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Semiconductor nanoparticles proved to be an important material in the composition of modern technologies. The most important properties which shape these nanoparticles include not only their atomic composition and size, but also surface chemistry. Here, we present an environmentally friendly method of their surface modification. The proposed method does not require any possibly toxic chemicals, it relies solely on the use of water and air and an inexpensive plasma-generating system. Water treated by discharge is known to produce the so-called plasma-activated water, containing a complex mixture of water- and air-originating reactive species. We show that water treated by transient spark discharge in a vessel with restricted air flow leads to a novel chemical composition of plasma activated water, beneficial for the modification of the surface of nanoparticles. After the treatment of silicon nanoparticles with our plasma activated water, their photoluminescence quantum yield increases several times and their dispersibility in water is significantly improved. The modification is stable at laboratory conditions for at least several weeks and when the liquid is dried out from the sample. We demonstrate that the modification is caused by surface incorporation of nitrate-water complexes, which subsequently leads to a change of surface-oxide-related strain affecting the charge carrier radiative rates. The general applicability of the method is confirmed using commercial MgO and ZnO nanoparticles. Thus, the proposed method enables chemicals-free surface modification of nanoparticles and opens the door for a wide range of variations based on different liquids and discharge parameters.

We report on the growth of metal- and metal-oxide based nanoparticles (NPs) in heated polyol solutions. For this purpose, NPs are produced by the sputtering of a silver, gold, or a copper target to produce either silver, gold, or copper oxide NPs in pentaerythritol ethoxylate (PEEL) which has been annealed up to 200 °C. The objective of the annealing step is the fine modulation of their size. Thus, the evolution of the NP size and shape after thermal annealing is explained according to collision/coalescence kinetics and the affinity between the metal-/metal-oxide and PEEL molecule. Moreover, highlights of few phenomena arising from the annealing step are described such as (i) the reduction of copper oxide into copper by the polyol process and (ii) the effective formation of carbon dots after annealing at 200 °C.

Ultra-small nanoparticles of a size smaller than or comparable to cell membrane pores (1–5 nm) offer significant potential in the field of biomedicine. This study presents a systematic in vitro investigation of fundamental bio-chemical interactions of such ultra-small hydrogenated and oxidized detonation nanodiamonds (DNDs) with biomolecules and human cells. We apply mass spectrometry methods (LC-MS/MS) for the qualitative and quantitative analysis of the protein corona as a function of the surface chemistry and size of DNDs. We observe that protein interactions with DNDs are more related to their surface chemistry (H/O-termination) rather than size. Bioinformatics characterization of the identified proteins points to the strong influence of electrostatic interaction between proteins and DNDs depending on their termination. Such specific interaction leads to formation of different protein corona on 2 nm DNDs, which influences also interaction with cells including different level of cytotoxicity.

Here we present a one-step synthesis that provides silicon nanocrystals with a thin shell composed of a ceramic-like carbonyl based compound, embedded in a porous organosilicon film. The silicon nanocrystals were synthesised from hydrogen silsesquioxane molecules, modified with organic molecules containing carbonyl groups, which were annealed at 1000 °C in a slightly reducing 5% H2 : 95% Ar atmosphere. The organic character of the shell was preserved after annealing due to trapping of organic molecules inside the HSQ-derived oxide matrix that forms during the annealing. The individual silicon nanocrystals, studied by single dot spectroscopy, exhibited a significantly narrower emission peak at room temperature (lowest linewidth ∼ 17 meV) compared to silicon nanocrystals embedded in a silicon oxide shell (150 meV). Their emission linewidths are even significantly narrower than those of single CdSe quantum dots (>50 meV). It is hypothesized that the Si-core–thin shell structure of the nanoparticle is responsible for the unique optical properties. Its formation within one synthesis step opens new opportunities for silicon-based quantum dots. The luminescence from the produced nanocrystals covers a broad spectral range from 530–720 nm (1.7–2.3 eV) suggesting strong application potential for solar cells and LEDs, following the development of a suitable mass-fabrication protocol.

