Transition metal dichalcogenide nanospheres for high-refractive-index nanophotonics and biomedical theranostics.

Recent developments in the area of resonant dielectric nanostructures have created attractive opportunities for concentrating and manipulating light at the nanoscale and the establishment of the new exciting field of all-dielectric nanophotonics. Transition metal dichalcogenides (TMDCs) with nanopatterned surfaces are especially promising for these tasks. Still, the fabrication of these structures requires sophisticated lithographic processes, drastically complicating application prospects. To bridge this gap and broaden the application scope of TMDC nanomaterials, we report here femtosecond laser-ablative fabrication of water-dispersed spherical TMDC (MoS2 and WS2) nanoparticles (NPs) of variable size (5 to 250 nm). Such NPs demonstrate exciting optical and electronic properties inherited from TMDC crystals, due to preserved crystalline structure, which offers a unique combination of pronounced excitonic response and high refractive index value, making possible a strong concentration of electromagnetic field in the NPs. Furthermore, such NPs offer additional tunability due to hybridization between the Mie and excitonic resonances. Such properties bring to life a number of nontrivial effects, including enhanced photoabsorption and photothermal conversion. As an illustration, we demonstrate that the NPs exhibit a very strong photothermal response, much exceeding that of conventional dielectric nanoresonators based on Si. Being in a mobile colloidal state and exhibiting superior optical properties compared to other dielectric resonant structures, the synthesized TMDC NPs offer opportunities for the development of next-generation nanophotonic and nanotheranostic platforms, including photothermal therapy and multimodal bioimaging.

TiS3 Nanoribbons: A Novel Material for Ultra-Sensitive Photodetection across Extreme Temperature Ranges.

Photodetectors that can operate over a wide range of temperatures, from cryogenic to elevated temperatures, are crucial for a variety of modern scientific fields, including aerospace, high-energy science, and astro-particle science. In this study, we investigate the temperature-dependent photodetection properties of titanium trisulfide (TiS3)- in order to develop high-performance photodetectors that can operate across a wide range of temperatures (77 K-543 K). We fabricate a solid-state photodetector using the dielectrophoresis technique, which demonstrates a quick response (response/recovery time ~0.093 s) and high performance over a wide range of temperatures. Specifically, the photodetector exhibits a very high photocurrent (6.95 × 10-5 A), photoresponsivity (1.624 × 108 A/W), quantum efficiency (3.3 × 108 A/W·nm), and detectivity (4.328 × 1015 Jones) for a 617 nm wavelength of light with a very weak intensity (~1.0 × 10-5 W/cm2). The developed photodetector also shows a very high device ON/OFF ratio (~32). Prior to fabrication, the TiS3 nanoribbons were synthesized using the chemical vapor technique and characterized according to their morphology, structure, stability, and electronic and optoelectronic properties; this was performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a UV-Visible-NIR spectrophotometer. We anticipate that this novel solid-state photodetector will have broad applications in modern optoelectronic devices.

Nanoribbon Biosensor-Based Detection of microRNA Markers of Prostate Cancer.

Prostate cancer (PC) is one of the major causes of death among elderly men. PC is often diagnosed later in progression due to asymptomatic early stages. Early detection of PC is thus crucial for effective PC treatment. The aim of this study is the simultaneous highly sensitive detection of a palette of PC-associated microRNAs (miRNAs) in human plasma samples. With this aim, a nanoribbon biosensor system based on "silicon-on-insulator" structures (SOI-NR biosensor) has been employed. In order to provide biospecific detection of the target miRNAs, the surface of individual nanoribbons has been sensitized with DNA oligonucleotide probes (oDNA probes) complementary to the target miRNAs. The lowest concentration of nucleic acids, detectable with our biosensor, has been found to be 1.1 × 10-17 M. The successful detection of target miRNAs, isolated from real plasma samples of PC patients, has also been demonstrated. We believe that the development of highly sensitive nanotechnology-based biosensors for the detection of PC markers is a step towards personalized medicine.

Charge transport in the spatially correlated exponential random energy landscape: effect of the nonpositive correlation function.

Charge transport in amorphous semiconductors having spatially correlated exponential density of states (DOS) has been considered for the arbitrary behavior of the correlation function of random energies. Average carrier velocity is exactly calculated for the quasi-equilibrium (nondispersive) transport regime. For the symmetric exponential DOS with exponential tails for low and high energies and nonpositive correlation function the temperature of the transition to the dispersive transport regime depends on correlation properties and becomes greater than the traditional estimation based on the DOS decay energy kT = U0. Another new feature of the transport in the landscape having nonpositive correlation function is the decrease of the mobility with the field in the low field region and development of the universal mobility field dependence for stronger fields.

