Search

A nitric oxide (NO) photodonor (1) capable of releasing two NO molecules through a stepwise mechanism has been covalently grafted to blue-emitting N-doped carbon dots (NCDs). The resulting water-soluble nanoconjugate (NCDs-1), ca. 10 nm in diameter, exhibits a new absorption band not present in the simple physical mixture of the two components and is attributable to strong electronic interactions between them in the ground state. Blue light excitation of NCDs-1 leads to NO photogeneration with an efficiency almost one order of magnitude higher than that observed for 1 alone, probably due to a photoinduced electron transfer between the NCDs and the grafted 1. Photoexcitation of the nanoconjugate also results in effective photothermal conversion, which is negligible in the naked NCDs. Furthermore, in contrast to 1, the nanoconjugate liberates NO also under excitation with green light. Finally, the typical blue fluorescence of the NCDs is quenched in NCDs-1 but restored upon the photouncaging of the second NO molecule, providing readable and real-time information about the amount of NO photogenerated.

An inorganic wide-bandgap hole transport layer (HTL), copper(I) thiocyanate (CuSCN), is employed in inorganic planar hydrothermally deposited Sb 2 S 3 solar cells. With excellent hole transport properties and uniform compact morphology, the solution-processed CuSCN layer suppresses the leakage current and improves charge selectivity in an n-i-p-type solar cell structure. The device without the HTL (FTO/CdS/Sb 2 S 3 /Au) delivers a modest power conversion efficiency (PCE) of 1.54%, which increases to 2.46% with the introduction of CuSCN (FTO/CdS/Sb 2 S 3 /CuSCN/Au). This PCE is a significant improvement compared with the previous reports of planar Sb 2 S 3 solar cells employing CuSCN. CuSCN is therefore a promising alternative to expensive and inherently unstable organic HTLs. In addition, CuSCN makes an excellent optically transparent (with average transmittance >90% in the visible region) and shunt-blocking HTL layer in pinhole-prone ultrathin (<100 nm) semitransparent absorber layers grown by green and facile hydrothermal deposition. A semitransparent device is fabricated using an ultrathin Au layer (∼10 nm) with a PCE of 2.13% and an average visible transmittance of 13.7%., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The ferrozine (FZ) assay is a vital oxidation state-specific colorimetric assay for the quantification of Fe 2+ ions in environmental samples due to its sharp increase in absorbance at 562 nm upon addition of Fe 2+ . However, it has yet to be applied to corresponding fluoresence assays which typically offer higher sensitivites and lower detection limits. In this article we present for the first time its pairing with upconverting luminescent nanomaterials to enable detection of Fe 2+ via the inner filter effect using a low-power continuous wave diode laser (45 mW). Upon near infra-red excitation at 980 nm, the overlap of the upconversion emission of Er 3+ at approximately 545 nm and the absorbance of the FZ:Fe 2+ complex at 562 nm enabled measurement in the change of UCNP emission response as a function of Fe 2+ concentration in a ratiometric manner. We first applied large, ultra-bright poly(acrylic acid) (PAA)-capped Gd 2 O 2 S:Yb 3+ ,Er 3+ UCNPs upconverting nanoparticles (UCNPs) for the detection of Fe 2+ using FZ as the acceptor. The probe displayed good selectivity and sensitivity for Fe 2+ , with a low limit of detection (LoD) of 2.74 μM. Analogous results employing smaller (31 nm) PAA-capped hexagonal-phase NaYF 4 :Yb 3+ ,Er 3+ UCNPs synthesised in our lab were achieved, with a lower LoD towards Fe 2+ of 1.43 μM. These results illustrate how the ratiometric nature of the system means it is applicable over a range of particle sizes, brightnesses and nanoparticle host matrices. Preliminary investigations also found the probes capable of detecting micromolar concentrations of Fe 2+ in turbid solutions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Rare-earth doped nanoparticles (RENPs) are attracting increasing interest in materials science due to their optical, magnetic, and chemical properties. RENPs can emit and absorb radiation in the second biological window (NIR-II, 1000-1400 nm) making them ideal optical probes for photoluminescence (PL) in vivo imaging. Their narrow emission bands and long PL lifetimes enable autofluorescence-free multiplexed imaging. Furthermore, the strong temperature dependence of the PL properties of some of these RENPs makes remote thermal imaging possible. This is the case of neodymium and ytterbium co-doped NPs that have been used as thermal reporters for in vivo diagnosis of, for instance, inflammatory processes. However, the lack of knowledge about how the chemical composition and architecture of these NPs influence their thermal sensitivity impedes further optimization. To shed light on this, we have systematically studied their emission intensity, PL decay time curves, absolute PL quantum yield, and thermal sensitivity as a function of the core chemical composition and size, active-shell, and outer-inert-shell thicknesses. The results revealed the crucial contribution of each of these factors in optimizing the NP thermal sensitivity. An optimal active shell thickness of around 2 nm and an outer inert shell of 3.5 nm maximize the PL lifetime and the thermal response of the NPs due to the competition between the temperature-dependent back energy transfer, the surface quenching effects, and the confinement of active ions in a thin layer. These findings pave the way for a rational design of RENPs with optimal thermal sensitivity.

