Synthesis and Application of Salicylhydrazone Probes with High Selectivity for Rapid Detection of Cu2.

Using the aldehyde amine condensation procedure and the triphenylamine group as the skeleton structure, the new triphenylamine-aromatic aldehyde-succinylhydrazone probe molecule DHBYMH was created. A newly created acylhydrazone probe was structurally characterized by mass spectrometry (MS), NMR, and infrared spectroscopy (FTIR). Fluorescence and UV spectroscopy were used to examine DHBYMH's sensing capabilities for metal ions. Notably, DHBYMH achieved a detection limit of 1.62 × 10-7 M by demonstrating exceptional selectivity and sensitivity towards Cu2+ ions in an optimum sample solvent system (DMSO/H2O, (v/v = 7/3); pH = 7.0; cysteine (Cys) concentration: 1 × 10-4 M). NMR titration, high-resolution mass spectrometry analysis, and DFT computation were used to clarify the response mechanism. Ultimately, predicated on DHBYMH's reversible identification of Cu2+ ions in the presence of EDTA, a molecular logic gate was successfully designed.

Highly selective and sensitive fluorescent probe possessing AIEE and ICT properties for rapid detection of Pb2+ in aqueous medium and its applications in living cells.

In this paper, a novel rapid, highly selective and sensitive Pb2+ fluorescent probe (E)-N'-((2-(4'-(diphenylamino)-[1,1'-biphenyl]-4-yl)-2H-1,2,3-triazol-4-yl)methylene) (DBTBH) was synthesized. The probe DBTBH not only exhibited more excellent selectivity and sensitivity to Pb2+ detection compared with other analytes (include metal ions and anions) in H2 O:THF solution (v:v = 9:1, 10 mM Tris-HCl, 1 mM KI, pH 7.4), but also had excellent optical properties such as aggregation-induced emission enhancement (AIEE) and intramolecular charge transfer (ICT). Detection limit of the probe DBTBH towards Pb2+ was 4.49 × 10-8 M. The possible mechanism was verified by 1 H NMR titration and HR-MS. Furthermore, the successful detection of Pb2+ by DBTBH in real water samples and HeLa cells indicated that DBTBH has great potential for selective recognition of Pb2+ in the natural environment and biological systems. These findings will provide a promising new idea for designing better Pb2+ fluorescent probes in the future.

Amidation modified waste polystyrene foam as an efficient recyclable adsorbent for organic dyes removal.

Modifying environmentally harmful waste polystyrene foam as an efficient recyclable adsorbent for organic dyes is important. Amidation modified polystyrene (PS-SD) was prepared by the Friedel-Crafts reaction and N,N'-dicyclohexylcarbodiimide (DCC) dehydration condensation reaction of waste polystyrene foam. PS-SD had highly efficient removal performance for organic dyes in large volume water sample solutions, and equilibrium was achieved in 0.5 h. The maximum adsorption capacities for Methylene blue (MB) and Congo red (CR) were 881.62 and 1,880.91 mg/g, respectively, at room temperature according to the Langmuir adsorption isotherm (R2 > 0.99). The kinetic data of the two dyes followed pseudo-second-order kinetics. The removal percentage remained high (>85%) after eight filtration-regeneration cycles. Experimental results showed that PS-SD was an excellent adsorbent for water treatment with high recyclability and long life.

Acylhydrazone-functionalized starch for efficient removal of hazardous dyes, heavy metal ion, and sulfides from wastewater: Adsorption behavior and mechanism analysis.

Herein, a novel acylhydrazone biosorbent (GSL) with abundant three-dimensional porous structure was successfully prepared by using low-cost starch as raw material for water pollution remediation applications. Various analytical techniques were applied to characterize the morphological structure and chemical composition. Interestingly, the adsorption efficiency of the adsorbent towards Malachite green (MG), Safranin O (SO), Cu2+, and sulfide in the static adsorption experiment was extremely high due to presence of ample functional groups. Additionally, the adsorption isotherm and kinetic experiments revealed that the adsorption processes were based on monolayer chemisorption. The maximum sorption amounts were 2237.4961 mg/g for SO, 2101.6610 mg/g for MG, 410.7019 mg/g for Cu2+, and 483.0194 mg/g for sulfides at 298.15 k. The thermodynamic analysis also demonstrated that all adsorption processes were spontaneous heat processes. The adsorption mechanism was analyzed by FTIR, SEM-EDAX and XPS. The adsorption of SO onto GSL reached 1025.8617 mg/g in continuous adsorption experiments, and the experimental data were fitted through the Thomas model and Yoon-Nelson model. Furthermore, the GSL showed good reusability and salt resistance. Importantly, starch-based acylhydrazone as the adsorbent for the simultaneous removal of hazardous dyes, heavy metal ions and sulfhides has not yet been seen reported.

Novel polyamide/silica/chitosan covalent hybrid: One-step BIC/sol-gel preparation at room temperature and dual applications in Hg2+ electrochemical probing and dye adsorption.

Room-temperature preparation of polymer-based covalent hybrids, which with multiple functional characteristics, is instrumental to overcome the performance shortcomings of single-polymer materials and broaden their applications thus. