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Cleavage of siloxane bonds (Si-O) in organosiloxanes (OSs) is one of the most fundamentally and practically important challenges in the modern chemistry of silicones. However, no benign approaches have been found to cleave these bonds under mild conditions. In this paper, siloxane bond cleavage in polydimethylsiloxane (PDMS) was studied using a mixture of the “green” reagent dimethyl carbonate (DMC) and an environmentally benign reagent, tris(pentafluorophenyl)borane (B(C6F5)3). The obtained results indicate that the Si-O bonds are cleaved by reaction with DMC to form lower-weight polymer fragments with alkoxy end groups, while the addition of B(C6F5)3 to the depolymerizing mixture significantly increases the degree of PDMS depolymerization at room temperature or with increasing temperature. Quantum chemical calculations show that the DMC molecules form stable complexes with B(C6F5)3 by preferable formation of C=O····B bonds, which increases the solvation effects and kinetic energy upon collision with PDMS. This result provides an appropriate electronic structure and orientation for the complexes for more effective interaction with Si-O-Si via a concert mechanism. This proposed benign approach can be used for the production of new OS polymers, silicone recycling and functionalization of metal or metalloid oxides. We report a novel approach of siloxane bond splitting in organosiloxane using mixture of tris(pentafluorophenyl)borane and dimethyl carbonate. In the first part of this note, depolymerization of polydimethylsiloxane by dimethyl carbonate and with the addition of tris(pentafluorophenyl)borane is studied. Reactions are studied at different concentrations of above-mentioned reagents and temperature while the second part of this note represents theoretical calculation results which explain the mechanism of the depolymerization reaction.

We propose a novel non-toxic method of diagnostic biomarker extraction and concentration from biofluids. The method is based on the usage of (1) magnetic nanoparticles of a few nanometres in size bearing molecular traps for biomarkers on their surface and (2) additional larger (several tens of nanometres) magnetic nanoparticles for catching smaller magnetic nanoparticles in a strong magnetic field gradient with their consequent concentration into the detection area. It is shown that the interference of an external permanent gradient magnetic field with the magnetic field of large magnetic nanoparticles allows one to catch small magnetic nanoparticles from their trajectories in a fluid at a distance around ten radii of the large nanoparticles. Theoretical analysis and mathematical simulation show the validity of the proposed non-toxic method for fast and robust biomarker extraction and concentration for increasing the sensitivity of biomarker detection. We believe that the results presented herein can serve as a starting point in the development of a new subclass of biosensors and a human body diagnostic approach with enhanced sensitivity and selectivity.

In the present paper, we discuss the temperature-dependent epsilon-near-zero (ENZ) effect in graphene arising in the framework of its isotropic model. The effect was theoretically investigated in detail using a simplified model design of the slot line containing a graphene layer in which all other effects are eliminated allowing us to focus solely on the ENZ effect. With the reduction of graphene effective temperature, the ENZ effect in the near-IR wavelength range was found to become pronounced even for structures and metasurfaces for which it has been considered neglectable and has not been previously observed at room temperatures. This temperature-dependent behaviour was interpreted analytically within the approximation in which the real part of the graphene dielectric constant is considered vanishingly small in comparison with the imaginary part (this condition is always satisfied at the ENZ point in graphene). Furthermore, the results presented in the paper may be potentially helpful in the construction of an experiment designed to finally prove or disregard the applicability of the isotropic model of graphene.

In this paper, we provide a detailed three-dimensional numerical analysis of the optical properties of common and modified bowtie aperture antennas integrated onto a silicon waveguide platform, to discuss the influence of geometrical parameters on the electric field enhancement factor and waveguide transmission when such antennas are excited by the evanescent field of the Si waveguide mode. We demonstrate that waveguide transmission is severely affected by the interference between Si waveguide modes and surface plasmon polariton modes excited in the antenna, while the antenna's field enhancement factor is mainly determined by the localized surface plasmon resonance occurring in its nano-gap. These mechanisms lead to a mismatch between the wavelength at which the antenna's field enhancement factor is maximized, and the wavelength at which transmission through the Si waveguide is minimized, suggesting that in some multi-mode cases, the optical properties of integrated nanoantennas determined through direct measurement of Si waveguide transmission may be misleading. Methods for improving the electric field enhancement (such that it has a bigger modulation depth) that have minimal impact on the resonant wavelength, and for improving the shape and location of the corresponding hot spot of the bowtie aperture antennas, are also discussed and analyzed. We believe that this analysis will be helpful in design of on-chip bowtie-type optical antennas for surface enhanced Raman spectroscopy, near-field optical microscopy, high sensitivity detection, and plasmonic optical tweezers.