Upconversion nanoparticles (UCNPs) are some of the most promising nanomaterials for bioanalytical and biomedical applications. One important challenge to be still solved is how UCNPs can be optimally implemented into Förster resonance energy transfer (FRET) biosensing and bioimaging for highly sensitive, wash-free, multiplexed, accurate, and precise quantitative analysis of biomolecules and biomolecular interactions. The many possible UCNP architectures composed of a core and multiple shells doped with different lanthanoid ions at different ratios, the interaction with FRET acceptors at different possible distances and orientations via biomolecular interaction, and the many and long-lasting energy transfer pathways from the initial UCNP excitation to the final FRET process and acceptor emission make the experimental determination of the ideal UCNP-FRET configuration for optimal analytical performance a real challenge. To overcome this issue, we have developed a fully analytical model that requires only a few experimental configurations to determine the ideal UCNP-FRET system within a few minutes. We verified our model via experiments using nine different Nd-, Yb-, and Er-doped core-shell-shell UCNP architectures within a prototypical DNA hybridization assay using Cy3.5 as an acceptor dye. Using the selected experimental input, the model determined the optimal UCNP out of all theoretically possible combinatorial configurations. An extreme economy of time, effort, and material was accompanied by a significant sensitivity increase, which demonstrated the powerful feat of combining a few selected experiments with sophisticated but rapid modeling to accomplish an ideal FRET biosensor.

Au nanostructures exhibiting a localized surface plasmon resonance in the near-infrared spectral window are obtained in a single, green step at room temperature by pomegranate extract in the presence of a highly biocompatible β-cyclodextrin branched polymer, without the need of preformed seeds, external reducing and sacrificial agents, and conventional surfactants. The polymeric component makes the Au nanostructures dispersible in water, stable for weeks and permits their supramolecular assembling with the chemotherapeutic sorafenib and a nitric oxide (NO) photodonor (NOPD), chosen as representative for chemo- and photo-therapeutics. Irradiation of the plasmonic Au nanostructures in the therapeutic window with 808 nm laser light results in a good photothermal response, which (i) is not affected by the presence of either the chemo- or the phototherapeutic guests and (ii) does not lead to their photoinduced decomposition. Besides, irradiation of the hybrid Au nanoassembly with the highly biocompatible green light results in the NO release from the NOPD with efficiency similar to that observed for the free guest. Preliminary biological experiments against Hep-G2 hepatocarcinoma cell lines are also reported.

Heterogeneous photocatalysis is considered as one of the most appealing options for the treatment of organic pollutants in water. However, its definitive translation into industrial practice is still very limited because of both the complexity of large-scale production of catalysts and the problems involved in handling the powder-based photocatalysts in the industrial plants. Here, we demonstrate that the MOCVD approach can be successfully used to prepare large-scale supported catalysts with a good photocatalytic activity towards dye degradation. The photocatalyst consisted of nanostructured TiO 2 thin film deposited on a stainless steel mesh substrate. The film thickness, the morphological features, and the crystallographic properties of the different portions of the sample were correlated to the position in the reactor chamber and the reaction conditions. The photocatalytic activity was evaluated according to the international standard test ISO 10678:2010 based on methylene blue degradation. The photocatalytic activity is essentially constant (P MB over 40 µmol·m -2 ·h -1 ) throughout the film, except for the portion of sample placed at the very end of the reactor chamber, where the TiO 2 film is too thin to react properly. It was assessed that a minimum film thickness of 250-300 nm is necessary to reach the maximum photocatalytic performance.

