Recent Trends in Foliar Nanofertilizers: A Review.

It is estimated that 40-70%, 80-90% and 50-90% of the conventional macronutrients N, P and K applied to the soil are lost, respectively, resulting in considerable loss of resources. Compared to conventional fertilizers, nanofertilizers have the advantages of controlled release, high nutrient utilization, low cost and relatively low environmental pollution due to their small size (1-100 nm) and high specific surface area. The application of nanofertilizers is an up-and-coming field of agricultural research and is an attractive and economical substitute for common fertilizers which can boost global food productivity sustainably. Foliar fertilization is a popular way to satisfy the needs of higher plants. Because of its small application dose, faster nutrient uptake than soil application and relatively less environmental pollution, foliar fertilization is more popular among plants. It can be seen that nanofertilizers and foliar fertilization are the hotspots of attention at present and that current research on the foliar application of nanofertilizers is not as extensive as that on soil application. Based on this background, this paper provides an overview of various applications of foliar spraying of nanofertilizers in agriculture, including applications in improving crop yield and quality as well as mitigating heavy metal stress, salt stress and drought stress.

An aptamer-based colorimetric/SERS dual-mode sensing strategy for the detection of sulfadimethoxine residues in animal-derived foods.

Residues of sulfadimethoxine (SDM) in animal-derived foods have attracted widespread public concern. Herein, we propose an aptamer-based colorimetric/SERS dual-mode sensing strategy for the determination of SDM based on hexadecyl trimethyl ammonium bromide (CTAB) induced aggregation of nanoparticles. In the absence of SDM, the SDM aptamer formed a supramolecular composite with CTAB, and the 4-mercaptopyrimidine functionalized gold nanoparticles (AuNPs@4-MPY) remained dispersed due to the lack of CTAB. Upon the addition of SDM, the SDM aptamer preferentially combined with SDM, resulting in the release of CTAB and subsequent aggregation of AuNPs@4-MPY, and the solution color changed from red to blue and presented a dynamic UV-absorbance curve based on different aggregation states. On the other hand, when, gold-silver core-shell nanoparticles (Au@AgNPs) were added additionally, the released CTAB narrowed the nanogap between AuNPs@4-MPY and Au@AgNPs, thus exhibiting enhanced SERS intensity of 4-MPY. This strategy achieved colorimetric detection of SDM with a linear range of 4.00-200.00 ng mL-1 and a detection limit of 2.41 ng mL-1, while SERS had a detection range of 1.20-120.00 ng mL-1 with a detection limit of 0.89 ng mL-1. This strategy is simple and cost-effective for the rapid detection of SDM within 20 minutes. It was further applied for the detection of SDM in spiked milk and honey samples with satisfactory recoveries. Therefore, it exhibits great potential for fast and on-site SDM detection.

Rapid determination of thiram and atrazine pesticide residues in fruit and aqueous system based on surface-enhanced Raman scattering.

In this work, a rapid and sensitive strategy was developed to determine thiram (THI) and atrazine (ATZ) by surface-enhanced Raman scattering (SERS) technology. ß-cyclodextrin modified silver nanoparticles (ß-CD-AgNPs) were synthesized using ß-CD as a reducing agent and encapsulating agent under alkaline conditions and employed as SERS substrate. The existence of ß-CD can capture the molecules to form host-guest complex and fix molecular orientation in its cavity, thus ensuring the enhanced SERS signal intensity of THI and ATZ. The linear response extends from 2.56 × 10-8 to 2.56 × 10-3 mol/L for THI and 3.08 × 10-8 to 3.08 × 10-3 mol/L for ATZ, with the limits of detection (LOD) of 2.42 × 10-9 mol/L for THI and 7.26 × 10-9 mol/L for ATZ, respectively. The application of the proposed method in real samples including apple and water were investigated, and the results would help promote the application of SERS technology as a powerful analytical tool for detecting other pesticide residues. It is expected that this SERS strategy will provide great value for rapid detecting pesticide residues in food products and environmental systems.

Determination of antihypertensive drugs irbesartan and doxazosin mesylate in healthcare products and urine samples using surface-enhanced Raman scattering.

In this paper, a surface-enhanced Raman scattering (SERS) strategy was constructed for the determination of antihypertensive drugs irbesartan (IRB) and doxazosin mesylate (DOX). ß-Cyclodextrin-capped silver nanoparticles (CD-AgNPs) are employed as SERS-active substrate. The introduction of ß-CD with hydrophobic cavity can capture drug molecules to form host-guest complex, making the drug molecules closer to the electromagnetic enhancement field of the AgNPs, thereby enhancing the SERS signal of drug molecules with low Raman cross-section. The vibrational modes of IRB and DOX are assigned by density functional theory calculations. The linear response from 3.0 × 10-7 to 1.0 × 10-5 mol L-1 for IRB and 3.0 × 10-7 to 2.0 × 10-5 mol L-1 for DOX and low limits of detection (LOD) 7.5 × 10-8 mol L-1 for IRB and 8.6 × 10-8 mol L-1 for DOX can be achieved. Meanwhile, this SERS approach can be applicable to determine IRB and DOX in commercial drug tablets, healthcare products, and human urine samples with recoveries of 90.8-115.7% and 90.0-113.5%, respectively, with relative standard deviation (RSD) less than 4.5%. This designed SERS strategy enables for the rapid determination of IRB and DOX in drug quality monitoring and illegal additives in healthcare products as well as clinical applications.

