Halogen-Bonded Organic Frameworks (XOFs) Based on N⋯Br+⋯N Bonds: Robust Organic Networks Constructed by Fragile Bonds.

Organic frameworks face a trade-off between the framework stability and the bonds dynamics, which necessitates the development of innovative linkages that enable stable frameworks without hindering efficient synthesis. While iodine(I)-based halogen-bonded organic frameworks (XOFs) have been developed, constructing XOFs based on bromine(I) is desirable yet challenging due to the high sensitivity of bromine(I) species. Here, we present the inaugural construction of stable bromine(I)-bridged two-dimensional (2D) halogen-bonded organic frameworks, XOF(Br)-TPy-BF4/OTf, based on sensitive [N…Br…N]+ halogen bonds. The formation of XOF(Br)-TPy-BF4/OTf was monitored by 1H NMR, XPS, IR, SEM, TEM, HR-TEM, SEAD. Their framework structures were established by the results from PXRD, theoretical simulations and SAXS. More importantly, XOF(Br) exhibited stable two-dimensional framework structures in various organic solvents and aqueous media, even over a wide pH range (pH 3-12), while the corresponding modelcompounds BrPy2BF4/OTf decomposed quickly even in the presence of minimal water. Furthermore, the influence of the counterions were investigated by replacing BF4 with OTf, which obviously improved the stability of XOF(Br). This characteristic enabled XOF(Br) to serve as efficient oxidizing reagents in aqueous environments, contrasting with the sensitivity of BrPy2BF4/OTf, which performed well only in organic media. This study opens new avenues for the development and application of multifunctional XOFs.

Lignin microcapsules prepared on the basis of flexible skeleton with high foliar retention and UV shielding properties.

Lignin-based microcapsules are extremely attractive for their biodegradability and photolysis resistance. However, the water-soluble all-lignin shells were unsatisfactory in terms of rainfall and foliar retention, and lacked the test of agricultural production practices. Herein, a novel microcapsule based on a flexible skeleton formed by interfacial polymerization and absorbed with lignin particles (LPMCs) was prepared in this study. Further analysis demonstrated that the shell was formed by cross-linking the two materials in layers and showed excellent flexibility and photolysis resistance. The pesticide loaded LPMCs showed about 98.68 % and 73.00 % improvement in scour resistance and photolysis resistance, respectively, as compared to the bare active ingredient. The foliar retention performance of LPMCs was tested in peanut plantations during the rainy season. LPMCs loaded with pyraclostrobin (Pyr) and tebuconazole (Teb) exhibited the best foliar disease control and optimum plant architecture, resulting in an increase in yield of about 5.36 %. LPMCs have a promising application prospect in the efficient pesticide utilization, by controlling its deformation, adhesion and release, an effective strategy for controlling diseases and managing plant growth was developed.

Trapping and reversing neuromuscular blocking agent by anionic pillar[5]arenes: Understanding the structure-affinity-reversal effects.

Selective relaxant binding agents (SRBA) have great potential in clinical surgeries for the precise reversal of neuromuscular blockades. Understanding the relationship between the structure-affinity-reversal effects of SRBA and neuromuscular blockade is crucial for the design of new SRBAs, which has rarely been explored. Seven anionic pillar[5]arenes (AP5As) with different aliphatic chains and anionic groups at both edges were designed. Their binding affinities to the neuromuscular blocking agent decamonium bromide (DMBr) were investigated using 1H NMR, isothermal titration calorimetry (ITC), and theoretical calculations. The results indicate that the capture of DMBr by AP5As is primarily driven by electrostatic interactions, ion-dipole interactions and C-H‧‧‧π interactions. The optimal size matching between the carboxylate AP5As and DMBr was ∼0.80. The binding affinity increased with an increase in the charge quantity of AP5As. Further animal experiments indicated that the reversal efficiency increased with increasing binding affinity for carboxylate or phosphonate AP5As. However, phosphonate AP5As exhibited lower reversal efficiencies than carboxylate AP5As, despite having stronger affinities with DMBr. By understanding the structure-affinity-reversal relationships, this study provides valuable insights into the design of innovative SRBAs for reversing neuromuscular blockade.

Photoinduced Photocatalyst-Free Cascade Cyclization of Alkynes with Sodium Sulfinates for the Synthesis of Benzothiophenes and Thioflavones.

