Multilayer coatings based on gold nanoparticles and polymers with bovine serum albumin as a functional layer for the chiral separation in capillary electrochromatography.

In this study, we developed physically adsorbed multi-layer coatings using poly-l-lysine or poly(diallyldimethylammonium chloride) and gold nanoparticles, which were functionalized with bovine serum albumin for the chiral separation in electrochromatography. The approach involves sequentially depositing positively charged polymers and negatively charged citrate-stabilized gold nanoparticles. By repeating this modification cycle, we created two- and four-layer coatings, which were sequentially functionalized with albumin forming three- and five-layer coatings that were finally applied for the separation of enantiomers of dl-tryptophan. The formed coatings exhibit stability across a pH range of 2-10 and feature a dense, uniform surface, as confirmed by scanning electron microscope images. The number of layers impacted nanoparticle deposition density, with five-layer coatings being denser than three-layer ones. Five-layer coatings enable baseline separation of dl-tryptophan enantiomers, whereas three-layer coatings require the presence of albumin in the background electrolyte for separation. Therefore, increasing the number of layers and gold nanoparticles density enhances albumin active center concentration on capillary walls, improving the separation of dl-tryptophan enantiomers. The five-layer coatings can be easily fabricated and possess good repeatability of analytes migration time.

How is the Observation of High-Order Overtones and Combinations Elucidated by the Charge-Transfer Mechanism in SERS?

The charge-transfer chemical mechanism is responsible for altering the molecular spectral pattern and providing valuable insights into the properties of adsorbates. The impact of charge transfer becomes more pronounced in SERS spectra when CT states can gain intensity through vibronic coupling with high-intensity excitations. Experimental SERS spectra of diamino molecules, such as 4,4'-diaminostilbene (DAS) and 4,4'-diaminotolane (DAT), featuring bright CT transitions, have been compared to dipyridyl compounds, such as 1,2-bis(4-pyridyl) ethylene (BPE) and 1,2-di(4-pyridyl) acetylene (DPA), characterized by nearly dark CT excitations. This comparison aims to elucidate the effect of CT transitions on the presence of overtones and combination bands. We explain this distinction using Albrecht's formalism for resonance Raman spectroscopy within the framework of path integral time-dependent density functional theory considering the Herzberg-Teller corrections. It is worth noting that the energy gap between the highest occupied metallic orbital and the lowest unoccupied molecular orbital in diamino derivatives is noticeably smaller than in compounds featuring two pyridyl rings. The high-intensity SERS-CT spectra for diamino derivatives, primarily driven by the Albrecht A term, were acquired and used to elucidate the experimental observation of high-order modes with a significant Huang-Rhys factor. Conversely, the absolute intensity of SERS-CT for dipyridyl compounds is at least 106 times smaller than that for diamines, and the C term makes a significant contribution, explaining the silent overtones.

Behavioral Modeling of Memristors under Harmonic Excitation.

Memristors are devices built on the basis of fourth passive electrical elements in nanosystems. Because of the multitude of technologies used for memristor implementation, it is not always possible to obtain analytical models of memristors. This difficulty can be overcome using behavioral modeling, which is when mathematical models are constructed according to the input-output relationships on the input and output signals. For memristor modeling, piecewise neural and polynomial models with split signals are proposed. At harmonic input signals of memristors, this study suggests that split signals should be formed using a delay line. This method produces the minimum number of split signals and, as a result, simplifies behavioral models. Simplicity helps reduce the dimension of the nonlinear approximation problem solved in behavioral modeling. Based on the proposed method, the piecewise neural and polynomial models with harmonic input signals were constructed to approximate the transfer characteristic of the memristor, in which the current dynamics are described using the Bernoulli differential equation. It is shown that the piecewise neural model based on the feedforward network ensures higher modeling accuracy at almost the same complexity as the piecewise polynomial model.

One-Pot Synthesis of Silica-Coated Gold Nanostructures Loaded with Cyanine 5.5 for Cell Imaging by SERS Spectroscopy.

Anisotropic gold nanoparticles have been recognized as promising agents for medical diagnostics and cancer therapy due to their wide functionality, photothermal effect, and ability for optical signal amplification in the near-infrared range. In this work, a simple and rapid method for the preparation of bone-shaped gold nanoparticles coated with a dye-impregnated silica shell with an aminated surface is proposed. The possibility of further functionalization the nanostructures with a delivery vector using folic acid as an example is demonstrated. The average size of the resulting tags does not exceed 70 nm, meeting the criteria of cell endocytosis. The prepared tags exhibit surface-enhanced Raman scattering (SERS) spectra at excitation with lasers of 632.8 and 785 nm. Cell imaging is performed on HeLa cells based on the most pronounced SERS bands as a tracking signal. The obtained images, along with scanning electron microscopy of cell samples, revealed the tendency of tags to agglomerate during endocytosis followed by the "hot spots" effect. To evaluate the toxic and proliferative effect of the nanotags, an MTT assay was performed with two HeLa and HEP G2 cell lines. The results revealed higher viability for HEP G2 cells.

Comparative study of fluorescence core-shell nanotags with different morphology of gold core.

