The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose

The shape and size distribution of crystalline nanoparticles resulting from the sulfuric acid hydrolysis of cellulose from cotton, Avicel, and tunicate were investigated using transmission electron microscopy (TEM) and atomic force microscopy (AFM) as well as small- and wide-angle X-ray scattering (SAXS and WAXS). Images of negatively stained and cryo-TEM specimens showed that the majority of cellulose particles were flat objects constituted by elementary crystallites whose lateral adhesion was resistant against hydrolysis and sonication treatments. Moreover, tunicin whiskers were described as twisted ribbons with an estimated pitch of 2.4-3.2 microm. Length and width distributions of all samples were generally well described by log-normal functions, with the exception of tunicin, which had less lateral aggregation. AFM observation confirmed that the thickness of the nanocrystals was almost constant for a given origin and corresponded to the crystallite size measured from peak broadening in WAXS spectra. Experimental SAXS profiles were numerically simulated, combining the dimensions and size distribution functions determined by the various techniques.     

Size Confinement Effects on Electronic and Optical Properties of Silver Halide Nanocrystals as Probed by Cryo-EFTEM and EELS

Cryo-energy-filtering transmission electron microscopy and electron energy-loss spectroscopy have been applied to study size confinement effects on electronic, dielectric, and optical properties of Ag(Br, I) nanocrystals. The dielectric permittivity, optical joint density of states, refractive index, extinction, and absorption for nanocrystals derived via Kramers–Kronig relations have been compared with experimental data for Ag(Br, I) tabular microcystals and ab initio linear muffin-tin orbital method in its atomic spheres approximation calculations for AgBr. Contrast tuning with the selected energy window between 0 and 100 eV enabled visualizing valence electron excitations in silver halides because of plasmons superimposed with interband transitions and Mott–Wannier excitons. The nonuniform contrast of nanocrystals revealed by cryo-energy-filtering transmission electron microscopy was referred to a size-confined coupling of surface and volume losses that could lead to oscillations of the image intensity with the nanocrystal size. A size-dependent enhancement of interband transitions at 4 eV correlated with the enhancement of exciton luminescence from nanocrystals because of contributions to the energy-level structure from carrier confinement and surface states.     

Clustered magnetite nanocrystals cross-linked with PEI for efficient siRNA delivery

Magnetofection has been utilized as a powerful tool to enhance gene transfection efficiency via magnetic field-enforced cellular transport processes. The accelerated accumulation of nucleic acid molecules by applying an external magnetic force enables the rapid and improved transduction efficiency. In this study, we developed magnetite nanocrystal clusters (PMNCs) cross-linked with polyethylenimine (PEI) to magnetically trigger intracellular delivery of small interfering RNA (siRNA). PMNCs were produced by cross-linked assembly of catechol-functionalized branched polyethylenimine (bPEI) around magnetite nanocrystals through an oil-in-water (O/W) emulsion and solvent evaporation method. The physical properties of PMNC were characterized by TEM, DLS, TSA, and FT-IR. Finely tuned formulation of clustered magnetite nanocrystals with controlled size and shape exhibited superior saturation of magnetization value. Magnetite nanocrystal clusters could form nanosized polyelectrolyte complexes with negatively charged siRNA molecules, enabling efficient delivery of siRNA into cells upon exposure to an external magnetic field within a short time. This study introduces a new class of magnetic nanomaterials that can be utilized for magnetically driven intracellular siRNA delivery.     

Synthesis and characterization of pure cubic zirconium oxide nanocrystals by decomposition of bis-aqua, tris-acetylacetonato zirconium(IV) nitrate as new precursor complex

Pure zirconium oxide (ZrO₂) nanocrystals with diameters 10-30 nm are fabricated from bis-aqua, tris-acetylacetonato zirconium(IV) nitrate; [Zr(acac)₃(H₂O)₂](NO₃); by thermal decomposition. The different combinations of oleylamine, or polyethyleneglycol (PEG) and triphenylphosphine, were added as surfactants to control the particle size. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-Vis) spectroscopy, photoluminescence spectroscopy (PL), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to depict the phase and morphology. The synthesized ZrO₂ nanoparticles have a cubic structure. The FT-IR spectrum showed the purity of obtained ZrO₂ nanocrystals with cubic phase. The UV-Visible absorption peak for ZrO₂ was observed at 233 nm (5.3 eV in photon energy). The band at 363 nm for cubic ZrO₂ nanocrystals was found.     