Two-dimensional bimolecular recombination in amorphous organic semiconductors.

We consider the two-dimensional bimolecular recombination of charge carriers in amorphous organic semiconductors having the lamellar structure. We calculate the dependence of the effective recombination rate constant on the carrier density taking into account the correlated nature of the energetic disorder typical for organic semiconductors. The resulting recombination kinetics demonstrates a very rich variety of behaviors depending on the correlation properties of the particular semiconductor and relevant charge density range.

Effect of Multiplicity Fluctuation in Cobalt Ions on Crystal Structure, Magnetic and Electrical Properties of NdCoO3 and SmCoO3.

The structural, magnetic, electrical, and dilatation properties of the rare-earth NdCoO3 and SmCoO3 cobaltites were investigated. Their comparative analysis was carried out and the effect of multiplicity fluctuations on physical properties of the studied cobaltites was considered. Correlations between the spin state change of cobalt ions and the temperature dependence anomalies of the lattice parameters, magnetic susceptibility, volume thermal expansion coefficient, and electrical resistance have been revealed. A comparison of the results with well-studied GdCoO3 allows one to single out both the general tendencies inherent in all rare-earth cobaltites taking into account the lanthanide contraction and peculiar properties of the samples containing Nd and Sm.

99mTc-MIBI scintimammography and digital mammography in the diagnosis of multicentric breast cancer.

OBJECTIVE: To compare diagnostic accuracy of scintimammography (SMG) and digital mammography (DS) in the diagnosis of multicentric breast cancer. SUBJECTS AND METHODS: Three hundred and sixty seven women with histologically confirmed breast cancer were included in this analysis. All patients were candidates for conservative breast surgery and had cT1-3N0-1 stage of disease. Scintimammography was performed in prone position 5-10min after intravenous injection of 740MBq of technetium-99m-methoxy-isobtyl-isonitrile (99mTc-MIBI) with acquisition time of 10min for every lateral and anterior projection. Digital mammography was done in all women according to a standard clinical protocol. Final diagnosis was established by histopathology. Multicentric breast cancer was defined as 2 or more distinct invasive tumors located in more than one quadrant or additional lesions from the primary tumor of more than 4cm in size. RESULTS: According to histopathological examinations multicentric breast cancer was diagnosed in 47 of 367 (12.8%) patients. Scintimammography was more effective than mammography in detecting multicentric breast cancer: sensitivity: 83.0% vs 40.4% (P<0.001), specificity: 97.8% vs 95.3% (P=0.4), accuracy: 95.9% vs 88.3% (P<0.001), positive and negative predictive values: 84.8% vs 55.9% (P=0.004) and 97.5% vs 91.6% (P<0.001), respectively. Combination of DM and SMG was characterized by increased sensitivity (93.6%), worse specificity (93.4%), accuracy (93.4%) and worse predictive value (67.7%) as compared to only SMG. CONCLUSION: Scintimammography was significantly much better by all statistical parameters than DM in the detection of multicentric breast cancer. High positive predictive value of scintimammography (84.8%) advocates it as a tool for surgery and radiotherapy planning.

SPECT-CT localization of axillary sentinel lymph nodes for radiotherapy of early breast cancer.

PURPOSE: To evaluate the opportunities of single photon emission tomography/computerized tomography (SPECT-CT) for localization of axillary sentinel lymph nodes (ASLNs) and subsequent radiotherapy planning in women with early breast cancer. MATERIAL AND METHODS: Individual topography of ASLN was determined in 151 women with clinical T1-2N0M0 breast cancer. SPECT-CT visualization of ASLNs was initiated 120 min after intra-peritumoral injection of 99mTc-radiocolloids. Doses absorbed by virtual ASLNs after the whole breast irradiation with standard and extended tangential fields were calculated on a treatment planning station. RESULTS: SPECT-CT demonstrated a large variability of ASLN localization. They were detected in the central subgroup in 94 (61%) patients, in pectoral - in 77 (51%), and in interpectoral - in 4 (3%) patients. Sentinel lymph nodes "lying on the chest" were revealed in 35 (23%) cases.We found that with standard tangential fields coverage of ASLNs was obtained only in 20% of evaluated women. Extended tangential fields can effectively irradiate ASLNs localized in all axillary sub-regions with the exception of ASLNs "lying on the chest". CONCLUSION: SPECT-CT mapping of ASLNs in women with cT1-2N0M0 breast cancer reveals their variable localization. This information can be important for planning of radiation treatment in women that underwent breast conserving surgery without an axillary surgery.