The development of compact and highly active plasmonic nanotags tuned on the first transparency window of biological tissues is under demand for cell imaging applications. The optical activity of bare plasmonic nanoparticles is determined by morphology but the more complex core-shell systems require experimental verification as a shell may change the expected trends. A comparative study of fluorescence core-shell nanotags with different morphology of gold core is presented in this work. Four types of gold nanoparticles (nanostars, nanobones, short and long nanorods), differing in the surface roughness were used for preparation of complex nanotags with a polymer shell containing cyanine 5.5 dye inside and surface functionalized with folic acid as a model delivery vector. The obtained core-shell nanotags were characterized with transmission electron microscopy, UV-Vis absorption spectroscopy and zeta potential measurements. Imaging performance of the obtained nanotags was studied with a fluorescence microscope on human pancreatic cancer cells, indicating a successful internalization of all nanotags by cancer cells and fluorescence intensity depending on the spectral overlap between the dye, plasmonic band of gold core and laser wavelength. The tags based on gold nanorods showed the brightest fluorescence among the studied systems. Scanning electron microscopy of the cells incubated with nanotags proved their internalization in membrane and cytoplasm. The cell viability assay showed reduced cytotoxicity and good biocompatibility up to the concentration enough for cell imaging. The obtained results suggested that compact core-shell nanotags can be used for targeting the folate receptor positive tumor cells.

Dual Autoencoder Network with Separable Convolutional Layers for Denoising and Deblurring Images.

A dual autoencoder employing separable convolutional layers for image denoising and deblurring is represented. Combining two autoencoders is presented to gain higher accuracy and simultaneously reduce the complexity of neural network parameters by using separable convolutional layers. In the proposed structure of the dual autoencoder, the first autoencoder aims to denoise the image, while the second one aims to enhance the quality of the denoised image. The research includes Gaussian noise (Gaussian blur), Poisson noise, speckle noise, and random impulse noise. The advantages of the proposed neural network are the number reduction in the trainable parameters and the increase in the similarity between the denoised or deblurred image and the original one. The similarity is increased by decreasing the main square error and increasing the structural similarity index. The advantages of a dual autoencoder network with separable convolutional layers are demonstrated by a comparison of the proposed network with a convolutional autoencoder and dual convolutional autoencoder.

The Origin of the Non-Constancy of the Bulk Resistance of Ion-Selective Electrode Membranes within the Nernstian Response Range.

The dependence of the bulk resistance of membranes of ionophore-based ion-selective electrodes (ISEs) on the composition of mixed electrolyte solutions, within the range of the Nernstian potentiometric response, is studied by chronopotentiometric and impedance measurements. In parallel to the resistance, water uptake by the membranes is also studied gravimetrically. The similarity of the respective curves is registered and explained in terms of heterogeneity of the membranes due to the presence of dispersed aqueous phase (water droplets). It is concluded that the electrochemical equilibrium is established between aqueous solution and the continuous organic phase, while the resistance refers to the membrane as whole, and water droplets hamper the charge transfer across the membranes. In this way, it is explained why the membrane bulk resistance is not constant within the range of the Nernstian potentiometric response of ISEs.

Surface enhanced Raman scattering of new acridine based fluorophore adsorbed on silver electrode.

4,5-Bis(N,N-di(2-hydroxyethyl)iminomethyl)acridine (BHIA) is a new acridine based fluoroionophore and a highly-selective sensor for cadmium ion. The direct interaction of the aromatic nitrogen atom with a surface is impossible since there are bulky substituents in the 4,5-positions of the acridine fragment. Nevertheless BHIA molecule shows a reliable SERS spectrum while adsorbed on a silver electrode. The analysis of SERS spectra pH dependence reveals that BHIA species adsorbed on a surface can exist in both non-protonated and protonated forms. The adsorption of BHIA from alkaline solution is accompanied by carbonaceous species formation at the surface. The intensity of such "carbon bands" turned out to be related with the supporting electrolyte (KCl) concentration. Upon lowering the electrode potential the SERS spectra of BHIA do not undergo changes but the intensity of bands decreases. This indicates that the adsorption mechanism on the silver surface is realized via aromatic system of acridine fragment. In case of such an adsorption mechanism the chelate fragment of the BHIA molecule is capable of interaction with the solution components. Addition of Cd(2+) ions to a system containing BHIA adsorbed on a silver electrode in equilibrium with the solution leads to the formation of BHIA/Cd(2+) complex which desorption causes the loss of SERS signal.

Vaults bind directly to microtubules via their caps and not their barrels.

Vaults are large (13 Mda) ribonucleoprotein particles that are especially abundant in multidrug resistant cancer cells and have been implicated in nucleocytoplasmic drug transport. To understand how these large barrel-shaped complexes are transported through the cytosol, we examined the association of vaults with microtubules both in vitro and in vivo. Within cells, a subpopulation of vaults clearly associates with microtubules, and these vaults remain associated with tubulin dimers/oligomers when microtubules are disassembled by nocodazole treatment. In vitro, a microtubule-pull down assay using highly purified rat vaults and reassembled microtubules reveals that vaults exhibit concentration-dependent binding to microtubules that does not require the carboxyl terminal end of tubulin. Remarkably, negative staining for electron microscopy reveals that vault binding to microtubules is mediated by the vault caps; more than 82% of bound vaults attach to the microtubule lattice with their long axes perpendicular to the long axis of the microtubule. Five to six vault particles were bound per micron of microtubule, with no crosslinking of microtubules observed, suggesting that only one end of the vault can bind microtubules. Taken together, the data support the model of vaults as barrel-shaped containers that transiently interact with microtubules.