Plasmon-driven substitution of 4-mercaptophenylboronic acid to 4-nitrothiophenol monitored by surface-enhanced Raman spectroscopy.

Plasmon-driven reactions on plasmonic nanoparticles (NPs) occur under significantly different conditions from those of classical organic synthesis and provide a promising pathway for enhancing the efficiency of various chemical processes. However, these reactions can also have undesirable effects, such as 4-mercaptophenylboronic acid (MPBA) deboronation. MPBA chemisorbs well to Ag NPs through its thiol group and can subsequently bind to diols, enabling the detection of various biological structures by surface-enhanced Raman scattering (SERS), but not upon its deboronation. To avoid this reaction, we investigated the experimental conditions of MPBA deboronation on Ag NPs by SERS. Our results showed that the level of deboronation strongly depends on both the morphology of the system and the excitation laser wavelength and power. In addition, we detected not only the expected products, namely thiophenol and biphenyl-4,4-dithiol, but also 4-nitrothiophenol (NTP). The crucial reagent for NTP formation was an oxidation product of hydroxylamine hydrochloride, the reduction agent used in Ag NP synthesis. Ultimately, this reaction was replicated by adding NaNO2 to the system, and its progress was monitored as a function of the laser power, thereby identifying a new reaction of plasmon-driven -B(OH)2 substitution for -NO2.

Characterization of the interaction between the tumour suppressor p53 and heme and its role in the protein conformational dynamics studied by various spectroscopic techniques and hydrogen/deuterium exchange coupled with mass spectrometry.

The tumour suppressor p53 regulates the expression of a myriad of proteins that are important for numerous cellular processes, including apoptosis, cell cycle arrest, DNA repair, metabolism, and even autophagy and ferroptosis. Aside from DNA, p53 can interact with many types of partners including proteins and small organic molecules. The ability of p53 to interact with heme has been reported so far. In this study, we used various spectroscopic studies to conduct a thorough biophysical characterization of the interaction between p53 and heme concerning the oxidation, spin, coordination, and ligand state of heme iron. We found that the p53 oligomeric state and zinc biding ability are preserved upon the interaction with heme. Moreover, we described the effect of heme binding on the conformational dynamics of p53 by hydrogen/deuterium exchange coupled with mass spectrometry. Specifically, the conformational flexibility of p53 is significantly increased upon interaction with heme, while its affinity to a specific DNA sequence is reduced by heme. The inhibitory effect of DNA binding by heme is partially reversible. We discuss the potential heme binding sites in p53 with respect to the observed conformational dynamics changes and perturbed DNA-binding ability of p53 upon interaction with heme.

Factor analysis of the time series of SERS spectra reveals water arrangement and surface plasmon changes in Ag nanoparticle systems.

The enhancement of Raman signals of molecules localized in the vicinity of plasmonic nanoparticles, known as surface-enhanced Raman scattering (SERS) effect, is strongly influenced by the selected excitation wavelength. The optimal excitation wavelength in SERS measurements is given by the position of the surface plasmon extinction (SPE) band of the studied system. Even a small change of the SPE band intensity, position and/or shape during the measurement may influence the SERS signal significantly. In this work, we prepared several systems of Ag nanoparticles, which were used for the demonstration how the information about SPE changes can be obtained by multivariate statistical analysis (factor analysis; FA) from SERS spectral sets, and employed in more precise and more comprehensive interpretation of the results. In non-aggregated Ag colloidal systems measured at the excitation wavelength of 445 nm, SPE band changes could be monitored by the analysis of water stretching vibration together with the vibrations in the fingerprint region. The FA of the water stretching band region was shown to provide unique information on both arrangement and disarrangement of water molecules in the vicinity of Ag NPs during the time evolution of these SERS active systems. In addition, the FA of the fingerprint region helped to monitor a rapid metalation of meso-tetrakis(N-methyl-4-pyridyl)porphine in etched SERS systems with Ag+ ions released from the NPs surface. In aggregated Ag colloidal systems measured at the excitation wavelength of 785 nm, the FA of SERS spectral sets enabled us to reveal the contribution of the 2nd electromagnetic enhancement to the overall SERS signal. The reliability of our conclusions was verified by comparing the results obtained from FA of SERS spectral sets with the data obtained from the parallel SPE measurements of the studied systems.

