattering) spectra as a function of the porphyrin concentrations in systems with unmodified and chloride-modified Ag nanoparticles and protoporphyrin IX (PPIX) are reported. TEM images have shown formation of compact aggregates in systems with chloride modified Ag nanoparticles, as opposed to systems with the unmodified particles constituted by isolated particles. SERRS spectra of PPIX as a function of PPIX concentration were measured and subjected to factor analysis. Two spectral components were identified and tentatively attributed to unperturbed PPIX and to Ag+ -PPIX surface species. Concentration value of the SERRS spectral detection limit of the latter species was determined to be nearly three orders of magnitude lower in the system with the compact aggregates than in the system with separated nanoparticles and achieves the value of 1 x 10(-10) M in a macrosampling Raman experiment. TEM images and SERRS-micro-Raman spectra of single compact aggregates of chloride-modified Ag nanoparticles incorporating PPIX molecules were acquired from a sample prepared by attachment of the aggregates to amine groups of derivatized, SiOx/formvar coated copper grids for TEM. The SERRS signal has shown large temporal fluctuations as well as variations from one aggregate to another. Within the signal fluctuations, a SERRS spectrum showing the characteristic bands of both SERRS spectral forms of PPIX and originating most probably from a few PPIX molecules located in hot spots in the interstices between the Ag nanoparticles, was obtained.

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“…Synthesis of [Cu I 10 Cu II 2 (mt) 12 Cl 2 ] and [Cu(PhTm Me )] 2 . LiPhTm Me (60 mg, 0.138 mmol) was dissolved in a small quantity of methanol in a small vial, and the vessel filled/layered slowly with blank methanol.…”

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confidence: 99%

“…The small vial was then placed inside the large vial and methanol layered on top until the small vial was submerged. The vial was left in a vibration-free vicinity for approximately 1 month after which time very dark blue needles ([Cu I 10 Cu II 2 (mt) 12 Cl 2 ]) and pale lilac blocks ([Cu(PhTm Me )] 2 ) had grown at the solvent interfaces. Similar results were obtained when copper(II) chloride was replaced with copper-(II) nitrate or tetrafluoroborate salts.…”

Section: Supporting Informationmentioning

confidence: 99%

“…Second, we have recently shown that Tm Me is a good surface modifier for colloidal coinage metal nanoparticles. 12 To explore the mode of complexation to the metal surface, model compounds of copper, silver, and gold with these ligands are desirable. Thus, the present study concerns the preparation and characterization of complexes of the PhTm Me ligand with the group 11 elements, copper, silver, and gold in the monovalent and higher oxidation states.…”

Section: Introductionmentioning

confidence: 99%

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Coinage Metal Complexes of a Boron-Substituted Soft Scorpionate Ligand

et al. 2006

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An improved synthesis of lithium phenyltris(methimazolyl)borate, Li[PhTm(Me)], (methimazole = 1-methylimidazole-2-thione) is described, and the structure of the methanol-solvated [Li(OHMe)4][PhTm(Me)] has been determined. The syntheses and characterization of complexes [M(PhTm(Me))(PR3)] (M = Cu, Ag, Au; R = Et, Ph;) are reported, and the complexes [Cu(PhTm(Me))(PPh3)], [Ag(PhTm(Me))(PEt3)] and [Au(PhTm(Me))(PEt3)] are crystallographically characterized, showing a progression from pseudo-tetrahedral geometry (copper, S3P coordination) to trigonal planar geometry (silver, S2P coordination) to linear geometry (gold, SP coordination). In addition, the copper(I) and silver(I) triphenylphosphine complexes of the adventitiously formed phenylhydrobis(methimazolyl)borate ligand, [M(PhBm(Me))(PPh3)], have been crystallographically characterized, showing both species to have a trigonal planar primary coordination sphere, with a secondary M...H-B interaction. Finally, reaction of copper(II) chloride with Li[PhTm(Me)] results in formation of a compound analyzing as [Cu(II)(PhTm(Me))Cl], although its extreme insolubility and marked instability have precluded its complete characterization. Attempts to prepare this by ultra-slow diffusion of the reactants through solvent blanks has led to isolation of a mixed-valence copper(I/II) methimazolate cluster, [Cu(I)10Cu(II)2(mt)12Cl2] and a copper(I) dimeric complex [Cu2(PhTm(Me))2], indicating that copper(II) ions oxidatively decompose the phenyltris(methimazolyl)borate anion.

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Altering the Surface Characteristics of Coated Silver Surfaces. Soft Donors Allow the Direct Detection of Isolated Porphyrins Using Surface-Enhanced Resonance Raman Spectroscopy

Cited by 6 publications

References 21 publications

Soft Scorpionate Ligands Based on Imidazole‐2‐thione Donors

Soft Scorpionate Ligands Based on Imidazole‐2‐thione Donors

Probing strong optical fields in compact aggregates of silver nanoparticles by SERRS of protoporphyrin IX

Coinage Metal Complexes of a Boron-Substituted Soft Scorpionate Ligand

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