Investigation on the pH‐independent photoluminescence emission from carbon dots impregnated on polymer matrix

Highly luminescent, polymer nanocomposite films based on poly(vinyl alcohol) (PVA), and monodispersed carbon dots (C‐dots) derived from multiwalled carbon nanotubes (MWCNTs), as coatings on substrates as well as free standing ones are obtained via solution‐based techniques. The synthesized films exhibit pH‐independent photoluminescence (PL) emission, which is an advantageous property compared with the pH‐dependent photoluminescence intensity variations, generally observed for the C‐dots dispersed in aqueous solution. The synthesized C‐dots and the nanocomposite films are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infra‐red spectroscopy ( FTIR), ultraviolet (UV) ? visible spectroscopy and photoluminescence spectroscopy (PL) techniques. The TEM image provides clear evidence for the formation of C‐dots of almost uniform shape and average size of about 8 nm, homogeneously dispersed in aqueous medium. The strong anchoring of C‐dots within the polymer matrix can be confirmed from the XRD results. The FTIR spectral studies conclusively establish the presence of oxygen functional groups on the surfaces of the C‐dots. The photoluminescence (PL) emission spectra of the nanocomposite films are broad, covering most part of the visible region. The PL spectra do not show any luminescence intensity variations, when the pH of the medium is changed from 1 to 11. The pH‐independent luminescence, shown by these films offers ample scope for using them as coatings for designing diagnostic and imaging tools in bio medical applications. The non‐toxic nature of these nanocomposite films has been established on the basis of cytotoxicity studies.     

Quantitative characterization of virus-like particles by asymmetrical flow field flow fractionation, electrospray differential mobility analysis, and transmission electron microscopy

Here we characterize virus-like particles (VLPs) by three very distinct, orthogonal, and quantitative techniques: electrospray differential mobility analysis (ES-DMA), asymmetric flow field-flow fractionation with multi-angle light scattering detection (AFFFF-MALS) and transmission electron microscopy (TEM). VLPs are biomolecular particles assembled from viral proteins with applications ranging from synthetic vaccines to vectors for delivery of gene and drug therapies. VLPs may have polydispersed, multimodal size distributions, where the size distribution can be altered by subtle changes in the production process. These three techniques detect subtle size differences in VLPs derived from the non-enveloped murine polyomavirus (MPV) following: (i) functionalization of the surface of VLPs with an influenza viral peptide fragment; (ii) packaging of foreign protein internally within the VLPs; and (iii) packaging of genomic DNA internally within the VLPs. These results demonstrate that ES-DMA and AFFFF-MALS are able to quantitatively determine VLP size distributions with greater rapidity and statistical significance than TEM, providing useful technologies for product development and process analytics.     

Fluorescence Quenching of CdTe Nanocrystals by Bound Gold Nanoparticles in Aqueous Solution

Water-soluble gold nanoparticles with an average diameter of 5 nm were prepared with carboxylic acid terminated thiol ligands. These ligands contain zero to eight methylene moieties. CdTe nanocrystals with an average diameter of 5 nm were synthesized with aminoethanethiol capping. These nanocrystals displayed characteristic absorption and emission spectra of quantum dots. The amine terminated CdTe nanocrystals and carboxylic-acid-terminated gold nanoparticles were conjugated in aqueous solution at pH 5.0 by electrostatic interaction, and the conjugation was monitored with fluorescence spectroscopy. The CdTe nanocrystals were significantly quenched upon binding with gold nanoparticles. The quenching efficiency was affected by both the concentration of gold nanoparticles in the complex and the length of spacer between the CdTe nanocrystal and Au nanoparticle. The observed quenching was explained using Förster resonance energy transfer (FRET) mechanism, and the Förster distance was estimated to be 3.8 nm between the donor–acceptor pair.     

Intraband optical activity of semiconductor nanocrystals

Here we review our three recently developed analytical models describing the intraband optical activity of semiconductor nanocrystals, which is induced by screw dislocations, ionic impurities, or irregularities of the nanocrystal surface. The models predict that semiconductor nanocrystals can exhibit strong optical activity upon intraband transitions and have large dissymmetry of magnetic‐dipole absorption. The developed models can be used to interpret experimental circular dichroism spectra of nanocrystals and to advance the existing techniques of enantioseparation, biosensing, and chiral chemistry.     