In this paper, we present experimental results on speckle noise suppression using a completely passive method. The passivity of the method is achieved owing to the absence of any mechanical, electr...

Three poly(organosiloxanes) (hydromethyl-, dimethyl-, and epoxymethylsiloxane) of different chain lengths and pendant groups and their mixtures of dimethyl (DMC) or diethyl carbonates (DEC) were applied in the modification of fumed silica nanoparticles (FSNs). The resulting modified silicas were studied in depth using 29Si, 1H, and 13C solid-state NMR spectroscopy, elemental analysis, and nitrogen adsorption-desorption (BET) analysis. The obtained results reveal that the type of grafting, grafting density, and structure of the grafted species at the silica surface depend strongly on the length of organosiloxane polymer and on the nature of the “green” additive, DMC or DEC. The spectral changes observed by solid-state NMR spectroscopy suggest that the major products of the reaction of various organosiloxanes and their DMC or DEC mixtures with the surface are D (RR’Si(O0.5)2) and T (RSi(O0.5)3) organosiloxane units. It was found that shorter methylhydro (PMHS) and dimethylsiloxane (PDMS) and their mixtures with DMC or DEC form a denser coverage at the silica surface since S BET diminution is larger and grafting density is higher than the longest epoxymethylsiloxane (CPDMS) used for FSNs modification. Additionally, for FSNs modified with short organosiloxane PMHS/DEC and also medium organosiloxane PDMS/DMC, the dense coverage formation is accompanied by a greater reduction of isolated silanols, as shown by solid-state 29Si NMR spectroscopy, in contrast to reactions with neat organosiloxanes. The surface coverage at FSNs with the longest siloxane (CPDMS) greatly improves with the addition of DMC or DEC. The data on grafting density suggest that molecules in the attached layers of FSNs modified with short PMHS and its mixture of DMC or DEC and medium PDMS and its mixture of DMC form a “vertical” orientation of the grafted methylhydrosiloxane and dimethylsiloxane chains, in contrast to the reaction with PDMS/DEC and epoxide methylsiloxane in the presence of DMC or DEC, which indicates a “horizontal” chain orientation of the grafted methyl and epoxysiloxane molecules. This study highlights the major role of solid-state NMR spectroscopy for comprehensive characterization of solid surfaces. Graphical abstract

This work was financially supported by the EPSRC (EP/P510968/1). New nanocomposites have been prepared by combining tin selenide (SnSe) with graphene oxide (GO) in a simple aqueous solution process followed by ice templating (freeze casting). The resulting integration of SnSe within the GO matrix leads to modifications of electrical transport properties and the possibility of influencing the power factor (S2σ). Moreover, these transport properties can then be further improved (S, σ increased) by funtionalisation of the GO surface to form modified nanocomposites (SnSe/GOmod) with enhanced power factors in comparison to unmodified nanocomposites (SnSe/GO) and “bare” SnSe itself. Functionalising the GO by reaction with octadecyltrimethoxysilane (ODTS; C21H46O3Si) and triethylamine (TEA;(CH3CH2)3N) switches SnSe from p-type to n-type conductivity with an appreciable Seebeck coefficient and high electrical conductivity (1257 S·m-1 at 539 K); yielding a 20-fold increase in the power factor compared to SnSe itself, prepared by the same route. These findings present new possibilities to design inexpensive and porous nanocomposites based on metal chalcogenides and functionalized carbon-derived matrices. Postprint

In this paper, we propose a modified platform for on-chip integrated photonics. The platform allows one to efficiently connect a tapered optical fiber or fiber lens to an on-chip waveguide with high alignment precision and to mechanically fix the fiber on the chip to prevent defocusing, lateral shift, and angular detuning during device operation. The metal screen of the connector-made of gold-prevents any penetration of the background radiation into the optical circuit, something which is not possible to achieve in all the cases using tapers or grating couplers. We performed impedance-matching analysis based on transmission line theory and numerically optimized the platform, allowing us to achieve a tapered fiber mode to on-chip waveguide mode transformation efficiency as high as 96% (-0.177 dB) at wavelengths of 785 and 1550 nm. The platform bandwidth (transformation efficiency ≥80%) is 151 nm. At the same time, transformation efficiency is stable (reduction less than 1%) in an offset range of ±2 nm-enough for modern on-chip and off-chip coherent light sources. The horizontal and vertical lateral alignment tolerances for the platform are 700 and 600 nm, respectively, at a transformation efficiency ≥80% while the longitudinal alignment tolerance is approximately 70 nm. Due to the relatively high lateral and longitudinal tolerances, it is possible to produce the platform at high efficiency using existing fabrication nanotechnologies. We believe that this platform accelerates the realization of fully on-chip Raman spectroscopes and may be of practical importance in other on-chip integrated photonic devices.