Background Aggregation of the neuronal protein α-synuclein into amyloid fibrils is a hallmark of Parkinson's disease. The propensity of α-synuclein to aggregate increases with the protein concentration. For the development of efficient inhibitors of α-synuclein aggregation, it is important to know the critical concentration of aggregation (the concentration of monomeric protein, below which the protein does not aggregate). Methods We performed in vitro aggregation studies of α-synuclein at low concentrations (0.11–20 μM). Aggregation kinetics was measured by ThT fluorescence. Obtained aggregates were characterized using CD-spectroscopy, fluorescent spectroscopy, dynamic light scattering and AFM imaging. Results Monomeric α-synuclein at concentrations 0.45 μM and above was able to bind to fibril ends resulting in fibril growth. At the protein concentrations below 0.4 μM, monomers did not fibrillize, and fibrils disaggregated. In the absence of seeds, fibrils were formed only at monomer concentrations higher than 10 μM. At low micromolar concentrations, we observed formation of prefibrillar amyloid aggregates, which are able to induce fibril formation in α-synuclein solutions of high concentrations. Conclusions The critical concentration of α-synuclein fibril growth is ~0.4 μM. Prefibrillar amyloid aggregates appear at concentrations between 0.45 and 3 μM and are an intermediate state between monomers and fibrils. Although morphologically different from fibrils, prefibrillar aggregates have similar properties to those of fibrils. General significance We determined the critical concentration of α-synuclein fibril growth. We showed that fibrils can grow at much lower monomer concentrations than that required for de novo fibril formation. We characterized a prefibrillar intermediate species formed upon aggregation of α-synuclein at low micromolar concentration.

The great application potential of photoluminescent silicon nanocrystals, especially in biomedicine, is significantly reduced due to their limited radiative rate. One of the possible ways to overcome this limitation is enhancing the luminescence by localized plasmons of metallic nanostructures. We report an optimized fabrication of gold nanorod – silicon nanocrystal core–shell nanoparticles with the silica shell as a tunable spacer. The unprecedented structural quality and homogeneity of our hybrid nanoparticles allows for detailed analysis of their luminescence. A strong correlation between dark field scattering and luminescence spectra is shown on a single particle level, indicating a dominant role of the longitudinal plasmonic band in luminescence enhancement. The spacer thickness dependence of photoluminescence intensity enhancement is investigated using a combination of experimental measurements and numerical simulations. An optimal separation distance of 5 nm is found, yielding a 7.2× enhancement of the luminescence intensity. This result is mainly attributed to an increased quantum yield resulting from the Purcell enhanced radiative rate in the nanocrystals. The ease of fabrication, low cost, long-term stability and great emission properties of the hybrid nanoparticles make them a great candidate for bio-imaging or even targeted cancer treatment.

Effective methods for the synthesis of high-purity nanoparticles (NPs) have been extensively studied for a few decades. Among others, cold plasma-based sputtering metals onto a liquid substrate appears to be a very promising technique for the synthesis of high-purity NPs. The process enables the production of very small NPs without using any toxic reagents and complex chemical synthesis routes, and enables the synthesis of alloy NPs which can be the first step towards the formation of porous NPs. In this paper, the synthesis of gold-copper alloy NPs has been performed by co-sputtering gold and copper targets over pentaerythritol ethoxylate. The resulting solutions contain a mixture of gold, copper oxide, and alloy NPs having a radius of few angstroms. The annealing of these NPs, inside the solution, has been performed in order to increase their size and further induce the dealloying of the Au-Cu NPs. The resulting NPs exhibit either a nanoporous structure or are self-organized in an agglomerate of small NPs.