Novel Metallo-Supramolecular Polymers with 1-Thioxophosphole Main-Chain Units and Remarkable Photoinduced Changes in Their Resonance Raman Spectra.

New low-bandgap unimers, with the central thiophene-(1-thioxophosphole)-thiophene (TPT) ring sequence and 2,2':6',2″-terpyridin-4'-yl (tpy) end groups connected to the central unit via conjugated linkers of different size, are prepared and assembled with Zn(II) and Fe(II) ions to metallo-supramolecular polymers (MSPs) that are studied regarding their properties. The most interesting feature of Zn-MSPs is the luminescence extended deep into the NIR region. Fe-MSPs not only show the metal-to-ligand charge transfer (MLCT) manifested by the MLCT band (an expected feature) but also an as-yet-undescribed remarkable phenomenon: specific damping of the bands of the TPT sequence in the resonance Raman spectra taken from solid Fe-MSPs using the excitation to the MLCT band (532 nm). The damping is highly reversible at the low laser power of 0.1 mW but gradually becomes irreversible as the power reaches ca. 5 mW. The revealed phenomenon is not shown by the same Fe-MSPs in solutions, nor by Fe-MSPs containing no phosphole units. A hypothesis is proposed that explains this phenomenon and its dependence on the irradiation intensity as a result of the interplay of three factors: (i) enhancement of the MLCT process by excitation radiation, (ii) the electron-acceptor character of the 1-thioxophosphole ring, and (iii) morphological changes of the lattice and their dependence on the population of new structures in the lattice.

Plasmon-catalysed decarboxylation of dicarboxybipyridine ligands in Ru(II) complexes chemisorbed on Ag nanoparticles: conditions, proposed mechanism and role of Ag(0) adsorption sites.

Plasmon-catalyzed decarboxylation reactions of Ru(II) bis(2,2'-bipyridine)(4,4'-dicarboxy-bipyridine) denoted as Ru(bpy)2(dcbpy) and Ru(II) tris(4,4'-dicarboxy-bipyridine) denoted as Ru(dcbpy)3 complexes in hydrosol systems with Ag nanoparticles (NPs) conditioned by the presence of Ag(0) adsorption sites on Ag NP surfaces have been revealed by surface-enhanced (resonance) Raman scattering (SERRS and/or SERS) spectral probing and monitoring further supported by factor analysis. Interpretation of the experimental results was based on an identification of specific marker bands of the Ru-dcbpy and of the Ru-bpy units. Furthermore, by a series of specifically targeted SERRS and/or SERS experiments complemented by UV/vis spectral measurements and TEM imaging of deposited Ag NPs, plasmon catalysis by charge carriers, namely hot electrons (e-) and hot holes (h+), has been established as the most probable mechanism of decarboxylation reactions undergone by the carboxylate-chemisorbed Ru-dcbpy units of the complexes. The presence of Ag(0) adsorption sites on Ag NP surfaces as the necessary condition of the reaction progress is in full accord with the charge carrier mechanism of plasmon catalysis. In particular, the neutral Ag(0) sites create the interface required for the transport of hot e- to H+ co-reactants complementing thus the C-C bond breaking and CO2 formation caused by hot h+.

Resonance Raman Excitation Profiles of Fe(II)-Terpyridine Complexes: Electronic Effects of Ligand Modifications.