Au nanoparticles decorated covalent organic framework composite for SERS analyses of malachite green and thiram residues in foods.

A three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrate composed of gold nanoparticles (AuNPs) self-assembled covalent organic frameworks (COFs) was fabricated via the electrostatic interaction between positively charged COFs and negatively charged AuNPs, which exhibited excellent SERS performance and were successfully applied for the analyses of malachite green (MG) residue in different seafood products as well as thiram residue in several kinds of fruit juice. The raspberry-like structure SERS substrate has a larger surface area that can provide more adsorption sites in testing and improve the efficiency of sample enrichment. By using this developed SERS substrate, the detection linearity ranges are 1.0 × 10-9 mol·L-1-1.0 × 10-6 mol·L-1 for MG and 5.0 × 10-8 mol·L-1-1.0 × 10-5 mol·L-1 for thiram (R2 ≥ 0.995). The detection limits are 6.2 × 10-10 mol·L-1 for MG and 1.7 × 10-8 mol·L-1 for thiram, respectively. The COF-AuNPs substrate was actually applied for analysis of MG in seafood products and thiram in different fruit juice, with the recoveries in the ranges of 94.67-108.99 % for MG and 95.00-107.58 % for thiram, and both of the relative standard deviation (RSD) are no more than 5.88 %. This work indicates that the developed COF-AuNPs substrate is promising for SERS analyses and detections of residues in foods.

Metal-organic framework modified by silver nanoparticles for SERS-based determination of sildenafil and pioglitazone hydrochloride.

A versatile surface-enhanced Raman scattering (SERS) assay has been established that can realize rapid and sensitive determination of sildenafil (SIL) and pioglitazone hydrochloride (PIO) adulteration in healthcare products. Metal-organic frameworks-silver nanoparticles (MOFs-AgNPs) with SERS activity were successfully prepared via in situ synthesis AgNPs on the MOFs surface. By virtue of the adsorptivity of MOFs, the MOFs-AgNPs could effectively concentrate the drug molecules on the electromagnetic enhancement areas of AgNPs. Moreover, the MOFs-AgNPs substrate exhibited more sensitive SERS activity than classical AgNPs with linear range of 1.0 × 10-7-1.0 × 10-5 mol L-1 for SIL and 8.0 × 10-7-3.0 × 10-5 mol L-1 for PIO and limit of detection (LOD) of 4.8 × 10-8 mol L-1 for SIL and 1.4 × 10-7 mol L-1 for PIO. The designed method realized the determination of SIL and PIO in commercial tablets and healthcare products with recoveries of 93.8-108.0% and 93.0-104.0%, respectively, with relative standard deviation (RSD) of 2.7-4.1% and 2.2-4.2%, respectively. The present system displayed little interference effect on determination. This work provides a multifunctional route for the determination of other drugs via the SERS technology.

Rapid determination of propylthiouracil and methimazole by surface-enhanced Raman scattering based on sodium alginate-protected silver nanoparticles.

A rapid, ultrasensitive and selective method has been established to determine antithyroid drugs [propylthiouracil (PTU) and methimazole (MTZ)] by surface-enhanced Raman scattering (SERS). Silver nanoparticles (AgNPs) were synthesized by reduction of silver nitrate (AgNO3) with sodium alginate (SA) and were used as SERS substrates. Through optimization of the SERS conditions, including the volume of SA-protected AgNPs solution, pH of Britton-Robinson (BR) buffer solution and concentration of NaCl solution, linear responses were obtained for PTU and MTZ in the concentration ranges of 3.02 × 10-9-1.06 × 10-5 mol L-1 and 1.21 × 10-9-1.21 × 10-5 mol L-1, respectively. By the present method, the limits of detection (LODs) for the determination of PTU and MTZ were as low as 1.58 × 10-10 mol L-1 and 2.97 × 10-11 mol L-1. The method was successfully applied for the determination of PTU and MTZ in real samples. The recovery of PTU and MTZ from actual samples ranged between 97.20 and 104.80%, with relative standard deviations (RSDs) less than 3.63%.

Emissions of terbium metal-organic frameworks modulated by dispersive/agglomerated gold nanoparticles for the construction of prostate-specific antigen biosensor.

Herein, a universal and multifunctional fluorescence sensor platform is designed by the interaction of aggregation/dispersion gold nanoparticles (AuNPs) with Tb-metal-organic frameworks (Tb-MOFs). It is found that the dispersed AuNPs rather than the aggregated ones can quench effectively the fluorescence of Tb-MOFs, and the quenching process presumably involves the mechanism of inner filter effect (IFE), dynamic quenching effect (DQE), and fluorescence resonance energy transfer (FRET). The different affinities of aptamer and aptamer-target complex toward AuNPs are employed to modulate the fluorescence signal change of Tb-MOFs. As the proof of concept, prostate-specific antigen (PSA), an efficient tumor indicator for prostate cancer, is selected as the target. At first, the PSA aptamer can protect AuNPs against salt-induced aggregation, leading to the fluorescence of Tb-MOFs quenching. Subsequently, upon PSA introduction, the rigid aptamer-PSA complex is formed and cannot stabilize AuNPs in high salt conditions, so the AuNPs aggregate significantly and the fluorescence of Tb-MOFs is restored. The linear range of PSA is achieved from 1 to 100 ng/mL with a detection limit of 0.36 ng/mL. Finally, this method has been validated to be sensitive and specific for PSA in human urine samples. Graphical abstract.