Direct Amplitude-Phase Near-Field Observation of Higher-Order Anapole States.

Anapole states associated with the resonant suppression of electric-dipole scattering exhibit minimized extinction and maximized storage of electromagnetic energy inside a particle. Using numerical simulations, optical extinction spectroscopy, and amplitude-phase near-field mapping of silicon dielectric disks, we demonstrate high-order anapole states in the near-infrared wavelength range (900-1700 nm). We develop the procedure for unambiguously identifying anapole states by monitoring the normal component of the electric near-field and experimentally detect the first two anapole states as verified by far-field extinction spectroscopy and confirmed with the numerical simulations. We demonstrate that higher-order anapole states possess stronger energy concentration and narrower resonances, a remarkable feature that is advantageous for their applications in metasurfaces and nanophotonics components, such as nonlinear higher-harmonic generators and nanoscale lasers.

Lymph flow guided irradiation of regional lymph nodes in patients with cervical cancer: Preliminary analysis of scintigraphic data.

PURPOSE: To evaluate patterns of lymph flow from primary lesions in patients with cervical cancer and to determine how useful for radiotherapy planning this information can be. MATERIALS AND METHODS: SPECT-CT visualization of sentinel (SLN) lymph nodes (LNs) was performed in 36 primary patients with IB-IIB cervical cancer. The acquisition started 120-240 min after 4 peritumoral injections of 99mTc-radiocolloids (150-300 MBq in 0.4-1 ml). We determined localization of LN with uptake of radiocolloids, type of lymph flow (mono-, bi-lateral) and lymph flow patterns (supraureteral paracervical, infraureteral paracervical and directly to para-aortic LNs). RESULTS: SLNs were visualized in 31 of 36 women. Bilateral lymph-flow was detected in 22 (71%), monolateral - in the other 9 (29%) cases. The distribution of SLNs was as follows: external iliac - 64.5%, internal iliac - 54.8%, obturator - 32.2%, common iliac - 35.5% and pre-sacral 3.2%. Para-aortic LNs were visualized in 5 (16.1%) patients. The supraureteral paracervical pattern of lymph flow was identified in 22, infraureteral paracervical - in 4 and their combination - in the other 5 women. CONCLUSION: Visualization of an individual pattern of lymph flow from primary cervical cancer can be considered as a promising tool for optimization of the volume of irradiated regional LNs.

Highly Stable Monocrystalline Silver Clusters for Plasmonic Applications.

Plasmonic sensor configurations utilizing localized plasmon resonances in silver nanostructures typically suffer from the rapid degradation of silver under ambient atmospheric conditions. In this work, we report on the fabrication and detailed characterization of ensembles of monocrystalline silver nanoparticles (NPs), which exhibit a long-term stability of optical properties under ambient conditions without any protective treatments. Ensembles with different densities (surface coverages) of size-selected NPs (mean diameters of 12.5 and 24 nm) on quartz substrates are fabricated using the cluster-beam technique and characterized by linear spectroscopy, two-photon-excited photoluminescence, surface-enhanced Raman scattering microscopy, and transmission electron, helium ion, and atomic force microscopies. It is found that the fabricated ensembles of monocrystalline silver NPs preserve their plasmonic properties (monitored with optical spectroscopy) and strong field enhancements (revealed by surface-enhanced Raman spectroscopy) at least 5 times longer as compared to chemically synthesized silver NPs with similar sizes. The obtained results are of high practical relevance for the further development of sensors, resonators, and metamaterials utilizing the plasmonic properties of silver NPs.

Why do we need irradiation of internal mammary lymph nodes in patients with breast cancer: Analysis of lymph flow and radiotherapy studies.

AIM: Using clinical data and results of lymphoscintigraphy to calculate probability of internal mammary lymph node (IMLN) invasion by breast cancer (BC). To evaluate clinical value of lymphoscintigraphy as the guide for irradiation of IMLN. METHODS: Using the data of eight published studies that analyzed lymph flow from primary BC (4541pts) after intra-peri-tumoral injection of nanosized 99mTc-colloids we determined probability of lymph-flow from internal-central and external BC to IMLN. In 7 studies (4359pts) axillary staging was accompanied by IMLN biopsy (911pts) that helped us to estimate probability of IMLN metastatic invasion in relation to the status of axillary LN. Finally, we estimated probability of IMLN invasion by BC in five randomized and observation studies that analyzed effect of IMLN irradiation on overall survival (OS). We calculated possible gain in survival if they would be treated according to lymph-flow guided radiotherapy to IMLN. RESULTS: Lymph-flow from internal/central BC to IMLN was mentioned in 35% from external lesions - in 16% cases. In women with negative axillary LN metastases in IMLN were revealed in 7.8%pts, in the case of positive axillary nodes average risk of IMLN invasion increased to 38.1%. Calculated probability of IMLN metastatic invasion in pts included in evaluated trials did not exceed 10%. If lymphoscintigraphy would drive decision about irradiation of IMLN than 72-78% of pts included in these studies would escape radiotherapy to IMLN. In the remaining 21-28%pts with lymph-flow to IMLN their irradiation probably would increase gain in OS from 1.0-3.3% to 4.3-16.8%. CONCLUSION: Lymphoscintigraphy can be used to optimize the strategy of IMLN irradiation.