Luminescent upconversion nanocrystals (UCNCs) have become one of the most promising nanomaterials for biosensing, imaging, and theranostics. However, their ultimate translation into robust luminescent probes for daily use in biological and medical laboratories requires comprehension and control of the many possible deactivation pathways that cause upconversion luminescence (UCL) quenching. Here, we demonstrate that thorough modeling of UCL rise and decay kinetics using a freely accessible software can identify the UCL quenching mechanisms in small (<40 nm) UCNCs with spatial and temporal resolution. Applied to the most relevant β-NaYF 4 :Yb 3+ ,Er 3+ UCNCs, our model showed that only a few distinct nonradiative low-energy transitions were deactivated via specific solvent and ligand vibrations with a strong downstream effect on the population and depopulation dynamics of the emitting states. UCL quenching could penetrate ca. 4 nm inside the UCNC, which resulted in significant size-dependent changes of UCL intensities and spectra. Despite the large surface-to-volume ratios and UCL quenching via the UCNC surface, we found strong contributions of the outer layers to the overall UCL, which will be highly important for the design of UCNPs to investigate biomolecular interactions via distance-dependent energy transfer methods. Our advanced kinetic model is easily scalable to different UCNC architectures, environments, and energy transfer interactions such that relatively simple modeling of UCL kinetics can be used for efficiently optimizing UCNCs for their final application as practical luminescent probes.

Upconverting nanoparticles are attracting extensive interest as a multimodal imaging tool. In this work, we report on the synthesis and characterization of gadolinium-enriched upconverting nanoparticles for bimodal magnetic resonance and optical luminescence imaging. NaYF 4 :Gd 3+ ,Yb 3+ ,Tm 3+ core upconverting nanoparticles were obtained by a thermal coprecipitation of lanthanide oleate precursors in the presence of oleic acid as a stabilizer. With the aim of improving the upconversion emission and increasing the amount of Gd 3+ ions on the nanoparticle surface, a 2.5 nm NaGdF 4 shell was grown by the epitaxial layer-by-layer strategy, resulting in the 26 nm core-shell nanoparticles. Both core and core-shell nanoparticles were coated with poly(ethylene glycol) (PEG)-neridronate (PEG-Ner) to have stable and well-dispersed upconverting nanoparticles in a biological medium. FTIR spectroscopy and thermogravimetric analysis indicated the presence of ∼20 wt % of PEG-Ner on the nanoparticle surface. The addition of inert NaGdF 4 shell resulted in a total 26-fold enhancement of the emission under 980 nm excitation and also affected the T 1 and T 2 relaxation times. Both r 1 and r 2 relaxivities of PEG-Ner-modified nanoparticles were much higher compared to those of non-PEGylated particles, thus manifesting their potential as a diagnostic tool for magnetic resonance imaging. Together with the enhanced luminescence efficiency, upconverting nanoparticles might represent an efficient probe for bimodal in vitro and in vivo imaging of cells in regenerative medicine, drug delivery, and/or photodynamic therapy., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The biological application of photoactivatable ruthenium anticancer prodrugs is limited by the need to use poorly penetrating high-energy visible light for their activation. Upconverting nanoparticles (UCNPs), which produce high-energy light under near-infrared (NIR) excitation, can solve this issue, provided that they form stable, water (H 2 O)-dispersible nanoconjugates with the prodrug and that there is efficient energy transfer from the UCNP to the ruthenium complex. Herein, we report on the synthesis and photochemistry of the ruthenium(II) polypyridyl complex [Ru(bpy) 2 ( 3 H )](PF 6 ) 2 ([ 1 ](PF 6 ) 2 ), where bpy = 2,2-bipyridine and 3 H is a photocleavable bis(thioether) ligand modified with two phosphonate moieties. This ligand was coordinated to the ruthenium center through its thioether groups and could be dissociated under blue-light irradiation. Complex [ 1 ](PF 6 ) 2 was bound to the surface of NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 :Nd 3+ @NaYF 4 core-shell-shell (CSS-)UCNPs through its bis(phosphonate) group, thereby creating a H 2 O-dispersible, thermally stable nanoconjugate (CSS-UCNP@[ 1 ]). Conjugation to the nanoparticle surface was found to be most efficient in neutral to slightly basic conditions, resulting in up to 2.4 × 10 3 Ru II ions per UCNP. The incorporation of a neodymium-doped shell layer allowed for the generation of blue light using low-energy, deep-penetrating light (796 nm). This wavelength prevents the undesired heating seen with conventional UCNPs activated at 980 nm. Irradiation of CSS-UCNP@[ 1 ] with NIR light led to activation of the ruthenium complex [ 1 ](PF 6 ) 2 . Although only one of the two thioether groups was dissociated under irradiation at 50 W·cm -2 , we provide the first demonstration of the photoactivation of a ruthenium thioether complex using 796 nm irradiation of a H 2 O-dispersible nanoconjugate.