We report on a novel effect of temperature-dependent modulation in graphene-supported metamaterials. The effect was observed during the theoretical analysis of a model graphene-supported electro-optical modulator having silicon dioxide (SiO2) or hafnium dioxide (HfO2) as a buffer dielectric layer. Comparative analysis of the two materials showed that they provide approximately the same maximum values for transmission and reflection modulation depths. However, in the case of a HfO2 buffer layer, a lower chemical potential of the graphene is required to achieve the maximum value. Moreover, theoretical calculations revealed that a lower gate voltage (up to 6.4 times) is required to be applied in the case of a HfO2 layer to achieve the same graphene chemical potential. The graphene layer was found to possesses high absorption (due to the additional resonance excitation) for some values of chemical potential and this effect is extremely temperature dependent. The discovered modulation effect was demonstrated to further increase the transmission modulation depth for the simple model structure up to 2.7 times (from 18.4% to 50.1%), while for the reflection modulation depth, this enhancement was equal to 2.2 times (from 24.4% to 52.8%). The novel modulation effect could easily be adopted and applied over a wide range of metadevices which would serve as a quick booster for the development of related research areas.

In this paper, we analyze the ultrafast temporal and spectral responses of optical fields in tapered and metalized optical fibers (MOFs) and optical plasmon nanostrip probes (NPs). Computational experiment shows that output pulses of the NPs are virtually unchanged in shape and duration for input pulses with a duration of >1 fs and are not sensitive to changes in the parameters of the probe (such as convergence angle and taper length), while local enhancement of the electric field intensity reaches 300 times at the NP apex. Compared with the NPs, MOFs lead to significant output pulse distortions, even for input pulses with a duration of 10 fs. In addition, the temporal response at the MOF apex is critically sensitive to changes in MOF parameters and cannot provide any significant local enhancement of the electric field. These findings reveal the high potential of optical plasmon nanostrip probes as an ultrashort pulse delivery system to nanometer-size areas and indicate that its usage can be promising for a wide variety of techniques studying ultrafast processes in nanoscopic volumes.

Three poly(organosiloxanes) (hydromethyl-, dimethyl-, and epoxymethylsiloxane) of different chain lengths and pendant groups and their mixtures of dimethyl (DMC) or diethyl carbonates (DEC) were applied in the modification of fumed silica nanoparticles (FSNs). The resulting modified silicas were studied in depth using 29Si, 1H, and 13C solid-state NMR spectroscopy, elemental analysis, and nitrogen adsorption-desorption (BET) analysis. The obtained results reveal that the type of grafting, grafting density, and structure of the grafted species at the silica surface depend strongly on the length of organosiloxane polymer and on the nature of the “green” additive, DMC or DEC. The spectral changes observed by solid-state NMR spectroscopy suggest that the major products of the reaction of various organosiloxanes and their DMC or DEC mixtures with the surface are D (RR’Si(O0.5)2) and T (RSi(O0.5)3) organosiloxane units. It was found that shorter methylhydro (PMHS) and dimethylsiloxane (PDMS) and their mixtures with DMC or DEC form a denser coverage at the silica surface since SBET diminution is larger and grafting density is higher than the longest epoxymethylsiloxane (CPDMS) used for FSNs modification. Additionally, for FSNs modified with short organosiloxane PMHS/DEC and also medium organosiloxane PDMS/DMC, the dense coverage formation is accompanied by a greater reduction of isolated silanols, as shown by solid-state 29Si NMR spectroscopy, in contrast to reactions with neat organosiloxanes. The surface coverage at FSNs with the longest siloxane (CPDMS) greatly improves with the addition of DMC or DEC. The data on grafting density suggest that molecules in the attached layers of FSNs modified with short PMHS and its mixture of DMC or DEC and medium PDMS and its mixture of DMC form a “vertical” orientation of the grafted methylhydrosiloxane and dimethylsiloxane chains, in contrast to the reaction with PDMS/DEC and epoxide methylsiloxane in the presence of DMC or DEC, which indicates a “horizontal” chain orientation of the grafted methyl and epoxysiloxane molecules. This study highlights the major role of solid-state NMR spectroscopy for comprehensive characterization of solid surfaces. Graphical abstract Electronic supplementary material The online version of this article (10.1186/s11671-019-2982-2) contains supplementary material, which is available to authorized users.

