A Survey on Analytical Methods for the Characterization of Green Synthesized Nanomaterials.

Nowadays, nanotechnologies are well established and the uses of a great variety of nanomaterials show exponential growth. The development of green synthesis procedures experienced a great development thanks to the contribution of researchers of diverse origins. The versatility of green chemistry allows producing a wide range of organic and inorganic nanomaterials with numerous promising applications. In all cases, it is of paramount importance to carefully characterize the resulting nanomaterials because their properties will determine their correct performance to accomplish the function to which they were synthesized or even their detrimental effects like nanotoxicological behavior. This review provides an overview of frequently employed characterization methods and their applications for green synthesized nanomaterials. However, while several different nanoscale materials and their associated green construction methodology are being developed, other important techniques would be extensively incorporated into this field soon. The aim is to encourage researchers in the field to employ a variety of these techniques for achieving an exhaustive characterization of new nanomaterials and for contributing to the development of validated green synthesis procedures.

Surfactantless Emulsions Containing Eugenol for Imidacloprid Solubilization: Physicochemical Characterization and Toxicity against Insecticide-Resistant Cimex lectularius.

Synthetic insecticides have been used for a long time as one of the most effective tools for insect pest control. However, the re-emergence of insect pests and their fast development of resistance, as has occurred for pyrethroid-resistant bed bugs Cimex lectularius L., make it necessary to develop new and safe strategies for effective pest control. This has fostered the research on new eco-sustainable formulations based on essential oils, which allows reducing the impact associated with the intensive use of synthetic insecticides on the environment and their effects on human health. This research explores the stability of water/eugenol/ethanol surfactantless emulsions loaded with imidacloprid (0.003 wt%), and their toxicity against a resistant bed bug strain. The results have shown that these emulsions enable the solubilization of a poorly water-soluble drug, such as the imidacloprid, without any significant modification of their stability. Furthermore, the application of the obtained formulations against the pyrethroid-resistant bed bug results in mortality in the 50-85% range upon topical and spray applications, with the increase of the eugenol content enhancing the effectiveness of the formulations. It may be expected that the ternary water/eugenol/ethanol mixtures could be further developed in the preparation of ready to use formulations, enabling the dispersion of insecticides for pest control.

Silica Nanoparticles for Insect Pest Control.

To date, control strategies used against insect pest species are based on synthetic insecticide applications. In addition, the efficacy of these treatments could be decreased due to insecticide resistance in insect populations. Also, the irrational use of chemical control strategies has negative consequences of non-target organisms and threatening human health. Designing nanomaterial for pest insect control is a promising alternative to traditional insecticide formulations. In particular, it has been proven that silica nanoparticles have the potential for molecules delivery, release control improvement and also their toxicity as insecticide alone. In this work, we summarized the state of knowledge on silica nanoparticles (SiNPs) used in pest insect management. Besides, aspects of their synthesis, mode of action, and toxic effects on non-target organisms and environment are reviewed.

Evaluation of Resistance to Different Insecticides and Metabolic Detoxification Mechanism by Use of Synergist in the Common Bed Bug (Heteroptera: Cimicidae).

Bed bugs have become a common urban pest with consequences on human health and economic costs to the hotel and tourism sectors. Insecticide resistance is considered an important factor in the current bed bug resurgence, and multiple resistance mechanisms could be working in the resistant bed bug populations. In the present study, we determined the resistance profile to four insecticides with a different mode of action in Cimex lectularius L. (Heteroptera: Cimicidae) field-collected colonies from Argentina. Furthermore, the synergism effect of piperonyl butoxide (PBO) with deltamethrin was investigated to explore the contribution of detoxification metabolism to resistance. Our results showed that most of the field-collected colonies are extremely resistant to deltamethrin and propoxur, much more than to azametiphos and imidacloprid. The differences in resistance ratios among field-collected colonies could be associated with different modes of action of insecticides used in control pest and the mechanisms involved in the resistance. PBO pretreatment led to a significantly decreased RR in pyrethroid-resistant colonies, suggesting an upturn of monooxygenase activity for deltamethrin detoxification. However, the high RR detected could involve other mechanisms as part of the whole resistant phenotype in colonies of C. lectularius resistant to pyrethroids.

Pyrethroid Resistance Associated With a Decreased DEET Repellency in the Common Bed Bug (Hemiptera: Cimicidae).

The global resurgence of the bed bug (Cimex lectularius L.) and the widespread resistance of this insect to pyrethroid insecticides have created the need to find alternatives to chemical control. Thus, synthetic or natural repellents have been considered as a suitable choice to control bed bug infestations. Repellents not only keep insects away from their hosts, but also allow a decrease in insecticide selection pressure. The aim of this study was to evaluate the repellence effectivity of DEET against two bed bug colonies from Argentina (a susceptible one and a field-collected pyrethroid-resistant one), under two starving periods. We found different repellent effects of DEET on the two C. lectularius colonies and no differences between the two starving periods. In fact, DEET had a lower effect on the insecticide-resistant colony. The methodology used in this study proved to be useful to test the variation of the effect of DEET between pyrethroid-susceptible and -resistant bed bugs.

Beating the odds: Sustained Chagas disease vector control in remote indigenous communities of the Argentine Chaco over a seven-year period.