Metal 2,2':6',2″-terpyridine (tpy) complexes are readily used as building blocks in metallo-supramolecular polymers that stand out for their photophysical properties in solar energy assemblies. Furthermore, Resonance Raman (RR) excitation profiles are sensitive indicators of the electronic properties of chromophores. Previously, using RR spectroscopy, we studied the [Fe(tpy)2]2+ complex and metallo-supramolecular polymers formed by tpy derivatives and Fe(II) ions. Here, we compare RR spectra of iron (Fe(II)) complexes with 4'-substituted tpy ligands─[Fe(4'-R-tpy)2]2+, with R = H (1a), Cl (2a), 4-chlorophenyl (3a), and 2-thienyl (4a) to describe changes in their electronic structure after functionalization. By combining theoretical calculations, RR, and UV/vis spectra, we elucidated differences in the RR excitation profiles of 1a, 2a, and 4a complexes. In all Raman modes, complexes 1a and 2a showed maximal enhancement only at 532 nm excitation, whereas complex 4a exhibited maximal enhancement selectively at either 532 or 633 nm excitations. Based on our calculations, the mixed metal/ligand character of the highest occupied molecular orbital (HOMO) of 4a complex manifests itself through selective enhancement of vibration modes, mainly localized on the 2-thienyl unit at 633 nm excitation, which may explain the unique behavior of this complex. Therefore, complex 4a is a prospective candidate for further detailed photophysical explorations toward developing sensitizers for solar cells.

Polymer Labelling with a Conjugated Polymer-Based Luminescence Probe for Recycling in the Circular Economy.

In this paper, we present the use of a disubstituted polyacetylene with high thermal stability and quantum yield as a fluorescence label for the identification, tracing, recycling, and eventually anti-counterfeiting applications of thermoplastics. A new method was developed for the dispersion of poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA) into polymer blends. For such purposes, four representative commodity plastics were selected, i.e., polypropylene, low-density polyethylene, poly(methyl methacrylate), and polylactide. Polymer recycling was mimicked by two reprocessing cycles of the material, which imparted intensive luminescence to the labelled polymer blends when excited by proper illumination. The concentration of the labelling polymer in the matrices was approximately a few tens ppm by weight. Luminescence was visible to the naked eye and survived the simulated recycling successfully. In addition, luminescence emission maxima were correlated with polymer polarity and glass transition temperature, showing a marked blueshift in luminescence emission maxima with the increase in processing temperature and time. This blueshift results from the dispersion of the labelling polymer into the labelled polymer matrix. During processing, the polyacetylene chains disentangled, thereby suppressing their intermolecular interactions. Moreover, shear forces imposed during viscous polymer melt mixing enforced conformational changes, which shortened the average conjugation length of PTMSDPA chain segments. Combined, these two mechanisms shift the luminescence of the probe from a solid- to a more solution-like state. Thus, PTMSDPA can be used as a luminescent probe for dispersion quality, polymer blend homogeneity, and processing history, in addition to the identification, tracing, and recycling of thermoplastics.

Controlled Tuning of the Size of Ag-Hydrosol Nanoparticles by Nonstabilized THF and Detection of Peroxides in THF.

Surface plasmon extinction (SPE) spectra of plasmonic nanoparticles (NPs) are sensitive indicators of their composition, size, shape, interparticle interactions, and of the dielectric constant of their ambient. In this study, rapid changes in SPE spectra of Ag NPs suggesting variations in NP size and concentration were detected after addition of aged tetrahydrofuran (THF). Using time-dependent UV/vis spectroscopy combined with factor analysis, transmission electron microscopy imaging, selected-area electron diffraction, and energy-dispersive X-ray analysis, we observed that an over-limit amount of aged THF fully dissolved Ag NPs with no plasmon recovery. By contrast, an under-limit amount led to incomplete dissolution of Ag NPs and, after reaching the turnover point, to spontaneous recrystallization on residual Ag nuclei, as demonstrated by the SPE band intensity recovery to the original or even higher values. The newly formed Ag NPs were isometric, and their diameter was dependent on the added amount of THF. Furthermore, both Ag NP dissolution and recrystallization were caused by THF peroxides and their reduction products. Therefore, the dissolution of Ag NPs and the resulting hydrosol bleaching may be used as an indicator of the presence of peroxides in THF. Moreover, the reaction of aged THF with Ag NPs can be employed as a tool for tuning the size of Ag NPs in hydrosols.