The subject of this investigation is a new method for the construction of sulfonylated heterocycles which overcomes the limitations of classical approaches using a cheap feedstock sulfonylating agent, especially under photocatalyst- and metal-free conditions.

Encapsulation of Imazalil in HKUST-1 with Versatile Antimicrobial Activity.

Based on high surface areas, adjustable porosity and microbicide activity, metal-organic frameworks (MOFs) HKUST-1 are widely used as drug release carriers for their slow degradation characteristics under slightly acidic conditions. In this work, porous HKUST-1 was reacted rapidly by cholinium salt (as the deprotonation agent and template) in an aqueous solution at room temperature. A novel antimicrobial system based on an imazalil encapsulated metal organic framework (imazalil IL-3@HKUST-1) was established. Imazalil IL-3@HKUST-1 could achieve synergism in inhibiting pathogenic fungi and bacteria. Moreover, six days after treatment, the slow and constant release of imazalil from imazalil IL@HKUST-1 exhibited better sustainability and microbicidal activity than imazalil. We believe that the method may provide a new strategy for related plant diseases caused by bacteria or fungi.

Zeolitic Imidazole Framework-90-Based Pesticide Smart-Delivery System with Enhanced Antimicrobial Performance.

Multimodal antimicrobial technology is regarded as a promising strategy for controlling plant diseases because it enhances antimicrobial efficacy by blocking multiple pesticide-resistance pathways. In this work, a pH-responsive multimodal antimicrobial system was constructed based on ZIF-90 for the controlled release of kasugamycin (KSM). A series of physicochemical characterizations confirmed the successful fabrication of ZIF-90-KSM. The results indicated that the loading capacity of ZIF-90-KSM for KSM was approximately 6.7% and that the ZIF-90 nanocarriers could protect KSM against photodegradation effectively. The acid pH at the site of disease not only decompose the Schiff base bonds between KSM and ZIF-90, but also completely dissolved the nanocarriers. The simultaneous release of KSM and Zn2+ ions was able to achieve multimodal antimicrobial functions during disease occurs. A bioactivity survey indicated that ZIF-90-KSM had superior fungicidal activity and longer duration against Magnaporthe oryzae than KSM aqueous solution. In addition, the phytotoxicity assessment of ZIF-90-KSM on rice plants did not reveal any adverse effects. Therefore, ZIF-90-KSM prepared by Schiff base reaction has great potential for achieving synergistic antifungal functions and provides an eco-friendly approach to manage rice diseases.

Pectin functionalized metal-organic frameworks as dual-stimuli-responsive carriers to improve the pesticide targeting and reduce environmental risks.

Encapsulation of active ingredients into intelligent response controlled release carriers has been recognized as a promising approach to enhance the utilization efficiency and reduce the environmental risks of pesticides. In this work, an intelligent redox and pectinase dual stimuli-responsive pesticide delivery system was constructed by bonding pectin with metal-organic frameworks (FeMOF nanoparticles) which were loaded with pyraclostrobin (PYR@FeMOF-pectin nanoparticles). The successful fabrication of PYR@FeMOF-pectin nanoparticles was proved by a series of physicochemical characterizations. The results indicated that the loading capacity of PYR@FeMOF-pectin nanoparticles for pyraclostrobin was approximately 20.6%. The pectin covered on the surface of PYR@FeMOF nanoparticles could protect pyraclostrobin from photolysis and improve their spreadability on rice blades effectively. Different biological stimuli associated with Magnaporthe oryzae could trigger the release of pyraclostrobin from the pesticide-loaded core-shell nanoparticles, resulting in the death of pathogens. The bioactivity survey determined that PYR@FeMOF-pectin nanoparticles had a superior fungicidal activity and a longer duration against Magnaporthe oryzae than pyraclostrobin suspension concentrate. In addition, the FeMOF-pectin nanocarriers showed no obvious phytotoxicity and could enhance the shoot length and root length of rice plants. More importantly, PYR@FeMOF-pectin nanoparticles had an 8-fold reduction in acute toxicity to zebrafish than that of pyraclostrobin suspension concentrate. Therefore, the dual-responsive FeMOF-pectin nanocarriers have great potential for realizing site-specific pesticide delivery and promoting plant growth.