Development of high-entropy alloy (HEA) films is a promising and cost-effective way to incorporate these materials of superior properties in harsh environments. In this work, a refractory high-entropy alloy (RHEA) film of equimolar CuMoTaWV was deposited on silicon and 304 stainless-steel substrates using DC-magnetron sputtering. A sputtering target was developed by partial sintering of an equimolar powder mixture of Cu, Mo, Ta, W, and V using spark plasma sintering. The target was used to sputter a nanocrystalline RHEA film with a thickness of ∼900 nm and an average grain size of 18 nm. X-ray diffraction of the film revealed a body-centered cubic solid solution with preferred orientation in the (110) directional plane. The nanocrystalline nature of the RHEA film resulted in a hardness of 19 ± 2.3 GPa and an elastic modulus of 259 ± 19.2 GPa. A high compressive strength of 10 ± 0.8 GPa was obtained in nanopillar compression due to solid solution hardening and grain boundary strengthening. The adhesion between the RHEA film and 304 stainless-steel substrates was increased on annealing. For the wear test against the E52100 alloy steel (Grade 25, 700-880 HV) at 1 N load, the RHEA film showed an average coefficient of friction (COF) and wear rate of 0.25 (RT) and 1.5 (300 °C), and 6.4 × 10 -6 mm 3 /N m (RT) and 2.5 × 10 -5 mm 3 /N m (300 °C), respectively. The COF was found to be 2 times lower at RT and wear rate 10 2 times lower at RT and 300 °C than those of 304 stainless steel. This study may lead to the processing of high-entropy alloy films for large-scale industrial applications.

The capability of upconverting nanoparticles (UCNPs) to convert near infrared (NIR) into visible light has become an important feature for biosensing, imaging, therapy, and their combination. While significant achievements have been accomplished during the last decade developing nanohybrids based on UCNPs as energy donors in Förster resonance energy transfer (FRET) systems, it is still challenging to understand and control FRET from UCNPs to dyes and to adapt the NIR excitation wavelength. Here, we describe the synthesis, characterization, and steady-state and time-resolved FRET analysis of UCNP-DNA nanohybrids, in which dye labelled single stranded (ss)DNA was attached to Yb-Er-co-doped core UCNPs (c-UCNPs) and c-UCNPs with a thin Nd-doped shell and a second thin undoped shell (css-UCNPs). Despite differences in sizes, compositions, donor-acceptor distances, brightness, and excitation wavelength (980 nm for Yb 3+ and 808 nm for Nd 3+ ), all UCNP-DNA nanohybrids showed very similar concentration dependent FRET-quenching of UCNP luminescence with efficiencies between 0 and ∼20%. We analyzed luminescence intensities, decay times, and rise times and could show the entanglement of excitation and emission kinetics by simply changing the excitation wavelength from 980 nm to 808 nm for the same css-UCNPs. Time-gated FRET-sensitized dye luminescence showed dye-ssDNA concentration dependence over four orders of magnitude (1 nM to 10 μM), which suggested a possible application to nucleic acid biosensing for both 808 and 980 nm excitation.