Effect of Ethanethiolate Spacer on Morphology and Optical Responses of Ag Nanoparticle Array-Single Layer Graphene Hybrid Systems.

Single layer graphene (SLG) and two-dimensional (2-D) plasmonic Ag nanoparticle arrays assembled by chemisorption of ethanethiol (ET) molecules (AgNPs-ET) were employed as components of two types of hybrid systems designed for surface-enhanced Raman scattering (SERS) spectral probing of SLG localized in the vicinity of plasmonic NPs. Both hybrids were characterized by optical microscopy, transmission electron microscopy (TEM), surface plasmon extinction (SPE), and SERS microRaman spectral measurements at four excitation wavelengths spanning the 445-780 nm range. SERS spectral probing of the glass/SLG/AgNPs-ET hybrid prepared by overdeposition of SLG on glass by the array of ET-modified Ag NPs has shown that the chemisorbed ET acts as an efficient molecular spacer between SLG and Ag NPs surface which, in turn, enabled to obtain SERS spectra of SLG unperturbed by doping or strain. TEM imaging and SERS spectral probing of the second hybrid prepared by overdeposition of AgNPs-ET array on glass by SLG revealed removal of the adsorbed ET molecules and annealing of Ag NPs during the SLG deposition. The characteristics of the resulting glass/AgNPs/SLG hybrid system, namely (i) broad distribution of the annealed Ag NPs sizes and shapes, (ii) SPE curve covering the overall visible spectral region, (iii) absence of the ET spectral bands in SERS spectra, and (iv) fairly uniform SERS enhancement of the G and 2D mode of SLG in the 532-780 nm range in the straight sample geometry indicate that this hybrid can provide a suitable platform for investigation of the excitation wavelength dependence of combined SERS/GERS (graphene-enhanced Raman scattering) enhancement experienced by various molecular species brought into contact with SLG in this hybrid. Finally, weak optical effects attributed to increased reflectivity of SLG in the near field of Ag NPs arrays have been observed in the excitation wavelength dependence of the SERS spectra of both types of hybrid systems.

Arrays of Ag and Au Nanoparticles with Terpyridine- and Thiophene-Based Ligands: Morphology and Optical Responses.

The assembly of Ag and Au nanoparticles (NPs) into nanoparticulate arrays mediated by terpyridine (tpy), 4'-(2-thienyl)terpyridine (T-tpy), and short α,ω-bis(tpy)oligothiophene ligands has been accomplished at the interface between the Ag or Au NP hydrosol and a solution of the molecular species in dichloromethane. The relationship between the morphology and the optical responses of the arrays has been investigated by advanced methods of TEM (transmission electron microscopy) image analysis and surface plasmon extinction (SPE) spectra. It has been established that the size of islands of closely spaced NPs rather than the average interparticle distance affects the extent of delocalization of the surface plasmon excitations and thus also the SPE spectra. Furthermore, the structure of surface-adsorbate complexes formed in these arrays has been investigated by SERS spectral measurements carried out as a function of the excitation wavelength. Photoinduced charge transfer (CT) transitions from the neutral Ags0 and Aus0 adsorption sites on metal NPs to antibonding orbitals of the adsorbates have been identified for Ag/tpy, Ag/T-tpy, Au/tpy, and Au/T-tpy nanoparticulate arrays. Although the surface-adsorbate complexes displaying a photoinduced CT are known for Ag NPs, the Aus0 surface complexes with this CT are newly reported. Bis(tpy)oligothiophenes were found to be attached to both Ag and Au NPs via the tpy group(s). The match between the interparticle distances within the NP islands and the lengths of the oligomers molecules indicates that the molecules act as interparticle linkers. In this case, unequivocal spectral marker band evidence of the Ags0 as well as Aus0 surface complex formation has not been obtained.