Discussion on the synthesis of nanostructures

Made available in DSpace on 2020-12-12T02:36:22Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-05-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Herein we report the synthesis of highly-doped silver nanocluster in fluorophosphate glasses through the melting-quenching method in order to achieve sensitization with Tm3+ and Mn2+ ions. Blue and red emission belonging to Tm3+ (470 to 490 nm) and Mn2+ (550 to 750 nm) ions could be obtained via non-resonant excitation of Tm3+ and Mn2+. Slight decrease of the fluorescence decay times confirmed an energy transfer as a possible mechanism to explain the Tm3+ and Mn2+ emission. The composition of 5 mol% of AgNO3, 0.4 mol% of Tm2O3 and 0.2 mol% of MnF2 in our sample leads to distance between donor (silver nanoclusters) and acceptor (Tm3+-Mn2+) as short as 11 Å, which suggests that the main mechanism for blue and red emission from Tm3+ and Mn2+ is Förster Resonance Energy Transfer (FRET). The results presented here show that the studied material has potential application for multicolor generation as luminophore in white light emitting diodes (W-LED). Institute of Chemistry - São Paulo State University - UNESP Department of Chemical Physics and Optics Faculty of Mathematics and Physics Charles University, Ke Karlovu 3 Department of Chemistry and Chemical Engineering Chalmers University of Technology Institute of Chemistry - São Paulo State University - UNESP FAPESP: #2013/07793-6 FAPESP: #2016/16343-2 FAPESP: #2016/16900-9

Silicon nanoparticles as luminescent sensors

We employ time-dependent photoluminescence (PL) and steady-state PL excitation (PLE) measurements to study the size-dependent optical properties of ultrasmall silicon carbide (SiC) nanoparticles (N...

Misfolding of the protein α-synuclein (αSyn) into amyloid fibrils plays a central role in the development of Parkinson's disease. Most approaches for the inhibition of αSyn fibril formation are based on stabilizing the native monomeric form of the protein or destabilizing the fibrillized misfolded form. They require high concentrations of inhibitor and therefore cannot be easily used for therapies. In this work, we designed an inhibitor (Inh-β) that selectively binds the growing ends of αSyn fibrils and creates steric hindrance for the binding of monomeric αSyn. This approach permits the inhibition of fibril formation at Inh-β concentrations (IC50 =850 nm) much lower than the concentration of monomeric αSyn. We studied its kinetic mechanism in vitro and identified the reactions that limit inhibition efficiency. It is shown that blocking of αSyn fibril ends is an effective approach to inhibiting fibril growth and provides insights for the development of effective inhibitors of αSyn aggregation.

Aggregation of neuronal protein α-synuclein leads to the formation of amyloid fibrils, which are associated with the development of Parkinson's disease. The mechanism of α-synuclein pathology is not fully understood and is a subject of active research in the field. To tackle this problem, the fusions of fluorescent proteins to α-synuclein C-terminus are often used in cellular and animal studies. The effects induced by such α-synuclein sequence extension on α-synuclein aggregation propensity are, however, not systematically examined despite the evidence that the negatively charged C-terminus plays a critical role in the regulation of α-synuclein aggregation. In this work, we investigated how the charge and length variations of the C-terminus affect the aggregation propensity of α-synuclein. To address these questions, we prepared mutants of α-synuclein carrying additional moieties of different charge and length at the protein C-terminus. We determined the rates of two different aggregation stages (primary nucleation and elongation) based on a thioflavin T kinetic assay. We observed that all mutants bearing neutrally charged moieties of different length fibrilized slower than wild-type α-synuclein. The primary nucleation and elongation rates strongly decreased with increase of the C-terminal extension length. Meanwhile, charge variation of the C-terminus significantly changed the rate of α-synuclein nucleation, but did not markedly affect the rate of fibril elongation. Our data demonstrate that both the charge and length of the C-terminus play an important role at the stage of initial fibril formation, but the stage of fibril elongation is affected mainly by the length of C-terminal extension. In addition, our results suggest that there are at least two steps of incorporation of α-synuclein monomers into the amyloid fibril: namely, the initial monomer binding to the fibril end (charge-dependent, relatively fast), and the subsequent conformational change of the protein (charge-independent, relatively slow, and thus the rate-limiting step).

