Nanoparticles as stationary and pseudo-station+ary phases in chromatographic and electrochromatographic separations

To improve selectivity, chemical stability, and separation efficiency of chromatography, many past papers reported on nanoparticles (NPs) being used as stationary phases in chromatography. This article covers applications of NPs, including carbon nanotubes, fullerenes, gold NPs, silica NPs, zirconia NPs, and titanium-oxide NPs, as stationary phases in gas chromatography, high-performance liquid chromatography, capillary electrophoresis and capillary electrochromatography.We discuss the advantages and the disadvantages of nanomaterials as stationary phases compared to other materials, including traditional stationary phases. We also discuss future possibilities for developing nanomaterial-based stationary phases.     

On-line enhancement and separation of nanoparticles using capillary electrophoresis

We describe a rapid, simple, and highly efficient capillary electrophoresis (CE)-based method for the analysis of nanoparticles (NPs). In this study, we used the reversed electrode polarity stacking mode (REPSM) of CE to assess the feasibility of enhancing the detection of Au NPs and Au/Ag NPs, optimizing parameters such as the length of time for which the REPSM was applied, the concentrations of the buffer and the sodium dodecylsulfate (SDS) surfactant, and the pH. Under the optimized on-line enhancement conditions [buffer: SDS (40 mM) and 3-cyclohexylamino-1-propanesulfonic acid (CAPS; 10 mM) at pH 10.0; applied voltage: 20 kV; REPSM applied for 24s], the detection limits of the Au NPs and Au/Ag NPs increased by ca. 30- and 140-fold, respectively. In addition, when the NPs were subjected to on-line enhancement and separation by CE using diode array detection (DAD), this approach allowed chemical characterization of the NP species. Our results suggest that such CE analyses will be useful for accelerating the rates of fabrication and characterization of future nanomaterials.     

Disruption of supported lipid bilayers by semihydrophobic nanoparticles

Understanding the interaction between functional nanoparticles and cell membranes is critical to use nanomaterials for broad biomedical applications with minimal cytotoxicity. In this work, we have investigated the effect of adsorbed semihydrophobic nanoparticles (NPs) on the dynamics and morphology of model cell membranes. We have systematically varied the degree of surface hydrophobicity of carboxyl end-functionalized polystyrene NPs of varied size in buffer solutions with varied ionic strength. It is observed that semihydrophobic NPs can readily adsorb on neutral SLBs and drag lipids from SLBs to NP surfaces. Above a critical NP concentration, the disruption of SLBs is observed, accompanied with the formation and rapid growth of lipid-poor regions on NP-adsorbed SLBs. In the study of the effect of solution ionic strength on NP surface hydrophobic degree and the growth of lipid-poor regions, we have concluded that the hydrophobic interaction enhanced by screened electrostatic interaction underlies the envelopment of NPs by lipids that are attracted from SLBs to the surface of NPs or their aggregates. Hence, the formation and growth of lipid-poor regions, or vaguely referred as "pores" or "holes" in the literature, can be controlled by NP concentration, size, and surface hydrophobicity, which is critical to design functional nanomaterials for effective nanomedicine while minimizing possible cytotoxicity.     

Toxicity of nanomaterials

Nanoscience has matured significantly during the last decade as it has transitioned from bench top science to applied technology. Presently, nanomaterials are used in a wide variety of commercial products such as electronic components, sports equipment, sun creams and biomedical applications. There are few studies of the long-term consequences of nanoparticles on human health, but governmental agencies, including the United States National Institute for Occupational Safety and Health and Japan's Ministry of Health, have recently raised the question of whether seemingly innocuous materials such as carbon-based nanotubes should be treated with the same caution afforded known carcinogens such as asbestos. Since nanomaterials are increasing a part of everyday consumer products, manufacturing processes, and medical products, it is imperative that both workers and end-users be protected from inhalation of potentially toxic NPs. It also suggests that NPs may need to be sequestered into products so that the NPs are not released into the atmosphere during the product's life or during recycling. Further, non-inhalation routes of NP absorption, including dermal and medical injectables, must be studied in order to understand possible toxic effects. Fewer studies to date have addressed whether the body can eventually eliminate nanomaterials to prevent particle build-up in tissues or organs. This critical review discusses the biophysicochemical properties of various nanomaterials with emphasis on currently available toxicology data and methodologies for evaluating nanoparticle toxicity (286 references).     