Steady-state and time-resolved luminescence of Ru(II) polypyridine complexes attached to Ag nanoparticles: Effect of chemisorption in comparison with electrostatic bonding.

Steady state and nanosecond time resolved luminescence (namely, (3)MLCT phosphorescence) of [Ru(bpy)3](2+) and of [Ru(bpy)2(dcbpy)](2+)/bpy=2,2'-bipyridine; dcbpy=2,2'-bipyridyl-4,4'-dicarboxylic acid/attached to Ag NPs (the former by the electrostatic bonding, the latter by chemisorption) in non-aggregated Ag NP hydrosol systems has been investigated, and compared to the luminescence characteristics of the complexes in aqueous solutions. The intensity decrease of the 452 nm (and/or 455 nm, respectively) main band and elimination of the short wavelength shoulders in the excitation spectra and the intensity decrease of the emission spectra observed for both complexes upon their attachment to Ag NPs is attributed to the overlap of the excitation spectra with the surface plasmon extinction (SPE) of Ag NPs. The overlap leads to a loss of excitation energy by SPE as well as to a decrease of the (1)MLCT to (3)MLCT intersystem crossing efficiency. The time-resolved luminescence study shows that the (3)MLCT phosphorescence lifetimes of both complexes are markedly (by 3 and 4 orders of magnitude, respectively) shortened upon their attachment to Ag NPs. Nevertheless, the (3)MLCT lifetime of the chemisorbed [Ru(bpy)2(dcbpy)](2+) is by at least one order of magnitude shorter than that of the electrostatically bonded [Ru(bpy)3](2+), which indicates, that the phosphorescence lifetimes of these luminophores are strongly affected by the type of Ag NP surface-luminophore bonding.

Alcohol-soluble bis(tpy)thiophenes: new building units for constitutional dynamic conjugated polyelectrolytes.

New building units (unimers) for metallo-supramolecular polymers 2,5-bis(2,2':6',2''-terpyridine-4'-yl)thiophene, M, and 5,5'-bis(2,2':6',2''-terpyridine-4'-yl)(2,2'-bithiophene), B, with ionic groups attached to thiophene rings are prepared by the modification of corresponding bromo-precursors and assembled with Zn(2+) and Fe(2+) ions into alcohol-soluble conjugated constitutional-dynamic polyelectrolytes (polyelectrolyte dynamers). Ionization of side groups only slightly affects the absorption spectra of unimers as well as dynamers but dramatically changes their solubility. Cyclic conformations of unimer molecules resulting from intramolecular interactions between tpy end-groups and cationic or polar (-CH2Br) side groups are proposed to explain the spectral conformity of the M- and B-type unimers and their dynamers and also inhibition of the ionization reaction with tpy end-groups. The absorption spectra and excitation profiles of Raman spectra show that mainly the red arm of the metal-to-ligand charge transfer band of Fe-dynamers is significantly contributed with transitions involving thiophene rings. The constitutional dynamics of Zn-dynamers is fast while that of Fe-dynamers is so slow that it allows effective separation of the dynamer to fractions in SEC columns. Electronic spectra and viscosity measurements proved that excess of Fe(2+) ions results in shortening of the dynamer chains and their end-capping by these ions.

SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion.