The biological application of ruthenium anticancer prodrugs for photodynamic therapy (PDT) and photoactivated chemotherapy (PACT) is restricted by the need to use poorly penetrating high-energy photons for their activation, i.e., typically blue or green light. Upconverting nanoparticles (UCNPs), which produce high-energy light under near-infrared (NIR) excitation, may solve this issue, provided that the coupling between the UCNP surface and the Ru prodrug is optimized to produce stable nanoconjugates with efficient energy transfer from the UCNP to the ruthenium complex. Herein, we report on the synthesis and photochemistry of the two structurally related ruthenium(II) polypyridyl complexes [Ru(bpy) 2 ( 5 )](PF 6 ) 2 ([ 1 ](PF 6 ) 2 ) and [Ru(bpy) 2 ( 6 )](PF 6 ) 2 ([ 2 ](PF 6 ) 2 ), where bpy = 2,2-bipyridine, 5 is 5,6-bis(dodecyloxy)-2,9-dimethyl-1,10-phenanthroline, and 6 is 5,6-bis(dodecyloxy)-1,10-phenanthroline. [ 1 ](PF 6 ) 2 is photolabile as a result of the steric strain induced by ligand 5 , but the irradiation of [ 1 ](PF 6 ) 2 in solution leads to the nonselective and slow photosubstitution of one of its three ligands, making it a poor PACT compound. On the other hand, [ 2 ](PF 6 ) 2 is an efficient and photostable PDT photosensitizer. The water-dispersible, negatively charged nanoconjugate UCNP@lipid/[ 2 ] was prepared by the encapsulation of 44 nm diameter NaYF 4 :Yb 3+ ,Tm 3+ UCNPs in a mixture of 1,2-dioleoyl- sn -glycero-3-phosphate and 1,2-dioleoyl- sn -glycero-3-phosphocholine phospholipids, cholesterol, and the amphiphilic complex [ 2 ](PF 6 ) 2 . A nonradiative energy transfer efficiency of 12% between the Tm 3+ ions in the UCNP and the Ru 2+ acceptor [ 2 ] 2+ was found using time-resolved emission spectroscopy. Under irradiation with NIR light (969 nm), UCNP@lipid/[ 2 ] was found to produce reactive oxygen species (ROS), as judged by the oxidation of the nonspecific ROS probe 2',7'-dichlorodihydrofluorescein (DCFH 2- ). Determination of the type of ROS produced was precluded by the negative surface charge of the nanoconjugate, which resulted in the electrostatic repulsion of the more specific but also negatively charged 1 O 2 probe tetrasodium 9,10-anthracenediyl-bis(methylene)dimalonate (Na 4 (ADMBMA)).

The precise detection of flammable and explosive gases and vapors remains an important issue because of the increasing demand for renewable energy sources and safety requirements in industrial processes. Metal oxides (TiO 2 , SnO 2 , ZnO, etc.) are very attractive materials for the manufacturing of chemical gas sensors. However, their gas selectivity issues and further improvement in the sensing response remain a significant challenge. The incorporation of metal oxides with two-dimensional (2D) graphene oxide (GO) is considered to be a promising approach to obtaining hybrid structures with improved gas-sensing performance. Herein, we report the development of GO and niobium-doped titanium dioxide nanotube (NT) hybrid structures with a tunable selectivity and sensing response against hydrogen gas, achieved by properly controlling the degree of reduction and concentration of GO. The effects of these parameters are systematically studied in terms of the response amplitude and selectivity. It was found that, compared to undoped titanium dioxide nanotubes, the hybrid material with an optimal concentration of reduced-GO and the introduction of niobium shows an increase in hydrogen response of about an order of magnitude and a simultaneous reduction of the response to possible interfering compounds such as carbon monoxide and acetone, thus providing enhanced selectivity. This research may provide an efficient way to enhance the chemical sensing performance of metal oxide nanomaterials.