Bacteriochlorophyll c (BChl c) is a naturally occurring pigment which, as a monomer, exhibits strong absorption in the red region (600–700 nm), where the dyes used in the most efficient solar cells absorb only weakly. Herein, we investigate the plasmonic enhancement of photoconversion efficiencies in BChl c sensitized solar cells using gold nanoparticles of different morphologies. Using cyclic voltammetry, a favourable band offset (~0.72 eV) between the lowest unoccupied molecular orbital of BChl c and the conduction band edge of titania photoanode was established. Further, gold nanorods with a localized surface plasmon resonance (SPR) frequency overlapping the absorption maxima of BChl c at ~670 nm were used, and compared with gold nanospheres with a SPR maximum in a region (~525 nm) where BChl c has no absorption. Gold nanorod incorporated solar cells displayed the highest photoconversion efficiency with more than 30% increase in photocurrent, compared to devices containing nanospheres and only BChl c. The results are explained using boundary element method simulations, which show a significantly enhanced scattering cross-section and local electric field in the vicinity of gold nanorods compared to the nanospheres. Electrochemical impedance spectroscopy studies indicate reduced charge transport resistance in both gold nanorod and nanosphere incorporated devices.

Silicon (Si) nanostructures allow for the expansion of the application spectrum of this important semiconductor material with respect to the fields of optoelectronics and photonics. At the same time, the significant potential of Si quantum dots (SiQDs) has been revealed in terms of their potential application in the areas of biology and medicine due to their biocompatibility, low toxicity and natural biodegradability, unlike currently used semiconductor quantum dots. As far as this study is concerned, SiQDs co-doped with boron and phosphorus were used for the in vitro evaluation of their cytotoxicity in human osteoblasts. Two chemically identical types of SiQD differing in terms of their size and photoluminescence (PL) were studied. They both display long-lasting dispersion in methanol and even in aqueous media as well as PL which is not sensitive either to changes in the environment or surface modifications. Our experiments revealed significant differences between the two types of SiQD tested in regard to their behavior in a cell culture environment depending on increasing concentration (25–125 μg ml−1) and cultivation conditions (the presence or absence of proteins from the fetal bovine serum – a component of the cultivation medium). A detailed description of their optical parameters and the evaluation of zeta potential enhance the understanding of the complexities of the in vitro results obtained.

Various porous solid sorbents in the form of powder or monoliths have been developed over the last years, as a promising solution for reducing CO2 emissions. Although powder sorbents, due to higher porosities and efficient mass transport, exhibit higher capacities compared with monoliths, several factors limit their suitability for practical application. The most prominent is their low bulk density, which makes them difficult to handle and poses health risks due to dust inhalation. In this work, we prepared robust hierarchically porous carbon-based monoliths based on a simple three-step approach with the focus on combining efficient CO2 adsorption and transport with easy handling for practical applications. The approach is based on incorporation of polystyrene nanoparticles (PS NPs) and expanded graphite (EG) into a nitrogen-rich precursor, which is polymerized to form 3D monoliths. Incorporation of thermally unstable PS NPs or thermally stable EG enables us to control the formation of macropores during a precarbonization step, while variation of KOH concentration and mixing intensity during a subsequent activation step controls the formation of micropores. The resulting hierarchically porous monoliths with high nitrogen contents exhibited CO2 uptake capacities reaching 6.52 mmol g−1 at 273.15 K and 1 bar, which is among the highest reported for porous carbon monoliths. In addition, the materials also exhibited good reversibility of CO2 adsorption over several cycles with simple regeneration under mild conditions. Considering the high CO2 capture performance together with improvements in sorbent properties such as easy handling and reusability, the presented sorbents are promising candidates for practical applications.

Biexciton emission from individual silicon nanocrystals was detected at room temperature by time-resolved, single-particle luminescence measurements. The efficiency of this process, however, was found to be very low, about 10–20 times less than the single exciton emission efficiency. It decreases even further at low temperature, explaining the lack of biexciton emission line observations in silicon nanocrystal single-dot spectroscopy under high excitation. The poor efficiency of the biexciton emission is attributed to the dominant nonradiative Auger process. Corresponding measured biexciton decay times then represent Auger lifetimes, and the values obtained here, from tens to hundreds of nanoseconds, reveal strong dot-to-dot variations, while the range compares well with recent calculations taking into account the resonant nature of the Auger process in semiconductor nanocrystals.