Enhancement of two-photon photoluminescence and SERS for low-coverage gold films.

Electromagnetic field enhancement (FE) effects occurring in thin gold films 3-12-nm are investigated with two-photon photoluminescence (TPL) and Raman scanning optical microscopies. The samples are characterized using scanning electron microscopy images and linear optical spectroscopy. TPL images exhibit a strong increase in the level of TPL signals for films thicknesses 3-8-nm, near the percolation threshold. For some thicknesses, TPL measurements reveal super-cubic dependences on the incident power. We ascribe this feature to the occurrence of very strongly localized and enhanced electromagnetic fields due to multiple light scattering in random nanostructures that might eventually lead to white-light generation. Raman images exhibit increasing Raman signals when decreasing the film thickness from 12 to 6-nm and decreasing signal for the 3-nm-film. This feature correlates with the TPL observations indicating that highest FE is to be expected near the percolation threshold.

Sensing using plasmonic nanostructures and nanoparticles.

Nanoparticles are widely used in various fields of science and technology as well as in everyday life. In particular, gold and silver nanoparticles display unique optical properties that render them extremely attractive for various applications. In this review, we focus on the use of noble metal nanoparticles as plasmonic nanosensors with extremely high sensitivity, even reaching single molecule detection. Sensors based on plasmon resonance shifts, as well as the use of surface-enhanced Raman scattering and surface-enhanced fluorescence, will be considered in this work.

Comparison of two treatment strategies for irradiation of regional lymph nodes in patients with breast cancer: Lymph flow guided portals versus standard radiation fields.

AIM AND BACKGROUND: Radiotherapy being an essential part of breast cancer treatment, we evaluate various radiotherapy strategies in patients with breast cancer. MATERIALS AND METHODS: Lymph node (LN) scintigraphy was performed in 172 primary patients with BC. LN visualization started 30-360 min after intratumoral injection of 75-150 MBq of 99mTc-nanocolloids. Our standard recommendation for postoperative radiotherapy in patients with LN invasion by BC were as follows: for patients with external localization of tumour - breast + axillary (Ax) + sub-supraclavicular (SSCL) regions; with internal localization - all above + internal mammary nodes (IM). Proposed strategy of lymph flow guided radiotherapy is based on the assumption that only regions that contain 'hot' LNs must be included in a treatment volume. RESULTS: Among 110 patients with external localization of BC, Ax LNs were visualized in all cases and in 62 patients it was the only region with 'hot' LN. Twenty-three patients (20.9%) had drainage to Ax + SSCL, 12 (10.9%) - Ax + IM, 13 (11.8%) - Ax + SSCL + IM regions. After the visualization of lymph flow patterns, standard treatment volume was changed in 87/110 cases (79.1%): in 56.4%, reduced, in 22.7%, enlarged or changed. In 62 patients with tumours in internal quadrants, we revealed the following patterns of lymph-flow: only to the Ax region in 23 (37.1%); Ax + IM, 13 (21%); Ax + SSCL, 15 (24.2%); Ax + IM + ISSCL, 11 (17.7%) cases. After lymph-flow visualization, the standard irradiation volume was reduced in 53/62 (85.5%) cases. CONCLUSION: Visualization of an individual lymph flow pattern from BC can be used for the optimization of standard fields used for irradiation of regional LNs.

Pen-on-paper approach toward the design of universal surface enhanced Raman scattering substrates.