Hydrogen evolution reaction through electrolysis holds great potential as a clean, renewable, and sustainable energy source. Platinum-based catalysts are the most efficient to catalyze and convert water into molecular hydrogen; however, their large-scale application is prevented by scarcity and cost of Pt. In this work, we propose a new ternary composite of Ag 2 S, MoS 2 , and reduced graphene oxide (RGO) flakes via a one-pot synthesis. The RGO support assists the growth of two-dimensional MoS 2 nanosheets partially covered by silver sulfides as revealed by high-resolution transmission electron microscopy. Compared with the bare MoS 2 and MoS 2 /RGO, the Ag 2 S/MoS 2 anchored on the RGO surface (the ternary system Ag 2 S/MoS 2 /RGO) demonstrated a high catalytic activity toward hydrogen evolution reaction (HER). Its superior electrochemical activity toward HER is evidenced by the positively shifted (-190 mV vs reversible hydrogen electrode (RHE)) overpotential at a current density of -10 mA/cm 2 and a small Tafel slope (56 mV/dec) compared with a bare and binary system. The Ag 2 S/MoS 2 /RGO ternary catalyst at an overpotential of -200 mV demonstrated a turnover frequency equal to 0.38 s -1 . Electrochemical impedance spectroscopy was applied to understand the charge-transfer resistance; the ternary sample shows a very small charge-transfer resistance (98 Ω) at -155 mV vs RHE. Such a large improvement can be attributed to the synergistic effect resulting from the enhanced active site density of both sulfides and to the improved electrical conductivity at the interfaces between MoS 2 and Ag 2 S. This ternary catalyst opens up further optimization strategies to design a stable and cheap catalyst for hydrogen evolution reaction, which holds great promise for the development of a clean energy landscape.

Metal oxide semiconductors are interesting for next-generation flexible and transparent electronics because of their performance and reliability. Tin dioxide (SnO 2 ) is a very promising material that has already found applications in sensing, photovoltaics, optoelectronics, and batteries. In this work, we report on electrolyte-gated, solution-processed polycrystalline SnO 2 transistors on both rigid and flexible substrates. For the transistor channel, we used both unpatterned and patterned SnO 2 films. Since decreasing the SnO 2  area in contact with the electrolyte increases the charge-carrier density, patterned transistors operate in the depletion mode, whereas unpatterned ones operate in the enhancement mode. We also fabricated flexible SnO 2 transistors that operate in the enhancement mode that can withstand moderate mechanical bending.

The energetics of the catalytic oxidation of CO on a complex metal oxide are investigated for the first time via density functional theory calculations. The catalyst, Co-doped SrTiO 3 , is modelled using periodically repeated slabs based on the SrTiO 3 (100) surface. The comparison of the energy profiles obtained for the pure host and the Co-doped material reveals the actual pathway followed by the reaction, and shows that Co doping enhances the catalytic properties of SrTiO 3 by reducing the energy cost for the formation of oxygen vacancies.

The preparation, characterization, and surface modification of upconverting lanthanide-doped hexagonal NaGdF4 nanocrystals attached to light sensitive diiodido-Pt(IV) complexes is presented. The evaluation for photoactivation and cytotoxicity of the novel carboxylated diiodido-Pt(IV) cytotoxic prodrugs by near-infrared (NIR) light (λ = 980 nm) is also reported. We attempted two different strategies for attachment of light-sensitive diiodido-Pt(IV) complexes to Yb,Er- and Yb,Tm-doped β-NaGdF4 upconverting nanoparticles (UCNPs) in order to provide nanohybrids, which offer unique opportunities for selective drug activation within the tumor cells and subsequent spatiotemporal controlled drug release by NIR-to-visible light-upconversion: (A) covalent attachment of the Pt(IV) complex via amide bond formation and (B) carboxylate exchange of oleate on the surface of the UCNPs with diiodido-Pt(IV) carboxylato complexes. Initial feasibility studies showed that NIR applied by a 980 nm laser had only a slight effect on the stability of the various diiodido-Pt(IV) complexes, but when UCNPs were present more rapid loss of the ligand-metal-charge transfer (LMCT) bands of the diiodido-Pt(IV) complexes was observed. Furthermore, Pt released from the Pt(IV) complexes platinated calf-thymus DNA (ct-DNA) more rapidly when NIR was applied compared to dark controls. Of the two attachment strategies, method A with the covalently attached diiodido-Pt(IV) carboxylates via amide bond formation proved to be the most effective method for generating UCNPs that release Pt when irradiated with NIR; the released Pt was also able to bind irreversibly to calf thymus DNA. Nonetheless, only ca. 20% of the Pt on the surface of the UCNPs was in the Pt(IV) oxidation state, the rest was Pt(II), indicating chemical reduction of the diiodido-Pt(IV) prodrug by the UCNPs. Cytotoxicity studies with the various UCNP-Pt conjugates and constructs, tested on human leukemia HL60 cells in culture, indicated a substantial increase in cytotoxicity when modified UCNPs were combined with five rounds of 30 min irradiation with NIR compared to dark controls, but NIR alone also had a significant cytotoxic effect at this duration.

