Structural properties of nanocomposites based on resole-type phenol-formaldehyde oligomers and detonation nanodiamonds

Using the methods of infrared spectroscopy (IRS) and X-ray photoelectron spectroscopy (XPS), it was shown that short-term high-energy machining of detonation nanodiamonds (DND) leads to structural changes in the crystal structure and functional composition of the surface layer on particles. The possibility of spontaneous formation for stable colloidal systems with a narrow size distribution of mechanically activated DND in phenol-formaldehyde oligomers (PFO) was established. By molecular spectroscopy it was revealed that π → π* interactions of the aromatic rings of PFO are caused by orientational phenomena as a result of hydrogen bonds between an activated DND surface and functional groups of PFO. The effect of DND concentration on the curing reaction parameters ofpsgr the phenol-formaldehyde oligomer was determined by differential scanning calorimetry (DSC). The concentration effect of mechanically activated nanodiamonds on the physical and mechanical characteristics of a composite material based on phenol-formaldehyde binder and polyamide paper (Nomex) was studied. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48582.     

Quantum Sensing in a Physiological‐Like Cell Niche Using Fluorescent Nanodiamonds Embedded in Electrospun Polymer Nanofibers

Fluorescent nanodiamonds (fNDs) containing nitrogen vacancy (NV) centers are promising candidates for quantum sensing in biological environments. This work describes the fabrication and implementation of electrospun poly lactic‐co‐glycolic acid (PLGA) nanofibers embedded with fNDs for optical quantum sensing in an environment, which recapitulates the nanoscale architecture and topography of the cell niche. A protocol that produces uniformly dispersed fNDs within electrospun nanofibers is demonstrated and the resulting fibers are characterized using fluorescent microscopy and scanning electron microscopy (SEM). Optically detected magnetic resonance (ODMR) and longitudinal spin relaxometry results for fNDs and embedded fNDs are compared. A new approach for fast detection of time varying magnetic fields external to the fND embedded nanofibers is demonstrated. ODMR spectra are successfully acquired from a culture of live differentiated neural stem cells functioning as a connected neural network grown on fND embedded nanofibers. This work advances the current state of the art in quantum sensing by providing a versatile sensing platform that can be tailored to produce physiological‐like cell niches to replicate biologically relevant growth environments and fast measurement protocols for the detection of co‐ordinated endogenous signals from clinically relevant populations of electrically active neuronal circuits.     

Transient Absorption: A New Modality for Microscopic Imaging of Nanomaterials in Living Cells

Transient absorption is a secondary absorption that happens after a material has been excited through primary absorption. Different mechanisms can contribute to transient absorption. This universal photophysical process exists in almost all types of nanomaterials, making it an ideal modality to monitor the location, dynamics, and interactions of nanomaterials in living cells, tissues, or animals. With two beams of lasers and a scanning microscope, transient absorption microscopy is able to acquire high‐resolution, 3D images at high speed, without the need for labeling. Through time‐delay adjustments of pulse trains, this novel method can also reveal background‐free images of specific nanomaterials, even with the interference of high concentrations of fluorophores.     

Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio‐orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30‐nm fluorescent nanodiamonds (FNDs) in 10–20‐nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near‐spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio‐orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells.     

Polydopamine Encapsulation of Fluorescent Nanodiamonds for Biomedical Applications

Fluorescent nanodiamonds (FNDs) are promising bioimaging probes compared with other fluorescent nanomaterials such as quantum dots, dye‐doped nanoparticles, and metallic nanoclusters, due to their remarkable optical properties and excellent biocompatibility. Nevertheless, they are prone to aggregation in physiological salt solutions, and modifying their surface to conjugate biologically active agents remains challenging. Here, inspired by the adhesive protein of marine mussels, encapsulation of FNDs within a polydopamine (PDA) shell is demonstrated. These PDA surfaces are readily modified via Michael addition or Schiff base reactions with molecules presenting thiol or nitrogen derivatives. Modification of PDA shells by thiol terminated poly(ethylene glycol) (PEG‐SH) molecules to enhance colloidal stability and biocompatibility of FNDs is described. Their use as fluorescent probes for cell imaging is demonstrated; it is found that PEGylated FNDs are taken up by HeLa cells and mouse bone marrow‐derived dendritic cells and exhibit reduced nonspecific membrane adhesion. Furthermore, functionalization with biotin‐PEG‐SH is demonstrated and long‐term high‐resolution single‐molecule fluorescence based tracking measurements of FNDs tethered via streptavidin to individual biotinylated DNA molecules are performed. This robust polydopamine encapsulation and functionalization strategy presents a facile route to develop FNDs as multifunctional labels, drug delivery vehicles, and targeting agents for biomedical applications.     

The effect of surface modification on thermal stability of nanodiamonds

The paper addresses the influence of surface modification through alteration of the functional top surface layer on the thermal stability of nanodiamond. The modification of nanodiamond by a high-temperature activation of its surface, which is followed by chemical treatment, is found to reduce concentration of metal impurities and oxygen-containing surface groups that are desorbed at temperatures below 773 K. As a consequence, the rate of oxidation of the modified diamonds at temperatures up to 773 K is 1.7 times slower. The oxidation onset temperature is shifted by 100 degrees.     

Diamondoid Phosphines – Selective Phosphorylation of Nanodiamonds[1]

The diamondoids (nanodiamonds) diamantane and triamantane were selectively converted into diorganophosphinic acid chlorides by reacting them with phosphorus trichloride under Friedel–Crafts‐like conditions. The di‐diamondoid phosphinic acid chlorides were subsequently reduced with trichlorosilane to give the hitherto unknown corresponding di‐diamondoid phosphines. These diamondoid phosphinic acid chlorides and phosphines are of great utility as starting materials in organo‐element and coordination chemistry due to their extraordinary rigidity and steric bulk.     

Nitrogen and Luminescent Nitrogen‐Vacancy Defects in Detonation Nanodiamond

An efficient method to investigate the microstructure and spatial distribution of nitrogen and nitrogen‐vacancy (N‐V) defects in detonation nanodiamond (DND) with primary particle sizes ranging from approximately 3 to 50 nm is presented. Detailed analysis reveals atomic nitrogen concentrations as high as 3 at% in 50% of diamond primary particles with sizes smaller than 6 nm. A non‐uniform distribution of nitrogen within larger primary DND particles is also presented, indicating a preference for location within the defective central part or at twin boundaries. A photoluminescence (PL) spectrum with well‐pronounced zero‐phonon lines related to the N‐V centers is demonstrated for the first time for electron‐irradiated and annealed DND particles at continuous laser excitation. Combined Raman and PL analysis of DND crystallites dispersed on a Si substrate leads to the conclusion that the observed N‐V luminescence originates from primary particles with sizes exceeding 30 nm. These findings demonstrate that by manipulation of the size/nitrogen content in DND there are prospects for mass production of nanodiamond photoemitters based on bright and stable luminescence from nitrogen‐related defects.