Detoxification of the Toxic Sulfur Mustard Simulant by a Supramolecular Antidote in Vitro and in Vivo.

Although great potential hazards and threats still occur from sulfur mustard, there are no specific medicine or therapy for the intoxication of sulfur mustard. Herein, we have demonstrated a supramolecular approach for the detoxification of the sulfur mustard simulant CEES (4) in vitro and in vivo by carboxylatopillar[5]arene potassium salts (CP[5]AK 1) efficiently based on host-guest interactions. The encapsulation of CEES (4) by the cavity of the pillar[5]arene 2 is driven by C-H···π interactions between CEES (4) and the electron-rich cavity of pillar[5]arene 2, which was investigated by 1H NMR titration, density functional theory studies, and the independent gradient model studies. CEES (4) is degradated to the reactive sulfonium salts quickly in aqueous media, resulting in the alkylation of DNA and proteins. The sulfonium salts can be encapsulated by CP[5]AK 1 efficiently, which accelerates the degradation of the sulfonium salts about 14 times. The cell and animal experiments indicated that the bioactivities of the sulfonium salts are inhibited with the formation of stable host-guest complexes, and CP[5]AK 1 has a good therapeutic effect on the damages caused by CEES (4) at either pre- or post-treatments. Due to the low cytotoxicity and good therapeutic effect, the anionic pillar[5]arenes are expected to be developed as specific antidotes against sulfur mustard (HD).

Fabrication of pH-responsive nanoparticles for high efficiency pyraclostrobin delivery and reducing environmental impact.

In this work, a pH-responsive pesticide delivery system using mesoporous silica nanoparticles (MSNs) as the porous carriers and coordination complexes of Cu ions and tannic acid (TA-Cu) as the capping agent was established for controlling pyraclostrobin (PYR) release. The results showed the loading capacity of PYR@MSNs-TA-Cu nanoparticles for pyraclostrobin was 15.7 ± 0.5% and the TA-Cu complexes deposited on the MSNs surface could protect pyraclostrobin against photodegradation effectively. The nanoparticles had excellent pH responsive release performance due to the decomposition of TA-Cu complexes under the acid condition, which showed 8.53 ± 0.37%, 82.38 ± 1.67% of the encapsulated pyraclostrobin were released at pH 7.4, pH 4.5 after 7 d respectively. The contact angle and adhesion work of PYR@MSNs-TA-Cu nanoparticles on rice foliage were 86.3° ± 2.7° and 75.8 ± 3.1 mJ/m2 after 360 s respectively, indicating that TA on the surface of the nanoparticles could improve deposition efficiency and adhesion ability on crop foliage. The control effect of PYR@MSNs-TA-Cu nanoparticles against Rhizoctonia solani with 400 mg/L of pyraclostrobin was 85.82% after 7 d, while that of the same concentration of pyraclostrobin EC was 53.05%. The PYR@MSNs-TA-Cu nanoparticles did not show any phytotoxicity to the growth of rice plants. Meanwhile, the acute toxicity of PYR@MSNs-TA-Cu nanoparticles to zebrafish was decreased more than 9-fold compared with that of pyraclostrobin EC. Thus, pH-responsive PYR@MSNs-TA-Cu nanoparticles have great potential for enhancing targeting and environmental safety of the active ingredient.

Diversity-oriented synthesis and antifungal activities of novel pimprinine derivative bearing a 1,3,4-oxadiazole-5-thioether moiety.

Based on the strategy of diversity-oriented synthesis and the structures of natural product pimprinine and streptochlorin, two series of novel pimprinine derivatives containing 1,3,4-oxadiazole-5-thioether moieties were efficiently synthesized under the optimized reaction conditions. Biological assays conducted at Syngenta showed the designed derivatives displayed an altered pattern of biological activity, of which 5h was identified as the most promising compound with strong activity against Pythium dissimile and also a broad antifungal spectrum in primary screening. Further structural optimization of pimprinine and streptochlorin derivatives is well under way, aiming to discover synthetic analogues with improved antifungal activity. Two series of novel pimprinine derivatives containing 1,3,4-oxadiazole-5-thioether moieties were efficiently synthesized through diversity-oriented synthesis strategy under the optimized conditions. Biological assays showed the designed derivatives exhibited potential activity.