The role played by the counter electrode (CE) in quantum dot sensitized solar cells (QDSSCs) is crucial: it is indeed responsible for catalyzing the regeneration of the redox electrolyte after its action to take back the oxidized light harvesters to the ground state, thus keeping the device active and stable. The activity of CE is moreover directly related to the fill factor and short circuit current through the resistance of the interface electrode-electrolyte that affects the series resistance of the cell. Despite that, too few efforts have been devoted to a comprehensive analysis of this important device component. In this work we combine an extensive electrochemical characterization of the most common materials exploited as CEs in QDSSCs (namely, Pt, Au, Cu2S obtained by brass treatment, and Cu2S deposited on conducting glass via spray) with a detailed characterization of their surface composition and morphology, aimed at systematically defining the relationship between their nature and electrocatalytic activity.

Layered multi-oxide concept was applied for fabrication of photoanodes for dye-sensitized solar cells based on ZnO and SnO2, capitalizing on the beneficial properties of each oxide. The effect of different combinations of ZnO@SnO2 layers was investigated, aimed at exploiting the high carrier mobility provided by the ZnO and the higher stability under UV irradiation pledged by SnO2. Bi-oxide photoanodes performed much better in terms of photoconversion efficiency (PCE) (4.96%) compared to bare SnO2 (1.20%) and ZnO (1.03%). Synergistic cooperation is effective for both open circuit voltage and photocurrent density: enhanced values were indeed recorded for the layered photoanode as compared with bare oxides (Voc enhanced from 0.39 V in case of bare SnO2 to 0.60 V and Jsc improved from 2.58 mA/cm(2) pertaining to single ZnO to 14.8 mA/cm(2)). Improved functional performances of the layered network were ascribable to the optimization of both high chemical capacitance (provided by the SnO2) and low recombination resistance (guaranteed by ZnO) and inhibition of back electron transfer from the SnO2 conduction band to the oxidized species of the electrolyte. Compared with previously reported results, this study testifies how a simple electrode design is powerful in enhancing the functional performances of the final device.

The encapsulation of [Eu(dbm)3phen] into functionalized mesoporous silica nanoparticles (MSN) has been carried out to study the effect of chemical environments on the photoluminescence properties of the rare-earth complex. Surface functionalization was achieved by the reaction of the silanol groups on the surface of mesoporous silica with different organosilylating agents such as (3-aminopropyl)-triethoxysilane (APTES), (3-mercaptopropyl)-trimethoxysilane (MPTMS), and ethoxytrimethylsilane (ETMS). A change in the luminescence properties of the Eu(dbm)3phen complex has been observed on its encapsulation into surface modified mesoporous silica nanoparticles. The modification of photophysical properties is attributed to the interaction of Eu(dbm)3phen with the different chemical environments in the functionalized mesoporous silica nanoparticles (MSN). The luminescence properties of the rare-earth complex in surface-modified MSN increase in the order MSN < MSN-ETMS < MSN-MPTMS < MSN-APTES. The Eu(dbm)3phen complex encapsulated in the functionalized mesoporous silica nanoparticles shows an enhanced luminescence and an increased lifetime compared to the pure rare-earth complex in the solid state and that in unmodified MSN. This implies that some interactions of the lanthanide complexes take place during their incorporation process into the organically modified mesoporous silica nanoparticles. The organically modified mesoporous silica nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR) and N2 adsorption desorption measurements. The luminescence properties of the encapsulated Eu(dbm)3phen were studied in detail. Moreover, the effect of functionalized MSNs on the structural behaviour of the Eu(dbm)3phen was investigated by solid state nuclear magnetic resonance (SSNMR) techniques using an analogous diamagnetic model complex, Y(dbm)3phen, encapsulated into functionalized MSNs. These studies indicate that the encapsulated rare-earth complex shows some interactions with the functional groups anchored on the surface of MSNs.

N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO2, TiO2 and SnO2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110-250 ns for TiO2 films and in the range of 100-170 ns for SnO2 films for PbS cores with diameters in the 3-4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.