The luminescence linewidth of individual silicon nanocrystals was characterized by single-dot spectroscopy, and an ultranarrow linewidth of similar to 200 mu eV at 10 K was found. This value is, in fact, limited by system resolution and represents only the upper limit of the homogeneous linewidth. In addition, the effect of the matrix was investigated for nanocrystals coated with organic ligands, embedded in silicon dioxide, as well as for nanocrystals with only a thin passivating layer. It was found that, depending on the matrix, the room-temperature bandwidth may vary by an order of magnitude, where values as small as similar to 12 meV (similar to 5 nm) at 300 K were detected for nanocrystals with a thin passivation. The observed values for silicon nanocrystals are similar and even surpass some of those for direct-band-gap quantum dots. The narrow linewidth at room temperature enables the use of silicon nanocrystals for nontoxic narrow-band labeling of biomolecules and for application as phosphors in white-light-emitting devices. QC 20141114

The number of newly developed nanomaterials is steadily increasing but only a few are suitable for applications in biology. These nanomaterials are often made from harmful compounds and there is no convenient technique to remove them from the body after application. This study is focused on silicon nanocrystals and nanodiamonds, which are two promising nanomaterials for bio-applications. Silicon nanocrystals (Si-NCs) are exceptional since they provide several desired properties: low cytotoxicity, suitability for chemical activation, efficient photoluminescence, and bio-degradability. All these parameters promote application of Si-NCs in living organisms and even human medicine. Nanodiamonds (NDs), on the other hand, are non-biodegradable which limits their use to mostly long term in vitro studies. However, when using these nanomaterials one needs to address the effect of accumulation and aggregation of such materials in cells and how it contributes to the overall cytotoxicity. Here, we present studies on the interaction of two promising nanomaterials Si-NCs and NDs with actin structure of mammalian cells, evaluation of their cytotoxicity by various methods, and observation of single nanoparticle luminescence spectra within living cells. According to our results Si-NCs are more promising for application in nanomedicine compared to NDs.

We have prepared colloidal solutions of clusters composed from porous silicon nanoparticles in methanol, water and phosphate-buffered saline (PBS). Even if the size of the nanoclusters is between 60 and 500 nm, due to their highly porous “cauliflower”-like structure, the porous silicon nanoparticles are composed of interconnected nanocrystals having around 2.5 nm in size and showing strong visible luminescence in the orange-red spectral region (centred at 600–700 nm). Hydrophilic behaviour and good solubility of the nanoclusters in water and water-based solutions were obtained by adding hydrogen peroxide into the etching solution during preparation and 16 min long after-bath in hydrogen peroxide. By simple filtration of the solutions with syringe filters, we have extracted smaller nanoclusters with sizes of approx. 60–70 nm; however, these nanoclusters in water and PBS solution (pH neutral) are prone to agglomeration, as was confirmed by zeta potential measurements. When the samples were left at ambient conditions for several weeks, the typical nanocluster size increased to approx. 330–400 nm and then remained stable. However, both freshly filtered and aged samples (with agglomerated porous silicon nanoparticles) of porous silicon in water and PBS solutions can be further used for biological studies or as luminescent markers in living cells.

The microscopic origin of the bright nanosecond blue-green photoluminescence (PL), frequently reported for synthesized organically terminated Si quantum dots (Si-QDs), has not been fully resolved, hampering potential applications of this interesting material. Here a comprehensive study of the PL from alkyl-terminated Si-QDs of 2-3 nm size, prepared by wet chemical synthesis is reported. Results obtained on the ensemble and those from the single nano-object level are compared, and they provide conclusive evidence that efficient and tunable emission arises due to radiative recombination of electron-hole pairs confined in the Si-QDs. This understanding paves the way towards applications of chemical synthesis for the development of Si-QDs with tunable sizes and bandgaps.