The translation of a technology from the laboratory into the real world should meet the demand of economic viability and operational simplicity. Inspired by recent advances in conductive ink pens for electronic devices on paper, we present a "pen-on-paper" approach for making surface enhanced Raman scattering (SERS) substrates. Through this approach, no professional training is required to create SERS arrays on paper using an ordinary fountain pen filled with plasmonic inks comprising metal nanoparticles of arbitrary shape and size. We demonstrate the use of plasmonic inks made of gold nanospheres, silver nanospheres and gold nanorods, to write SERS arrays that can be used with various excitation wavelengths. The strong SERS activity of these features allowed us to reach detection limits down to 10 attomoles of dye molecules in a sample volume of 10 µL, depending on the excitation wavelength, dye molecule and type of nanoparticles. Furthermore, such simple substrates were applied to pesticide detection down to 20 ppb. This universal approach offers portable, cost effective fabrication of efficient SERS substrates at the point of care. This approach should bring SERS closer to the real world through ink cartridges to be fixed to a pen to create plasmonic sensors at will.

Crystallinity as a factor of SERS stability of silver nanoparticles formed by Ar+ irradiation.

The plasmonic sensors based on silver nanoparticles are limited in application due to their relatively fast degradation in the ambient atmosphere. The technology of ion-beam modification for the creation of monocrystalline silver nanoparticles (NPs) with stable plasmonic properties will expand the application of silver nanostructures. In the present study, highly-stable monocrystalline NPs were formed on the basis of a thin silver film by low-energy ion irradiation. Combined with lithography, this technique allows the creation of nanoparticle ensembles in variant forms. The characterization of the nanoparticles formed by ion-beam modification showed long-term outstanding for Ag nanoparticles stability of their plasmonic properties due to their monocrystalline structure. According to optical spectroscopy data, the reliable plasmonic properties in the ambient atmosphere are preserved for up to 39 days. The mapping of crystal violet dye via surface-enhanced Raman spectroscopy (SERS) revealed a strong amplification factor sustaining at least thrice as long as the one of similarly sized polycrystalline silver NPs formed by annealing. The plasmonic properties sustain more than a month of storage in the ambient atmosphere. Thus, ion-beam modification of silver film makes it possible to fabricate NPs with stable plasmonic properties and form clusters of NPs for sensor technology and SERS applications.

Wandering principal optical axes in van der Waals triclinic materials.

Nature is abundant in material platforms with anisotropic permittivities arising from symmetry reduction that feature a variety of extraordinary optical effects. Principal optical axes are essential characteristics for these effects that define light-matter interaction. Their orientation - an orthogonal Cartesian basis that diagonalizes the permittivity tensor, is often assumed stationary. Here, we show that the low-symmetry triclinic crystalline structure of van der Waals rhenium disulfide and rhenium diselenide is characterized by wandering principal optical axes in the space-wavelength domain with above π/2 degree of rotation for in-plane components. In turn, this leads to wavelength-switchable propagation directions of their waveguide modes. The physical origin of wandering principal optical axes is explained using a multi-exciton phenomenological model and ab initio calculations. We envision that the wandering principal optical axes of the investigated low-symmetry triclinic van der Waals crystals offer a platform for unexplored anisotropic phenomena and nanophotonic applications.

Exploring van der Waals materials with high anisotropy: geometrical and optical approaches.

The emergence of van der Waals (vdW) materials resulted in the discovery of their high optical, mechanical, and electronic anisotropic properties, immediately enabling countless novel phenomena and applications. Such success inspired an intensive search for the highest possible anisotropic properties among vdW materials. Furthermore, the identification of the most promising among the huge family of vdW materials is a challenging quest requiring innovative approaches. Here, we suggest an easy-to-use method for such a survey based on the crystallographic geometrical perspective of vdW materials followed by their optical characterization. Using our approach, we found As2S3 as a highly anisotropic vdW material. It demonstrates high in-plane optical anisotropy that is ~20% larger than for rutile and over two times as large as calcite, high refractive index, and transparency in the visible range, overcoming the century-long record set by rutile. Given these benefits, As2S3 opens a pathway towards next-generation nanophotonics as demonstrated by an ultrathin true zero-order quarter-wave plate that combines classical and the Fabry-Pérot optical phase accumulations. Hence, our approach provides an effective and easy-to-use method to find vdW materials with the utmost anisotropic properties.

Demonstration of magnetic dipole resonances of dielectric nanospheres in the visible region.

Strong resonant light scattering by individual spherical Si nanoparticles is experimentally demonstrated, revealing pronounced resonances associated with the excitation of magnetic and electric modes in these nanoparticles. It is shown that the low-frequency resonance corresponds to the magnetic dipole excitation. Due to high permittivity, the magnetic dipole resonance is observed in the visible spectral range for Si nanoparticles with diameters of ∼200 nm, thereby opening a way to the realization of isotropic optical metamaterials with strong magnetic responses in the visible region.