Changes in morphology, surface reactivity and surface-enhancement of Raman scattering induced by modification of borate-stabilized Ag nanoparticles by adsorbed chlorides have been explored using TEM, EDX analysis and SERS spectra of probing adsorbate 2,2'-bipyridine (bpy) excited at 514.5 nm and evaluated by factor analysis. At fractional coverages of the parent Ag nanoparticles by adsorbed chlorides <0.6, the Ag colloid/Cl(-)/bpy systems were found to be constituted by fractal aggregates of Ag nanoparticles fairly uniform in size (10 +/- 2 nm) and SERS spectra of Ag(+)-bpy surface species were detected. The latter result was interpreted in terms of the presence of oxidized Ag(+) and/or Ag(n)(+) adsorption sites, which have been encountered also in systems with the chemically untreated Ag nanoparticles. At chloride coverages >0.6, a fusion of fractal aggregates into the compact aggregates of touching and/or interpenetrating Ag nanoparticles has been observed and found to be accompanied by the formation of another surface species, Ag-bpy, as well as by the increase of the overall SERS enhancement of bpy by factor of 40. The same Ag-bpy surface species has been detected under the strongly reducing conditions of reduction of silver nitrate by sodium borohydride in the presence of bpy. The formation of Ag-bpy is thus interpreted in terms of the stabilization of reduced Ag(0) adsorption sites by adsorbed bpy. The formation of reduced adsorption sites on Ag nanoparticle surfaces at chloride coverages >0.6 is discussed in terms of local changes in the work function of Ag. Finally, the SERS spectral detection of Ag-bpy species is proposed as a tool for probing the presence of reduced Ag(0) adsorption sites in systems with chemically modified Ag nanoparticles.

Bimetallic (Ag)Au nanoparticles prepared by the seed growth method: two-dimensional assembling, characterization by energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and surface enhanced raman spectroscopy, and proposed mechanism of growth.

Layered core-shell bimetallic silver-gold nanoparticles were prepared by overdeposition of Au over Ag seeds by the seed-growth method using tetrachloroauric acid, with hydroxylamine hydrochloride as the reductant. The effects of pH, reduction rate, and seeding conditions on the morphology and surface plasmon extinction of the bimetallic nanoparticles were investigated. Nanoparticles prepared by a rapid reduction in the neutral ambient and assembled into two-dimensional nanoparticulate films by adsorption of 2,2'-bipyridine were characterized by energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, surface-enhanced Raman scattering spectroscopy, and transmission electron microscopy. The results are consistent with Ag core and Ag/Au-alloyed shell composition of the nanoparticles. Evidence of the presence of Ag on the surface of the nanoparticles, of enrichment of the Ag/Au alloy shell by Ag toward or at the nanoparticle surface, and of modification of the nanoparticle surface by adsorbed chlorides is also provided. Reduction of the size of the Ag seeds, alloying of Ag and Au in the shell of the nanoparticles, and modification of their surfaces by adsorbed chlorides are tentatively attributed to positive charging of the nanoparticles during the electrocatalytic overdeposition of Au over Ag seeds.

Characterization and surface-enhanced Raman spectral probing of silver hydrosols prepared by two-wavelength laser ablation and fragmentation.

A four step Ag foil laser ablation-Ag nanoparticle fragmentation procedure in ultrapure water was carried out both under argon and in air. Pulses of a high power Nd/YAG laser were used for laser ablation (1064 nm) and for the three step Ag hydrosol treatment in the absence of Ag foil in the sequence 1064-532-1064 nm. Transmission electron microscopy (TEM) and surface plasmon (SP) extinction spectra provide evidence of Ag nanoparticle fragmentation in the second and third step of the procedure carried out under argon. While polydispersity of Ag hydrosol increases in the second step, both the polydispersity and the mean size of the nanoparticles are reduced in the third step. Qualitative and quantitative surface-enhanced Raman scattering (SERS)/surface-enhanced resonance Raman scattering (SERRS) spectral probing of systems with Ag hydrosols and the selected adsorbates at 514.5 nm excitation shows that Ag hydrosols obtained in the second step of the preparation procedure carried out in air are the most suitable substrates for SERS/SERRS experiments performed at this excitation wavelength.