Porous silicon and similar materials, like micro- and nanocrystalline silicon, are nowadays studied not only in physical research (e.g. optical gain studies, electro-optical devices, solar energy conversion), but they are very promising also in biological research as fluorescent labels, biological sensors, drug delivery systems or scaffold for various tissues. We are giving an overview of various approaches of preparation of micro- and nanocrystalline silicon and current studies of applications with main focus on biology and medicine. In contrast to other nanomaterials used in biological studies (e.g. carbon nanotubes, fullerenes, cadmium containing quantum dots) silicon based nanomaterials show very good biocompatibility and low cytotoxicity. Therefore, these materials have potential to become powerful tools for in vivo investigation of life processes on subcellular and molecular level. Our group concentrates on developing of gentle florescent label based on porous silicon for single molecule detection in the cell. (© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Pulverized porous silicon, fabricated by the electrochemical etching of silicon wafers, is used to prepare colloidal suspensions of silicon nanocrystals (ncSi) in various organic solvents including xylene. The porous silicon powder aggregates into large clumps, making the suspensions scatter light strongly. The suspensions are subsequently gently stirred in optical cuvettes for a period of weeks, in air and at room temperature. The temporal development of spatially resolved photoluminescence emission spectra in the cuvette with xylene+ncSi is monitored at regular intervals. The spectra show a slow evolution from the original orange color through blue to a yellow one. After approximately 5 weeks, a yellow emitting (∼560nm) transparent colloidal solution can be extracted from the cuvette, with a high and stable photoluminescence yield (∼20%).

Among the various properties of visual warning signals, colour seems to be especially important for avian predators. We tested the role of particular colours of an aposematic insect (firebug, Pyrrhocoris apterus; Heteroptera: Pyrrhocoridae) in unlearned avoidance, learning, memory and generalization of a naive avian predator (great tit, Parus major). The wild type of the firebug is aposematic, red-and-black, and its colour mutants (white, yellow, orange) retain the same black pattern; the bug can be made artificially nonaposematic (painted uniformly brown). Wild-caught great tits avoid the firebug depending on colour, and their reaction to variously coloured prey is a result of avoidance learning and may vary according to their experience. We trained naive great tits to avoid firebugs of different colours, and then gave some birds a memory test with firebugs of the same colour and other birds a generalization test with firebugs of a different colour. Naive, hand-reared great tits showed no initial avoidance and attacked firebugs irrespective of colour. They learned to avoid all the colour forms at a similar rate. The generalization was asymmetric: birds that learned to avoid red firebugs did not generalize their experience to yellow or white mutants whereas birds that learned to avoid yellow mutants generalized their experience to red firebugs. The red colour thus represents a more effective signal than the yellow; predation by birds could have played a crucial role in selectively favoured evolutionary transitions from yellow to red coloration in pyrrhocorids.

Spectra of individual silicon nanocrystals within porous Si grains are studied by the wide-field imaging microspectroscopy and their ON-OFF, blinking is detected by the confocal single-photon-counting microscopy. Observed spectral and blinking properties comprise all features reported before in differently prepared single Si nanocrystals (SiNCs). Former apparently contradictory results are shown to be due to different experimental conditions. When the effect of dark periods (OFF switching) is removed the common ultimate photoluminescence properties Of SiO2 passivated SiNCs are found, namely the quantum efficiency (QE) of about 10-20% up to the pumping rate corresponding to one exciton average excitation per quantum dot. At higher pump rates the QE is slowly decreasing as the 0.7th power of excitation. This is most likely due to Auger recombination which, however, seems to be weakened compared with measurements of nanocrystal assemblies. We conclude that SiNCs may be pumped above one exciton occupancy to yield a higher light emission, being advantageous for applications.