N-(2-Aminoethyl)-2-(hexylthio) Acetamide-Functionalized Pillar[5]arene for the Selective Detection of l-Trp through Guest-Adaptive Multisupramolecular Interactions.

Tryptophan (Trp) is very necessary for biosystems; therefore, high-efficient detection of Trp is an important subject. Hereof, based on our early research works on fluorescent sensors, we rationally designed and synthesized a fluorescent sensor (SNP5) based on N-(2-aminoethyl)-2-(hexylthio) acetamide-functionalized pillar[5]arene, which showed high selectivity and sensitive recognition for l-Trp (LOD = 2.19 × 10-8 M). Moreover, SNP5 exhibited aggregation-induced emission enhancement fluorescence. Within SNP5, the pillar[5]arene group could act as N-H···π- and C-H···π-interaction sites, as well as a H-bond-interaction site; meanwhile, the N-(2-aminoethyl)-2-(hexylthio) acetamide group also served as a multihydrogen-bonding site. As a result, SNP5 could selectively detect l-Trp through the synergy of the pillar[5]arene group and the N-(2-aminoethyl)-2-(hexylthio) acetamide group. Compared with previous work, the results of this work support the strategy that changing the functionalized group of the pillar[5]arene can adjust the selectivity of the pillar[5]arene-based sensor and achieve the detection of different amino acids. The detection mechanism was specifically researched through experiments and theoretical calculations including frontier orbitals, electrostatic potential, and the independent gradient model approach. Interestingly, these theoretical calculations not only supported the experimental results but also provided a visualized understanding of guest-adaptive multisupramolecular interactions between SNP5 and l-Trp.

Tailoring an HSO4- anion hybrid receptor based on a phenazine derivative.

A catechol-functionalized phenazine imidazole (PD) was tailored with 2,3-diaminophenazine and 3,4-dihydroxy benzaldehyde, and it served as a hybrid acceptor for capturing HSO4- anions. The selectivity and sensitivity of the PD receptor for anion sensing were studied. It was found that the PD receptor could not only display a preferable sensitivity to HSO4- ions with a "turn-off" fluorescence response, but also have a strong anti-interference ability toward other common anions, especially basic anions such as CH3COO-, HPO42-, and H2PO4-. The anion recognition mechanism of PD towards HSO4- is based on multiple hydrogen bond interactions. Finally, the strips for anion detection were prepared, which were verified to be a convenient and high-efficiency test kit for detecting HSO4- ions with the naked eye.

A pillar[5]arene-based fluorescent sensor for sensitive detection of L-Met through a dual-site collaborative mechanism.

L-Methionine (L-Met) is one of the essential amino acids in human health, efficiently detect L-Met is a significant issue. Herein, a concept "dual-site collaborative recognition" had been successfully introduced into the design and achieved high selective and sensitive recognition of L-Met. In order to realize the "dual-site collaborative recognition", we rationally designed and synthesized an ester functionalized pillar[5]arene-based fluorescent sensor (SP5). And it shows blue Aggregation-induced emission (AIE) fluorescence. In the SP5, the pillar[5]arene group act as C-H···π interactions site, and ester group serve as multi hydrogen bonding acceptor. Interestingly, the SP5 exhibited high selectivity and sensitivity (2.84 × 10-8 M) towards L-Met based on the collaboration of electron-rich cavernous pillar[5]arene group and ester group through C-H···π and H-bond interactions, respectively. This "dual-site collaborative recognition" mechanism has been investigated by 1H NMR, ESI-MS and theoretical calculation including frontier orbital (HOMO and LUMO), electrostatic potential (ESP) and the noncovalent interaction (NCI). These theoretical calculations not only support the proposed host-guest recognition mechanism, but also provided visualized information on the "dual-site collaborative recognition" mode. Furthermore, the concept "dual-site collaborative recognition" is an effective strategy for easily detecting biological molecules.

Fabrication of smart stimuli-responsive mesoporous organosilica nano-vehicles for targeted pesticide delivery.