Growth kinetics of CdSe nanocrystals generated inside three selected polymers (polyvinylpyrrolidone--PVP, polyethyleneglycol--PEG and polyvinylalcohol--PVA) are demonstrated to follow a self-catalytic path, with growth rates depending on the nature of the polymer, i.e. on the capability to activate the cadmium species present in the solution of a metal precursor. A two-step process drives the size evolution of nanocrystals and a critical diameter value can be identified at which the growth regime changes. The medium-term stability evaluation of nanocomposites indicates that, after an initial rearrangement, polymers keep stable the embedded CdSe nanocrystals.

The synthesis of strontium ferrite SrFeO(3-δ) has been explored through wet-chemistry methods in order to optimize a quick, easy and reproducible method to obtain the perovskite in pure crystalline form with a high yield. Among the three investigated synthetic paths, (i) coprecipitation of hydroxides, (ii) coprecipitation of oxalates and (iii) polyol-assisted coprecipitation, only the second one was effective in obtaining the desired perovskite modification as a single phase. The products were analyzed by means of powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), to determine the crystalline structure and the chemical composition of the sample surface, respectively, and to optimise the synthetic process. Pure samples were further characterised by means of inductively coupled plasma (ICP-AES) analysis, nitrogen adsorption, elemental analysis, temperature programmed reduction (TPR) and Mössbauer spectroscopy.

CdSe quantum dots stabilised by thiomalic acid have been synthesised by an aqueous biphasic ligand exchange reaction in air. The materials are completely water-soluble and were found to be stable over a long time. X-ray diffraction and transmission electron microscopy reveal the formation of CdSe nanocrystals with cubic structure (a=0.6077 nm; spatial group: F-43m). The average particle size is about 5 nm. Energy dispersive X-ray analysis shows that the nanocrystals are nonstoichiometric, with a Cd/Se ratio varying between 60/40 and 70/30, and indicates the presence of Cd(2+) ions at the nanocrystal surface. Diffuse reflectance infrared Fourier transform measurements suggest that thiomalic acid chelates CdSe through the thiol group and one carboxylic function, while the second COOH group is semi-free. A complex-like structure is proposed, in which thiomalic acid forms a five-membered chelate ring with the Cd(2+) ions present on the nanocrystal surface. Chelate effect accounts for the easiness of ligand exchange and is expected to additionally stabilise the nanosystem., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Octadecyl (C(18)) modified metal oxide substrates, including titania, zirconia, hafnia, and alumina, are prepared using two types of silylating reagents, n-octadecyltrihydridosilane and n-octadecyltrichlorosilane. Fourier transform infrared (FTIR) and solid-state (29)Si nuclear magnetic resonance (NMR) measurements are performed to examine the cross-linking of the silanes. Solid-state (13)C NMR spectroscopy provides information about the conformation and mobility of surface-immobilized alkyl chains. Variable temperature FTIR investigations are carried out to study the influence of the organosilane precursors and metal oxides on the conformational order of the alkyl modified systems. It is found that grafting by means of n-octadecyltrichlorosilane yields higher grafting densities than surface modification with n-octadecyltrihydridosilane. Combined pyridine adsorption and diffuse reflectance infrared Fourier transform (DRIFT) measurements are performed on the titania and hafnia substrates to evaluate potential surface heterogeneities, i.e. Lewis and Brønsted sites. Differences in the alkyl chain conformational order within the series of C(18) modified metal oxides are explained by the presence of island structures. The reduced C(18) conformational order for the samples grafted with n-octadecyltrihydridosilane is traced back to the lower grafting density which in turn points to a lower reactivity of this silylating reagent. The most striking result is the higher conformational order of the C(18) chains grafted in the present surface modified metal oxides when compared with silica-based systems. This finding is attributed to the lower porosity of the metal oxide supports along with more closely packed chains on the surface.

CeO(2)/YSZ nanocomposite powders, characterized by increasing Ce/Zr atomic ratio, were obtained by depositing, by wet impregnation, different amounts of CeO(2) on the yttria-stabilized zirconia (YSZ) surface. These powders were characterized by means of X-ray photoelectron spectroscopy, transmission electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Experimental results allow us to obtain interesting information concerning the growth mode, the morphology, and the dimensions of the CeO(2) clusters on the YSZ supporting surface. A 3-D growing mechanism was observed for the CeO(2) nanoparticles. With increasing Ce/Zr atomic ratio the CeO(2) clusters become more and more spherical. Moreover, XPS data also show the presence of Ce(III) and Ce(IV) ions at the interface supported/supporting oxides.