Boron (B) and phosphorous (P) codoped silicon quantum dots (Si QDs) are dispersible in polar solvents without organic ligands, and exhibit size controllable photoluminescence (PL) from 0.85 to 1.85 eV due to the electronic transitions between the donor and the acceptor states. We study the PL spectra of the codoped Si QDs at room temperature and at 77 K. We show that the broad PL band of codoped colloidal Si QDs (full width at half maximum is over 400 meV) is composed of narrower PL bands of individual QDs with different PL energies. We also show that the PL linewidth of individual codoped Si QDs is almost twice as large as those of undoped Si QDs. In contrast to the significant narrowing of the PL linewidth of undoped Si QDs at low temperatures, that of codoped Si QDs is almost independent of the temperature except for a few very small QDs. These results suggest that a large number of B and P are doped in a QD and there are a number of non-identical luminescence centers in each QD.

Silicon nanocrystals are an extensively studied light-emitting material due to their inherent biocompatibility and compatibility with silicon-based technology. Although they might seem to fall behind their rival, namely, direct band gap based semiconductor nanocrystals, when it comes to the emission of light, room for improvement still lies in the exploitation of various surface passivations. In this paper, we report on an original way, taking place at room temperature and ambient pressure, to replace the silicon oxide shell of luminescent Si nanocrystals with capping involving organic residues. The modification of surface passivation is evidenced by both Fourier transform infrared spectroscopy and nuclear magnetic resonance measurements. In addition, single-nanocrystal spectroscopy reveals the occurrence of a systematic fine structure in the emission single spectra, which is connected with an intrinsic property of small nanocrystals since a very similar structure has recently been observed in specially passivated semiconductor CdZnSe nanoparticles. The organic capping also dramatically changes optical properties of Si nanocrystals (resulting ensemble photoluminescence quantum efficiency 20%, does not deteriorate, radiative lifetime 10 ns at 550 nm at room temperature). Optically clear colloidal dispersion of these nanocrystals thus exhibits properties fully comparable with direct band gap semiconductor nanoparticles.

The presented work is aimed at the development of nontoxic nanocrystalline silicon fluorescence labels, biodegradable in living body and long-term stable, and of fluorescent nanodiamonds mainly for in vitro use. These novel fluorescence labels could be very good substitutes for commercially used quantum dots (e.g. cadmium compound quantum dots) which can be toxic according to the latest results. In this work, manufacturing of porous nanocrystalline silicon (por-Si) is described, several basic optical properties of por-Si are presented and the influence of Si nanocrystals, nanodiamonds, and milled silicon on the growth of a cell culture of L929 mouse fibroblast and HeLa cells is compared. Bio-interaction of nanoparticles was studied by optical transmission microscopy, time-lapse microphotography of cell culture evolution, fluorescence microscopy, fluorescence microspectroscopy, and scanning electron microscopy. The size and shape of nanocrystals were determined using atomic force microscopy (AFM).

The absolute photoluminescence (PL) quantum yield (QY) of oleic acid-capped colloidal PbS quantum dots (QDs) in toluene is thoroughly investigated as function of QD size, concentration, excitation photon energy, and conditions of storage. We observed anomalous decrease of QY with decreasing concentration for highly diluted suspensions. The ligand desorption and QD-oxidation are demonstrated to be responsible for this phenomenon. Excess of oleic acid in suspensions makes the QY values concentration-independent over the entire reabsorption-free range. The PL emission is shown to be dominated by surface-related recombinations with some contribution from QD-core transitions. We demonstrate that QD colloidal suspension stability improves with increasing the concentration and size of PbS QDs.

Colloidal suspensions of small silicon nanoparticles (diameter around 2nm) with fast and efficient ultraviolet-blue photoluminescence (PL) band are fabricated by enhanced electrochemical etching of Si wafers. The detailed study of photoluminescence excitation spectra in a wide range of excitation photon energies (270-420nm) reveals specific behavior of the Stokes shift of the fast PL band that agrees well with theoretical calculation of optical transitions in small silicon nanocrystals and is distinct from emission of silicon dioxide defects.

The commercially available semiconductor quantum dots have been proven to be slightly to significantly toxic by recent publications depending on the chemical composition. We are developing new non-toxic fluorescent labels based on (i) nanocrystalline silicon, suitable for in vivo studies due to their biodegrability, and on (ii) nanodiamonds, intended mainly for in vitro use due to their long-term stability and nondegradilibity.