It is highly desirable to construct stimuli-responsive nanocarriers for improving pesticides targeting and preventing the pesticides premature release. In this work, a novel redox and α-amylase dual stimuli-responsive pesticide delivery system was established by bonding functionalized starch with biodegradable disulfide-bond-bridged mesoporous silica nanoparticles which loaded with avermectin (avermectin@MSNs-ss-starch nanoparticles). The results demonstrated that the loading capacity of avermectin@MSNs-ss-starch nanoparticles for avermectin was approximately 9.3 %. The starch attached covalently on the mesoporous silica nanoparticles could protect avermectin from photodegradation and prevent premature release of active ingredient. Meanwhile, the coated starch and disulfide-bridged structure of nanoparticles could be decomposed and consequently release of the avermectin on demand when nanoparticles were metabolized by glutathione and α-amylase in insects. The bioactivity survey confirmed that avermectin@MSNs-ss-starch nanoparticles had a longer duration in controlling Plutella xylostella larvae compared to avermectin emulsifiable concentrate. In consideration of the superior insecticidal activity and free of toxic organic solvent, this target-specific pesticide release system has promising potential in pest management.

Development of glycine-copper(ii) hydroxide nanoparticles with improved biosafety for sustainable plant disease management.

Cabbage black rot caused by Xanthomonas campestris pv. campestris (Xcc) leads to decrease of the production of up to 70%. Copper biocides are widely used to control this disease because of their low-cost application and broad-spectrum antimicrobial activities. Extensive spraying of traditional copper biocides would cause undesirable effects on plants and the environment. In this work, a novel copper-based microbicide was prepared by binding copper with glycine in sodium hydroxide solution (Gly-Cu(OH)2 NPs) and characterized by inductively coupled plasma atomic emission spectroscopy, high-resolution transmission electron microscopy, Fourier transformation infrared spectroscopy, and dynamic light scattering. The results showed that the prepared Gly-Cu(OH)2 NPs had a mean diameter of 240 nm with copper content more than 25.0% and their antimicrobial efficacies against Xcc were significantly better than Kocide 3000 at 400-800 mg L-1 of copper after spraying for 14 days. The phytotoxicity tests under greenhouse conditions showed that Gly-Cu(OH)2 NPs were safer to plants than Kocide 3000 and obviously promoted the growth of plants, which led to the increase of fresh weights of Chinese cabbage and tomato seedlings by 6.34% and 3.88% respectively at a concentration of 800 mg L-1 of copper. As a novel copper-based microbicide, the Gly-Cu(OH)2 NPs can improve effective utilization of copper-based bactericides and reduce phytotoxicity to plants and would be a potential alternative for sustainable plant disease management.

Aggregation-induced emission supramolecular organic framework (AIE SOF) gels constructed from tri-pillar[5]arene-based foldamer for ultrasensitive detection and separation of multi-analytes.

In this study, a novel aggregation-induced emission supramolecular organic framework (AIE SOF) with ultrasensitive response, termed FSOF, was constructed using a tri-pillar[5]arene-based foldamer. Interestingly, benefiting from the noise signal shielding properties of FSOF as well as the competition between the cationπ and ππ interactions, the FSOF shows an ultrasensitive response for multi-analytes, such as Fe3+, Hg2+ and Cr3+. The limits of detection (LODs) of the FSOF for Fe3+, Hg2+ and Cr3+ are in the range of 9.40 × 10-10-1.86 × 10-9. More importantly, the xerogel of FSOF exhibits porous mesh structures, which could effect high-efficiency separation above metal ions from their aqueous solution, with adsorption percentages in the range 92.39-99.99%. In addition, by introducing metal ions into the FSOF, a series of metal ions coordinated supramolecular organic frameworks (MSOFs) were successfully constructed. Moreover, MSOFs show selective fluorescence "turn on" ultrasensitive detection CN- (LOD = 2.12 × 10-9) and H2PO4- (LOD = 1.78 × 10-9). This is a novel approach to construct SOFs through a tri-pillar[5]arene-based foldamer, and also provides a new way to achieve ultrasensitive detection and high-efficiency separation.

Targeted release mechanism of λ-cyhalothrin nanocapsules using dopamine-conjugated silica as carrier materials.