Direct‐methanol Fuel Cell Based on Functionalized Graphene Oxide with Mono‐metallic and Bi‐metallic Nanoparticles: Electrochemical Performances of Nanomaterials for Methanol Oxidation

The catalysts based on 2‐aminoethanethiol functionalized graphene oxide (AETGO) with several mono‐metallic and bi‐metallic nanoparticles such as rod gold (rAuNPs), rod silver (rAgNPs), rod gold‐platinum (rAu‐Pt NPs) and rod silver‐platinum (rAg‐Pt NPs) were synthesized. The successful synthesis of nanomaterials was confirmed by various methods. The effective surface area (ESA) of the rAu‐Pt NPs/AETGO is 1.44, 1.64 and 2.40 times higher than those of rAg‐Pt NPs/AETGO, rAuNPs/AETGO and rAgNPs/AETGO, respectively, under the same amount of Pt. The rAu‐Pt NPs/AETGO exhibited a higher peak current for methanol oxidation than those of comparable rAg‐Pt NPs/AETGO under the same amount of Pt loading.     

Macrophage-Targeted Isoniazid–Selenium Nanoparticles Promote Antimicrobial Immunity and Synergize Bactericidal Destruction of Tuberculosis Bacilli

Pathogenesis hallmarks for tuberculosis (TB) are the Mycobacterium tuberculosis (Mtb) escape from phagolysosomal destruction and limited drug delivery into infected cells. Several nanomaterials can be entrapped in lysosomes, but the development of functional nanomaterials to promote phagolysosomal Mtb clearance remains a big challenge. Here, we report on the bactericidal effects of selenium nanoparticles (Se NPs) against Mtb and further introduce a novel nanomaterial-assisted anti-TB strategy manipulating Ison@Man-Se NPs for synergistic drug-induced and phagolysosomal destruction of Mtb. Ison@Man-Se NPs preferentially entered macrophages and accumulated in lysosomes releasing Isoniazid. Surprisingly, Ison@Man-Se/Man-Se NPs further promoted the fusion of Mtb into lysosomes for synergistic lysosomal and Isoniazid destruction of Mtb. Concurrently, Ison@Man-Se/Man-Se NPs also induced autophagy sequestration of Mtb, evolving into lysosome-associated autophagosomal Mtb degradation linked to ROS-mitochondrial and PI3K/Akt/mTOR signaling pathways. This novel nanomaterial-assisted anti-TB strategy manipulating antimicrobial immunity and Mtb clearance may potentially serve in more effective therapeutics against TB and drug-resistant TB.     

Recycling Functional Colloids and Nanoparticles

The stability and separation of colloids and nanoparticles has been addressed in numerous studies. Most of the work reported to date requires high cost, energy intensive approaches such as ultracentrifugation and solvent evaporation to recover the particles. At this point of time, when green science is beginning to make a real impact, it is vital to achieve efficient and effective separation and recovery of colloids to provide environmental and economic benefits. This article explores recent advances in strategies for recycling and reusing functional nanomaterials, which indicate new directions in lean engineering of high‐value nanoparticles, such as Au and Pd.     

Applications of Non-precious Transition Metal Oxide Nanoparticles in Electrochemistry

Non-precious transition metal oxide nanomaterials offer numerous opportunities for various cost-effective electrochemical applications. This review article features the design and advancement of such nanomaterials with unique features applied for the fabrication of electrochemical devices. Also, it discusses various new syntheses of transition metal oxide nanoparticles (TMO NPs) via multiple chemicophysical and biological procedures. Further, the novel appliances of the TMO NPs with varying sizes and morphologies are appraised. The advantages and challenges of a number of investigations on the TMO NPs towards electrochemical applications are addressed with their standpoint of cost-effectiveness, applicability, and the efficiency of the introduced nanostructures for the industrial applications.     

Mesoporous silica hybrid membranes for precise size-exclusive separation of silver nanoparticles

One-dimensional (1D) nanomaterials have unique applications due to their inherent physical properties. In this study, hexagonally ordered mesoporous silica hybrid anodic alumina membranes (AAM) were synthesized using template-guided synthesis with a number of nonionic n-alkyl-oligo(ethylene oxide), Brij-type (C(x)EO(y)), which are surfactants that have different molecular sizes and characteristics. The hexagonal mesoporous silicas are vertically aligned in the AAM channels with a predominantly columnar orientation. The hollow mesostructured silicas had tunable pore diameters varying from 3.7 to 5.1 nm. In this synthesis protocol, the surfactant molecular natures (corona/core features) are important for the controlled generation of ordered structures throughout AAM channels. The development of ultrafiltration membranes composed of silica mesostructures could be used effectively in separating silver nanoparticles (Ag NPs) in both aqueous and organic solution phases. This would be relevant to the production of well-defined Ag NPs with unique properties. To create a size-exclusive separation system of Ag NPs, we grafted hydrophobic trimethylsilyl (TMS) groups onto the inner pores of the mesoporous silica hybrid AAM. The immobilization of the TMS groups allowed the columnar mesoporous silica inside AAM to retain this inner pore order without distortion during the separation of solution-phase Ag NPs in organic solvents that may cause tortuous-pore membranes. Mesoporous TMS-silicas inside 1D AAM channels were applicable as a size-exclusive separation system to isolate organic solution-phase Ag NPs of uniform morphology and size.     