Seeded Synthesis of CdSe/CdS Rod and Tetrapod Nanocrystals

We demonstrate a method for the synthesis of multicomponent nanostructures consisting of CdS and CdSe with rod and tetrapod morphologies. A seeded synthesis strategy is used in which spherical seeds of CdSe are prepared first using a hot-injection technique. By controlling the crystal structure of the seed to be either wurtzite or zinc-blende, the subsequent hot-injection growth of CdS off of the seed results in either a rod-shaped or tetrapod-shaped nanocrystal, respectively. The phase and morphology of the synthesized nanocrystals are confirmed using X-ray diffraction and transmission electron microscopy, demonstrating that the nanocrystals are phase-pure and have a consistent morphology. The extinction coefficient and quantum yield of the synthesized nanocrystals are calculated using UV-Vis absorption spectroscopy and photoluminescence spectroscopy. The rods and tetrapods exhibit extinction coefficients and quantum yields that are higher than that of the bare seeds. This synthesis demonstrates the precise arrangement of materials that can be achieved at the nanoscale by using a seeded synthetic approach.     

Reducing Liposome Size with Ultrasound: Bimodal Size Distributions

Sonication is a simple method for reducing the size of liposomes. We report the size distributions of liposomes as a function of sonication time using three different techniques. Liposomes, mildly sonicated for just 30 sec, had bimodal distributions when surface-weighted with modes at about 140 and 750 nm. With extended sonication, the size distribution remains bimodal but the average diameter of each population decreases and the smaller population becomes more numerous. Independent measurements of liposome size using Dynamic Light Scattering (DLS), transmission electron microscopy (TEM), and the nystatin/ergosterol fusion assay all gave consistent results. The bimodal distribution (even when number-weighted) differs from the Weibull distribution commonly observed for liposomes sonicated at high powers over long periods of time and suggests that a different mechanism may be involved in mild sonication. The observations are consistent with the following mechanism for decreasing liposome size. During ultrasonic irradiation, cavitation, caused by oscillating microbubbles, produces shear fields. Large liposomes that enter these fields form long tube-like appendages that can pinch-off into smaller liposomes. This proposed mechanism is consistent with colloidal theory and the observed behavior of liposomes in shear fields.     

Elucidating the chemical and biochemical applications of Citrus sinensis-mediated silver nanocrystal

Abstract

Synthesis of nanoparticles using biodegradable source is safer and echo-friendly. Here, we describe the synthesis of polycrystalline silver nanocrystals using Citrus sinensis acting as both reducing and capping agents. After exposing the silver ions to orange extract, rapid reduction of silver ions led to the formation of stable silver nanocrystals due to the reducing and stabilizing properties of orange fruit juice. The synthesized silver nanocrystals were characterized using various analytical techniques like UV–vis spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The biochemical activity of the synthesized nanocrystals was studied in the light of affinity to bovine serum albumin using several biophysical methods like absorbance, fluorescence and circular dichroism spectroscopy. Cytotoxic activity of these nanocrystals was also studied against Hep-2 cell line using fluorescence microscopy. It was also found that the synthesized nanocrystals can sense mercuric ion down to 50?µM in the presence of a number of cations. Furthermore, we established that the silver nanoparticles can effectively catalyse the reduction of methylene blue by ascorbic acid. The present study will enrich our knowledge on the chemical and biochemical activities of green-synthesized silver nanocrystals.     

Reducing liposome size with ultrasound: bimodal size distributions

Sonication is a simple method for reducing the size of liposomes. We report the size distributions of liposomes as a function of sonication time using three different techniques. Liposomes, mildly sonicated for just 30 sec, had bimodal distributions when surface-weighted with modes at about 140 and 750 nm. With extended sonication, the size distribution remains bimodal but the average diameter of each population decreases and the smaller population becomes more numerous. Independent measurements of liposome size using Dynamic Light Scattering (DLS), transmission electron microscopy (TEM), and the nystatin/ergosterol fusion assay all gave consistent results. The bimodal distribution (even when number-weighted) differs from the Weibull distribution commonly observed for liposomes sonicated at high powers over long periods of time and suggests that a different mechanism may be involved in mild sonication. The observations are consistent with the following mechanism for decreasing liposome size. During ultrasonic irradiation, cavitation, caused by oscillating microbubbles, produces shear fields. Large liposomes that enter these fields form long tube-like appendages that can pinch-off into smaller liposomes. This proposed mechanism is consistent with colloidal theory and the observed behavior of liposomes in shear fields.     