BACKGROUND: Rapid reinfestation of insecticide-treated dwellings hamper the sustained elimination of Triatoma infestans, the main vector of Chagas disease in the Gran Chaco region. We conducted a seven-year longitudinal study including community-wide spraying with pyrethroid insecticides combined with periodic vector surveillance to investigate the house reinfestation process in connection with baseline pyrethroid resistance, housing quality and household mobility in a rural section of Pampa del Indio mainly inhabited by deprived indigenous people (Qom). METHODOLOGY/PRINCIPAL FINDINGS: Despite evidence of moderate pyrethroid resistance in local T. infestans populations, house infestation dropped from 31.9% at baseline to 0.7% at 10 months post-spraying (MPS), with no triatomine found at 59 and 78 MPS. Household-based surveillance corroborated the rare occurrence of T. infestans and the house invasion of other four triatomine species. The annual rates of loss of initially occupied houses and of household mobility were high (4.6-8.0%). Housing improvements did not translate into a significant reduction of mud-walled houses and refuges for triatomines because most households kept the former dwelling or built new ones with mud walls. CONCLUSIONS/SIGNIFICANCE: Our results refute the assumption that vector control actions performed in marginalized communities of the Gran Chaco are doomed to fail. The larger-than-expected impacts of the intervention program were likely associated with the combined effects of high-coverage, professional insecticide spraying followed by systematic vector surveillance-and-response, broad geographic coverage creating a buffer zone, frequent housing replacement and residential mobility. The dynamical interactions among housing quality, mobility and insecticide-based control largely affect the chances of vector elimination.

Toxicological, Enzymatic, and Molecular Assessment of the Insecticide Susceptibility Profile of Triatoma infestans (Hemiptera: Reduviidae, Triatominae) Populations From Rural Communities of Santa Cruz, Bolivia.

A wide range of insecticide resistance profiles has been reported across Bolivian domestic and sylvatic populations of Triatoma infestans (Klug, 1834) (Hemiptera, Reduviidae), including some with levels proven to be a threat for vector control. In this work, the insecticide profile of domestic T. infestans was studied with standardized toxicological bioassays, in an area that has not undergone consistent vector control. F1 first-instar nymphs hatched in laboratory from bugs captured in three communities from the Santa Cruz Department were evaluated with different insecticides. Moreover, the enzymatic activity of esterases and cytochrome P450 monooxygenases was measured in individual insects to evaluate the possible mechanism of metabolic resistance to pyrethroids. In addition, the DNA sequence of sodium channel gene (kdr) was screened for two point mutations associated with pyrethroid resistance previously reported in T. infestans.All populations showed reduced susceptibility to deltamethrin and α-cypermethrin, albeit the RR50 values varied significantly among them. Increased P450 monooxygenases and permethrate esterases suggest the contribution, as detoxifying mechanisms, to the observed resistance to deltamethrin in all studied populations. No individuals presented either mutation associated to resistance in the kdr gene. The level of susceptibility to α-cypermethrin, the insecticide used by the local vector control program, falls within an acceptable range to continue its use in these populations. However, the observed RR50 values evidence the possibility of selection for resistance to pyrethroids, especially to deltamethrin. Consequently, the use of pyrethroid insecticides should be closely monitored in these communities, which should be kept under entomological surveillance and sustained interventions.

Innovative Immobilization Matrices.

We present a brief survey of some of the recent work of Professor Luis E. Díaz, performed together with his students and collaborators at the University of Buenos Aires. Dr Luis E. Díaz has been involved in research on biochemical and pharmaceutical sciences solving scientific and industry problems for over 40 years until he passed away. Prof. Díaz scientific interests included various topics from NMR spectroscopy to biomedicine but fundamentally he focused in various aspects of chemistry (analytical, organic, inorganic and environmental). This is not a complete survey but a sampling of prominent projects related to sol-gel chemistry with a focus on some of his recent publications.

Nanotoxicological Effects of SiO2 Nanoparticles on Spodoptera frugiperda Sf9 Cells.

The application of silica nanoparticles (NPs) in the biomedical field experienced a great development. The driving forces for these and future developments are the possibility to design NPs with homogeneous size and structure amenable to specific grafting. Moreover, it is possible to tune the characteristics of the NPs to meet the requirements of each specific cell and desired application. Herein, we analyzed the effect of silica NPs of various sizes and surface charge on the viability of Spodoptera frugiperda cells (Sf9 cell line) with the aim of extending the knowledge of possible toxicity of the NPs in the environment and development of new tools for insect control. Moreover, these results will also contribute to develop more effective systems for gene vectors delivery and recombinant proteins expression. Bare silica NPs of 14 nm, 380 nm and 1430 nm as well as amine-modified silica NPs of 131 nm and 448 nm were obtained by the Stöber method. The NPs were characterized by DLS and zeta potential measurements. The cell viability was assessed by the MTT test. It was observed that the 14 nm NPs possess the highest toxic effect. Indeed, after 24 h, the viability of the cells exposed to the lower concentration of NPs (0.12 mg/ml) was about 40% of the value obtained for the control cells not exposed to NPs. Moreover, the exposure to other negative charged NPs also causes a lower activity when compared with the control. Alternatively, lower concentrations of positive charged NPs (i.e.: 0.12 or 0.6 mg/ml) demonstrated to stimulate the proliferation of the cells and higher concentrations (i.e.: 7.2 mg/ml) did not present significant differences with the control. In conclusion, we have demonstrated that the NPs possess an effect that is highly influenced by the size, charge and concentration. Although, silica NPs are being used in the biomedical field, these results contribute to further understanding the risk that could be associated to nanoparticles and how these can be modified in order to meet the requirements of each desired application.