Ecotoxicity and analysis of nanomaterials in the aquatic environment

Nanotechnology is a major innovative scientific and economic growth area. However nanomaterial residues may have a detrimental effect on human health and the environment. To date there is a lack of quantitative ecotoxicity data, and recently there has been great scientific concern about the possible adverse effects that may be associated with manufactured nanomaterials. Nanomaterials are in the 1- to 100-nm size range and can be composed of many different base materials (carbon, silicon and metals, such as gold, cadmium and selenium) and they have different shapes. Particles in the nanometer size range do occur both in nature and as a result of existing industrial processes. Nevertheless, new engineered nanomaterials and nanostructures are different because they are being fabricated from the “bottom up”. Nanomaterial properties differ compared with those of the parent compounds because about 40–50% of the atoms in nanoparticles (NPs) are on the surface, resulting in greater reactivity than bulk materials. Therefore, it is expected that NPs will have different biological effects than parent compounds. In addition, release of manufactured NPs into the aquatic environment is largely an unknown. The surface properties and the very small size of NPs and nanotubes provide surfaces that may bind and transport toxic chemical pollutants, as well as possibly being toxic in their own right by generating reactive radicals. This review addresses hazards associated and ecotoxicological data on nanomaterials in the aquatic environment. Main weaknesses in ecotoxicological approaches, controversies and future needs are discussed. A brief discussion on the scarce number of analytical methods available to determinate nanomaterials in environmental samples is included.     

Macrophage‐Targeted Isoniazid–Selenium Nanoparticles Promote Antimicrobial Immunity and Synergize Bactericidal Destruction of Tuberculosis Bacilli

Pathogenesis hallmarks for tuberculosis (TB) are the Mycobacterium tuberculosis (Mtb) escape from phagolysosomal destruction and limited drug delivery into infected cells. Several nanomaterials can be entrapped in lysosomes, but the development of functional nanomaterials to promote phagolysosomal Mtb clearance remains a big challenge. Here, we report on the bactericidal effects of selenium nanoparticles (Se NPs) against Mtb and further introduce a novel nanomaterial‐assisted anti‐TB strategy manipulating Ison@Man‐Se NPs for synergistic drug‐induced and phagolysosomal destruction of Mtb. Ison@Man‐Se NPs preferentially entered macrophages and accumulated in lysosomes releasing Isoniazid. Surprisingly, Ison@Man‐Se/Man‐Se NPs further promoted the fusion of Mtb into lysosomes for synergistic lysosomal and Isoniazid destruction of Mtb. Concurrently, Ison@Man‐Se/Man‐Se NPs also induced autophagy sequestration of Mtb, evolving into lysosome‐associated autophagosomal Mtb degradation linked to ROS‐mitochondrial and PI3K/Akt/mTOR signaling pathways. This novel nanomaterial‐assisted anti‐TB strategy manipulating antimicrobial immunity and Mtb clearance may potentially serve in more effective therapeutics against TB and drug‐resistant TB.     

Self-assembly of DNA Nanostructures via Bioinspired Metal Ion Coordination

Despite a growing interest in DNA nanomaterials,their simple synthesis remains a challenge.A simple and general strategy for constructing DNA-based nanomaterials by metal ion coordination is reported.The me-tal-DNA nanoparticles(NPs)could be synthesized with DNA molecules of diverse sequence and various metal ions of intrinsic property,resulting in multifunctional NPs with the combined advantages of both inorganic and DNA building blocks.It is demonstrated that the hybrid metal-DNA NPs could be engineered for magnetic resonance and luminescence imaging,encapsulation of multifarious nucleic acids with controlled ratio,and co-assembly with small drug molecules.Furthermore,because these metal-DNA NPs exhibited enhanced cellular uptake compared to free synthetic DNA,they hold potential for applications in diagnostics and therapeutics.     

