Combined small and large magnetic nanoparticle extraction and concentration from biofluids for non-toxic detection of biomarkers.

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.

Surface Chemistry of Nanohybrids with Fumed Silica Functionalized by Polydimethylsiloxane/Dimethyl Carbonate Studied Using 1H, 13C, and 29Si Solid-State NMR Spectroscopy.

The investigation of molecular interactions between a silica surface and organic/inorganic polymers is crucial for deeper understanding of the dominant mechanisms of surface functionalization. In this work, attachment of various depolymerized polydimethylsiloxanes (PDMS) of different chain lengths, affected by dimethyl carbonate (DMC), to silica nanoparticles pretreated at different temperatures has been studied using 29Si, 1H, and 13C solid-state NMR spectroscopy. The results show that grafting of different modifier blends onto a preheated silica surface depends strongly on the specific surface area (SSA) linked to the silica nanoparticle size distributions affecting all textural characteristics. The pretreatment at 400 °C results in a greater degree of the modification of (i) A-150 (SSA = 150 m2/g) by PDMS-10/DMC and PDMS-1000/DMC blends; (ii) A-200 by PDMS-10/DMC and PDMS-100/DMC blends; and (iii) A-300 by PDMS-100/DMC and PDMS-1000/DMC blends. The spectral features observed using solid-state NMR spectroscopy suggest that the main surface products of the reactions of various depolymerized PDMS with pretreated nanosilica particles are the (CH3)3SiO-[(CH3)2SiO-]x fragments. The reactions occur with the siloxane bond breakage by DMC and replacing surface hydroxyls. Changes in the chemical shifts and line widths, as shown by solid-state NMR, provide novel information on the whole structure of functionalized nanosilica particles. This study highlights the major role of solid-state NMR spectroscopy for comprehensive characterization of functionalized solid surfaces.

Toward New Thermoelectrics: Tin Selenide/Modified Graphene Oxide Nanocomposites.

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 (S 2σ). Moreover, these transport properties can then be further improved (S, σ increased) by functionalization 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. Functionalizing the GO by reaction with octadecyltrimethoxysilane (C21H46O3Si) and triethylamine ((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.

Optical plasmon nanostrip probe as an effective ultrashort pulse delivery system.

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.

A 29Si, 1H, and 13C Solid-State NMR Study on the Surface Species of Various Depolymerized Organosiloxanes at Silica Surface.

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.

Signal of microstrip scanning near-field optical microscope in far- and near-field zones.

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.