Unimodal Tree Size Distributions Possibly Result from Relatively Strong Conservatism in Intermediate Size Classes

Tree size distributions have long been of interest to ecologists and foresters because they reflect fundamental demographic processes. Previous studies have assumed that size distributions are often associated with population trends or with the degree of shade tolerance. We tested these associations for 31 tree species in a 20 ha plot in a Dinghushan south subtropical forest in China. These species varied widely in growth form and shade-tolerance. We used 2005 and 2010 census data from that plot. We found that 23 species had reversed J shaped size distributions, and eight species had unimodal size distributions in 2005. On average, modal species had lower recruitment rates than reversed J species, while showing no significant difference in mortality rates, per capita population growth rates or shade-tolerance. We compared the observed size distributions with the equilibrium distributions projected from observed size-dependent growth and mortality. We found that observed distributions generally had the same shape as predicted equilibrium distributions in both unimodal and reversed J species, but there were statistically significant, important quantitative differences between observed and projected equilibrium size distributions in most species, suggesting that these populations are not at equilibrium and that this forest is changing over time. Almost all modal species had U-shaped size-dependent mortality and/or growth functions, with turning points of both mortality and growth at intermediate size classes close to the peak in the size distribution. These results show that modal size distributions do not necessarily indicate either population decline or shade-intolerance. Instead, the modal species in our study were characterized by a life history strategy of relatively strong conservatism in an intermediate size class, leading to very low growth and mortality in that size class, and thus to a peak in the size distribution at intermediate sizes.     

Particle Sizing of Liposomal Dispersions: A Critical Evaluation of Some Quasi-Elastic Light-Scattering Data-Analysis Software Programs

Abstract

The particle size of four liposomal dispersions was estimated by quasi-elastic light scattering. The data were analyzed by three different software programs. Comparing the estimated values for the average particle size and the particle size distribution, some differences became obvious. First, it was observed that the average values obtained by different calculation methods were hardly comparable, since some systematic deviations occurred. Comparing the estimated particle size distributions, the Malvern Automeasure software was shown to produce overly smoothed, broad monomodal distributions. On the other hand, the results of both the CONTIN and the Brookhaven ISDA package agreed much better with the particle size distributions estimated by image analysis of electron microscopic photographs, revealing that all samples studied were bimodal, containing small liposomes with a rather constant diameter as well as much bigger aggregates that were gradually broken down during sonication. Concerning the ISDA software in detail, more accurate results were obtained by the NNLS-based histogram method compared to the exponential sampling method. Overall, CONTIN seemed to yield the most reliable distributions, since the smaller liposomes were detected even in the unsonicated sample.     

The adequacy of aging techniques in vertebrates for rapid estimation of population mortality rates from age distributions

As a key parameter in population dynamics, mortality rates are frequently estimated using mark–recapture data, which requires extensive, long‐term data sets. As a potential rapid alternative, we can measure variables correlated to age, allowing the compilation of population age distributions, from which mortality rates can be derived. However, most studies employing such techniques have ignored their inherent inaccuracy and have thereby failed to provide reliable mortality estimates. In this study, we present a general statistical model linking birth rate, mortality rate, and population age distributions. We next assessed the reliability and data needs (i.e., sample size) for estimating mortality rate of eight different aging techniques. The results revealed that for half of the aging techniques, correlations with age varied considerably, translating into highly variable accuracies when used to estimate mortality rate from age distributions. Telomere length is generally not sufficiently correlated to age to provide reliable mortality rate estimates. DNA methylation, signal‐joint T‐cell recombination excision circle (sjTREC), and racemization are generally more promising techniques to ultimately estimate mortality rate, if a sufficiently high sample size is available. Otolith ring counts, otolithometry, and age‐length keys in fish, and skeletochronology in reptiles, mammals, and amphibians, outperformed all other aging techniques and generated relatively accurate mortality rate estimation with a sample size that can be feasibly obtained. Provided the method chosen is minimizing and estimating the error in age estimation, it is possible to accurately estimate mortality rates from age distributions. The method therewith has the potential to estimate a critical, population dynamic parameter to inform conservation efforts within a limited time frame as opposed to mark–recapture analyses.     

Tuneable luminescence properties of EDTA‐assisted ZnS:Mn nanocrystals from a yellow‐orange to a red emission band