Analysis and applications of nanoparticles in the separation sciences: A case of gold nanoparticles

Nanometer-sized gold particles—gold nanoparticles (Au NPs)—are attracting a great deal of attention for their use in various technologies, including catalysis, optical and electronic devices, and separation science. In the emerging field of nanomaterials, the design, synthesis, and characterization of nanostructures are critical features because the manipulation of these structures has a direct effect on their resulting macroscopic properties. Nanostructures fabricated in layers on surfaces—for example, through self-assembly processes—have several potential applications in separation science. This review provides an introduction to the characterizations of Au NPs using size exclusion chromatography, high performance liquid chromatography (HPLC), and electrophoresis, and their self-assembly onto solid supports for analyses based on HPLC, gas chromatography, and capillary electrophoresis. In addition, sample concentration strategies involving the use of self-assembly approaches for surface modification of Au NPs are also discussed.     

π-Conjugated Copper Phthalocyanine Nanoparticles as Highly Sensitive Sensor for Colorimetric Detection of Biomarkers

Though numerous nanomaterials with enzyme-like activities have been utilized as probes and sensors for detecting biological molecules, it is still challenging to construct highly sensitive detectors for biomarkers using polymeric materials. Benefiting from the π-d delocalization effect of electrons, excellent metal-chelating property, high electron transferability, and good chemical stability of π-conjugated phthalocyanine, the design of the copper phthalocyanine-based conjugated polymer nanoparticles (Cu-PcCP NPs) as a colorimetric sensor for a variety of biomarkers is reported. The Cu-PcCP NPs are synthesized through a simple microwave-assisted polymerization, and their chemical structures are thoroughly characterized. The colorimetric results of Cu-PcCP NPs demonstrate excellent peroxidase-like detecting activity and also great substrate selectivity than most of the reported Cu-based nanomaterials. The Cu-PcCP NPs can achieve a detection limit of 4.88 μM for the H₂O₂, 4.27 μM for the L-cysteine, and 21.10 μM for the glucose via a cascade catalytic system, which shows comparable detecting sensitivity as that of many earlier reported enzyme-like nanomaterials. Moreover, Cu-PcCP NPs present remarkable resistance to harsh conditions, including high temperature, low pH, and excessive salts. These highly specific π-conjugated copper-phthalocyanine nanoparticles not only overcome the current limitation of polymeric material-based sensors but also provide a new direction for designing next-generation enzyme-like nanomaterial-based colorimetric biosensors.     

Identification and characterization of organic nanoparticles in food

Interest in nanoparticles (NPs) has increased explosively over the past two decades. Using NPs, high loadings of vitamins and health-benefit actives can be achieved in food, and stable flavors as well as natural food-coloring dispersions can be developed. Detection and characterization of NPs are essential in understanding the benefits as well as the potential risks of the application of such materials in food. While many such applications are described in the literature, methods for detection and characterization of such particles are lacking. Organic NPs suitable for application in food are lipid-, protein- or polysaccharide-based particles, and this review describes current analytical techniques that are used, or could be used, for identification and characterization of such particles in food products. We divide the analytical approaches into four sections: sample preparation; separation; imaging; and, characterization.We discuss techniques and reported applications for NPs or otherwise related particle compounds. The results of this investigation show that, for a successful characterization of NPs in food, at least some kind of sample preparation will be required. While a simple sample preparation may be satisfactory for imaging techniques for known analytes, for other techniques, a further separation using chromatography, field-flow fractionation or ion-mobility separation is necessary. Subsequently, photon-correlation spectroscopy and especially mass spectrometry techniques as matrix-assisted laser desorption/ionization combined with time-of-flight mass spectrometry, seem suitable techniques for characterizing a wide variety of organic NPs.     

Analysis of silica nanoparticles by capillary electrophoresis coupled to an evaporative light scattering detector

A simple and rapid methodology has been developed to identify and separate silica nanoparticles (SiO₂NPs) of different sizes in aqueous solution by capillary zone electrophoresis coupled to an evaporative light scattering detector (CE-ELSD). SiO₂NPs were separated using 3 mM ammonium acetate buffer, containing 1% methanol at pH 6.9. SiO₂NPs of 20, 50 and 100 nm were successfully separated under the optimum experimental conditions. CE coupled to ELSD has been proven to be an effective separation technique to determine particles with such small sizes, although the peaks are very close to each other, and it is a promising technique that may allow the separation of other types of nanoparticles. Confirmation by TEM and quantification of the SiO₂ content was also carried out by inductively coupled plasma-mass spectrometry (ICP-MS). The new method was applied to the analysis of real samples, in order to assess its ability to avoid matrix effects in the determination of SiO₂NPs in these kinds of samples.     