In this study, we performed a three-dimensional computational experiment on ultrashort pulse propagation in an optical fiber-tip probe that is decorated with gold nanoparticles (NPs) using a constant structure for the probe’s dielectric taper and different spatial configurations of the gold nanoparticles. Interestingly, a hot spot with the highest amplitude of the electric field was found not along the same chain of the NPs but between terminal NPs of neighboring chains of NPs at the probe’s tip (the amplitude of the electric field in the hot spots between the NPs along the same chain was of the order of 101, while that between terminal NPs of neighboring chains was of the order of 103). We eventually identified a configuration with only six terminal nanoparticles (Config4) which is characterized by the highest electric field amplitude enhancement and can provide the highest spatial resolution in the SERS interrogation of an object of interest. The ultrashort temporal responses of the hot spots for all configurations exhibited relatively high pulse elongation (relative elongation was greater than 4.3%). At the same time, due to the reflection of the incident pulse and consequent interference, the temporal responses of most hot spots contained several peaks for all configurations except for the optimum Config4. Nonetheless, the ultrashort temporal responses of all hot spots for Config4 were characterized by a single peak but with a relatively large pulse elongation (relative elongation was 234.1%). The results indicate that further examination of this new structure of a nanoparticles-coated optical fiber-tip probe with only six terminal NPs may provide attractive characteristics for its practical applications.

The improved scheme of data recording process on an optical disc based on a substrate made of high-stable materials has been proposed. Information layer with depth of 115nm and width of 600nm has been obtained on sapphire substrate by ion-beam etching using improved scheme. These experimental results allow to create the sapphire optical discs for long-term data storage.

An analytical model of interference between an electromagnetic field of fundamental quasi-TM(EH)00-mode and an electromagnetic field of background radiation at the apex of a near-field probe based on an optical plasmon microstrip line (microstrip probe) has been proposed. The condition of the occurrence of electromagnetic energy reverse flux at the apex of the microstrip probe was obtained. It has been shown that the nature of the interference depends on the length of the probe. Numerical simulation of the sample scanning process was conducted in illumination-reflection and illumination-collection modes. Results of numerical simulation have shown that interference affects the scanning signal in both modes. However, in illumination-collection mode (pure near-field mode), the signal shape and its polarity are practically insensible to probe length change; only signal amplitude (contrast) is slightly changed. However, changing the probe length strongly affects the signal amplitude and shape in the illumination-reflection mode (the signal formed in the far-field zone). Thus, we can conclude that even small background radiation can significantly influence the signal in the far-field zone and has practically no influence on a pure near-field signal.

We propose a design for efficient end-fire coupling of surface plasmon polaritons in a metal-insulator-metal (MIM) waveguide with an optical fiber as part of a simple photoplastic connector. The design was analyzed and optimized using the three-dimensional finite-difference time-domain method. The calculated excitation efficiency coefficient of the waveguide is 83.7% (−0.77 dB) at a wavelength of 405 nm. This design enables simple connection of an optical fiber to a MIM waveguide and highly efficient local excitation of the waveguide. Moreover, the length of the metallic elements of the waveguide, and thus the dissipative losses, can be reduced. The proposed design may be useful in plasmonic-type waveguide applications such as near-field investigation of live cells and other objects with super-resolution.

Results of numerical simulation of near-field optical data storage using microstrip probe are presented. Simulation is carried out on the basis of the finite-difference time-domain method. Features of the information reading process from the ROM and RW (based on the phase transmissions of Ge2Sb2Te5 film) formats of optical discs under illumination and illumination-collection mode are analyzed and considered. Mathematical modeling has shown that the signal from the ROM-format disc under illumination mode, despite the fact that the probe has a significant far-field transmission coefficient, has a large crosstalk and small spatial resolution (significantly worse than a size of probe aperture). Unlike illumination mode, signal under illumination-collection mode (pure near-field method) has a resolution close to the size of the aperture, good amplitude and contrast, as well as relatively low crosstalk. However, information reading under illumination-collection mode from RW-format disc is not able to get the same good quality signal. Therefore the further optimization of the method is required to improve the signal quality of RW format.

Results of implementation of technical solution for long term data storage technology on the basis of single crystal sapphire are presented. The effect of birefringence on the distribution of the focused laser beam through a uniaxial birefringent medium having a vertical orientation of the optical axis is analyzed. An expression for the calculation of the geometric aberrations of the focused laser beam in single-crystal substrate of the optical disc has been presented. It is shown that the problem of data reading through a substrate of negative single crystal sapphire can be solved by using for reading a special optical system with a plate of positive single crystal materials. The experimental results confirm the efficiency of the proposed technical solution.