Luminescence technology has been improved with the help of semiconductor nanoparticles that possess novel optical and electrical properties compared with their bulk counterpart. The aim of this study was to design semiconductor nanocrystals in their pure (ZnS) or doped form (ZnS:Mn) with different concentrations of Mn²⁺ ions by a wet chemical route stabilized by ethylenediamine tetra‐acetic acid (EDTA) and to evaluate their luminescence properties. The nanocrystals were characterized by physicochemical techniques such as X‐ray diffraction (XRD), High‐resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), EDS, and ultraviolet (UV)–visible light and photoluminescence (PL) studies. These results showed the presence of cubic phase and spherically shaped nanocrystals. A blue shift with respect to their bulk counterpart was observed. PL emission spectra were observed with a fixed blue peak and the yellow‐orange bands were red shifted towards the red region under the same excitation wavelength. The orange‐red bands were attributed to the radiation transition of electrons in 3d5 unfilled shells of Mn²⁺ ions [⁴T₁(⁴G)‐⁶A₁(⁶S)]; the ZnS matrix varied with Mn²⁺ concentration. Shift and increase in the intensity of the PL and absorption bands were observed with increase in Mn content. The study showed that Mn²⁺‐doped ZnS nanocrystal emission bands can be tuned from the yellow‐orange to the red regions under a controlled synthesis process and could be used as promising luminescent emitters in the biology field upon functionalization with suitable materials. Further studies on construction with various other materials will be useful for practical applications.     

Isocyanate crosslinked reactive starch nanoparticles for thermo-responsive conducting applications

Hydrophobic nanoparticles and nanocomposite films of 1,4-hexamethylene diisocyanate (HMDI)-modified starch nanoparticles (SNPs) have been synthesized at ambient temperatures. The platelet-like starch nanocrystals become pseudospherical after modification with HMDI and the size increases or decreases depending on diisocyanate concentration compared to the ungrafted particles as revealed by transmission electron microscopy (TEM) results. The obtained nanocrystals were characterized by means of the FT-IR and X-ray diffraction (XRD) techniques. When compared with the hydrophobic performance of the unmodified starch nanocrystals, that of crosslinked starch nanocrystals significantly increased. X-ray diffraction reveals that the crystalline structure of modified starch nanocrystals was preserved. The resulting hydrophobic starch nanoparticles are versatile precursors to the development of nanocomposites. The polyether-polyurethane crosslinked with SNPs nanocomposite film exhibited thermo-responsive electrical conductivity.     

Preparation of TiO2 anatase nanocrystals by TiCl4 hydrolysis with additive H2SO4

A new methodology was developed to synthesize uniform titania anatase nanocrystals by the hydrolysis of titanium chloride in sulfuric acid aqueous solutions at 0-90°C. The samples were characterized by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM), electron diffraction (ED), and an Energy dispersive X-ray spectroscopy (EDS). The effects of the reaction temperature, mole ratio of SO(4)(2-) to Ti(4+), and the calcinations temperature on the particle size and crystal phase were investigated. Depending on the acidity, the hydrolysis temperature, and the calcination temperature, rhombic anatase nanocrystals sizes in the range of 10 nm to 50 nm were obtained. In the additive of sulfuric acid, Raman spectra and electron diffraction confirmed that the nanoparticles are composed of anatase TiO(2). No other titania phases, such as rutile or brookite, were detected.     

The importance of size-frequency relationships for predicting ecological impact of zebra mussel populations

Although most physiological processes of bivalves are highly size-dependent in a non-linear manner, often only total densities of populations of freshwater bivalves such as the zebra mussel are reported rather than size-frequency information. This can cause serious errors when trying to predict or assess the environmental impacts of these filter feeders on planktonic communities or the role of their pseudofeces in transferring materials from the plankton to the benthos. We used a bioenergetics model to examine the effect that differing size-frequency distribution has on influencing total phytoplankton consumption and pseudofeces production. We constructed different size-frequency distributions of 1000 zebra mussels with the same mean length or same mean body mass for comparison. In addition, we used several size-frequency distributions from the published literature. The size-frequency distribution of a population had a tremendous impact on both total consumption and pseudofeces production with rates varying by more than an order of magnitude (43.5 g consumption by 1000 smaller mussels to 654 g for a population dominated by large mussels). These data emphasize the importance of knowing not only population density, but population size structure in order to accurately understand and predict the impacts of zebra mussels, or any filter feeder on pelagic and benthic communities. This work also demonstrates the usefulness of a tool such as our bioenergetics model for partitioning the relative impacts of densities and size on a variety of factors such as consumption and pseudofeces production.     

Molecularly engineered nanocomposites: layer-by-layer assembly of cellulose nanocrystals

Cellulose nanocrystals are promising as a new class of reinforcing material for the preparation of nanostructured composites. We report here the preparation of cellulose nanocrystal multilayer composites with poly(diallyldimethylammonium chloride) using layer-by-layer assembly (LBL) technique. The LBL assembly was characterized with UV-Vis spectroscopy and ellipsometry. The average thickness of a single bilayer was found to be 11 nm. AFM and SEM characterization revealed uniform coverage and densely packed cellulose crystal surface.