Based on the specific binding between the receptors and ligands, novel targeted nanocapsules were prepared by using silica covalently bonded with dopamine to increase the insecticidal efficacy of λ-cyhalothrin. The targeted release mechanism of λ-cyhalothrin nanocapsules (NC) nanocapsules was verified by enzymatic analysis, fluorescent marking method and high performance liquid chromatograph. The results showed NC had uniform particle size (800 nm) and approximately 31% (w/w) loading efficiency of λ-cyhalothrin. The stability of λ-cyhalothrin in nanocapsuels was improved under different pH and temperature conditions. The NC showed sustainable release properties and the release kinetics mainly belonged to Fickian diffusion at all experimental conditions. Compared to λ-cyhalothrin emulsifiable concentrate and microcapsule suspension, the NC exhibited more excellent insecticidal activity. The micronucleus test indicated that NC significantly reduced the genotoxicity of λ-cyhalothrin to non-target organisms. This work offers a novel and efficient way to use targeted drug delivery system to improve the insecticidal activity, and may be extended to other pesticides in the future.

Development of triflumizole ionic liquids containing anions of natural origin for improving the utilization and minimizing the adverse impacts on aquatic ecosystems.

Triflumizole, a broad-spectrum systemic fungicide, has been widely used for the management of fungal diseases in plants. However, rapid photolysis and high risk to the aquatic environment limit its application. Ionic liquid (IL) forms of active pharmaceutical ingredients are innovative and promising agents that can optimize the application of the starting chemicals through the selection, or functionalization of the counterions (cation or anion). In this study, triflumizole was paired with various natural organic acids to develop novel ILs for improving the physicochemical properties and reducing the toxicity to fish. The results showed that the obtained ILs had low surface tension and lipophilicity and could protect triflumizole against degradation under UV irradiation as well as exhibit more excellent biological activity against Botrytis cinerea than triflumizole. The IL forms of triflumizole reduced the dosage and frequency of this fungicide, accordingly minimized the negative effect on environment. The IL contained salicylic acid as anion decreased > 4-fold toxicity to adult zebrafish over TFM. The results reported here create new application possibilities for imidazole fungicides and offer some heuristic rules for the design of active pharmaceutical ingredients-ionic liquids.

Lysobacter psychrotolerans sp. nov., isolated from soil in the Tianshan Mountains, Xinjiang, China.

A novel aerobic bacterial strain, designated ZS60T, with long, rod-shaped, Gram-staining-negative, aerobic cells was isolated from the soil in the Tianshan Mountains, Xinjiang, China. Phylogenetic analysis based on its 16S rRNA gene sequence indicated that strain ZS60T was affiliated with the genus Lysobacter, and was most closely related to Lysobacter daejeonensis GH1-9T (96.9 %), Lysobacter caeni BUT-8T (96.8 %) and Lysobacter ruishenii CTN-1T (96.7 %). The average nucleotide identity values between strain ZS60T, L. daejeonensis GH1-9T and L. ruishenii CTN-1T were 78.14 and 78.39 %, respectively. The DNA-DNA relatedness between strain ZS60T, L. daejeonensis GH1-9T and L. caeni BUT-8T were 44.8 and 39.1 %, respectively. The genomic DNA G+C content of the strain ZS60T was 67.7 mol% (draft genome sequence), and Q-8 was the predominant ubiquinone. The major cellular fatty acids of strain ZS60T were iso-C15 : 0 (23.4 %), iso-C17 : 0 (17.2 %) and iso-C17 : 1 ω9c (12.6 %). On the basis of genotypic, phenotypic and biochemical data, strain ZS60T is considered to represent a novel species of the genus Lysobacter, for which the name Lysobacterpsychrotolerans sp. nov. is proposed. The type strain is ZS60T (=CGMCC 1.15509T=NBRC 112614T).

Relationship between the Structure of Ionic Liquid and Its Enrichment Ability To Trace Fungicides from an Environmental Water Sample.

To elucidate the relationship between the structure of ionic liquid (IL) and its enrichment ability to trace pesticides from an environmental water sample, a series of imidazole-based ILs were synthesized to extract four fungicides (boscalid, cyprodinil, fluazinam, and pyrimethanil) through an in situ ionic liquid dispersive liquid-liquid microextraction method. The results showed that aromatic heterocyclic monocation ionic liquids (MILs) had better extraction ability to fungicides than other three alicyclic heterocyclic MILs. Dication ionic liquids (DILs) with the four carbons at the side chain had better ability to extract fungicides than MILs, and DILs with a long bridge carbon chain had better recoveries of fungicides with low Kow values. The proposed method showed high mean enrichment factors and high recoveries of the fungicides from real water samples. The rules of the relationship between the structure of IL and enrichment ability are instructive to the application of ILs in pretreatment of complex substances.