Recent Developments in the Plant‐Mediated Green Synthesis of Ag‐Based Nanoparticles for Environmental and Catalytic Applications

Among different metallic nanoparticles, sliver nanoparticles (Ag NPs) are one of the most essential and fascinating nanomaterials. Importantly, among the metal based nanoparticles, Ag NPs play a key role in various fields such as biomedicine, biosensors, catalysis, pharmaceuticals, nanoscience and nanotechnology, particularly in nanomedicine. A main concern about the chemical synthesis of Ag NPs is the production of hazardous chemicals and toxic wastes. To overcome this problem, many research studies have been carried out on the green synthesis of Ag NPs using green sources such as plant extracts, microorganisms and some biopolymers without formation of hazardous wastes. Among green sources, plants could be remarkably valuable to exploring the biosynthesis of Ag NPs. In this review, the green synthesis of Ag‐based nanocatalysts such as Ag NPs, AgPd NPs, Au?Ag NPs, Ag/AgPd NPs, Ag/Cu NPs, Ag@AgCl NPs, Au?Ag@AgCl nanocomposite, Ag?Cr‐AC nanocomposite and Ag NPs immobilized on various supports such as Natrolite zeolite, bone, ZnO, seashell, hazelnut shell, almond shell, SnO₂, perlite, ZrO₂, TiO₂, α‐Al₂O₃, CeO₂, reduced graphene oxide (rGO), h‐Fe₂O₃@SiO₂, and Fe₃O₄ using numerous plant extracts as reducing and stabilizing agents in the absence of hazardous surfactant and capping agents has been focused. This work describes the state of the art and future challenges in the biosynthesis of Ag‐based nanocatalysts. The fact about the application of living plants in metal nanoparticle (MNPs) industry is that it is a more economical and efficient biosynthesis biosynthetic procedure. In addition, the catalytic activities of the synthesized, Ag‐based recyclable nanocatalysts using various plant extracts in several chemical reactions such as oxidation, reduction, coupling, cycloaddition, cyanation, epoxidation, hydration, degradation and hydrogenation reactions have bben extensively discussed.     

In Situ Synthesis of Self‐Assembled Gold Nanoparticles on Glass or Silicon Substrates through Reactive Inkjet Printing

A facile and low cost method for the synthesis of self‐assembled nanoparticles (NPs) with minimal size variation and chemical waste by using reactive inkjet printing was developed. Gold NPs with diameters as small as (8±2) nm can be made at low temperature (120 °C). The size of the resulting NPs can be readily controlled through the concentration of the gold precursor and oleylamine ink. The pure gold composition of the synthesized NPs was confirmed by energy‐dispersive X‐ray spectroscopy (EDXS) analysis. High‐resolution SEM (HRSEM) and TEM (HRTEM), and X‐ray diffraction revealed their size and face‐centered cubic (fcc) crystal structure, respectively. Owing to the high density of the NP film, UV/Vis spectroscopy showed a red shift in the intrinsic plasmonic resonance peak. We envision the extension of this approach to the synthesis of other nanomaterials and the production of tailored functional nanomaterials and devices.     

Monitoring Stability and Sizes of Au/Pd Core/Shell Nanoparticles by SEC

This paper describes how size exclusion chromatography (SEC) can be used to rapidly characterize Au/Pd core/shell nanoparticles (NPs). We monitored the sizes of Au/Pd core/shell NPs by effecting SEC separation using a mobile phase of 10 mM sodium dodecyl sulfate (SDS); the plot of retention time with respect to the standard size of the Au NPs was linear (R ² = 0.991) for diameters falling in the range from 12.1 to 59.9 nm; for five consecutive runs, the relative standard deviations of these retention times were less than 0.4%. Under the optimized separation conditions, we found that the addition of the surfactant SDS stabilized the Au/Pd core/shell NP samples. In addition, SEC analysis revealed that the sizes of the Au/Pd core/shell NPs could be controlled via modification of the rate of addition of the reducing agent and the use of adequate volumes of the seed and shell precursor metal ion solutions. When using these conditions to analyze the Au/Pd core/shell NPs produced through seed-assisted synthesis, a good correlation existed between the sizes determined through SEC and transmission electron microscopy. Our results suggest that SEC is a useful technique for monitoring the sizes of NPs and nanomaterials in general.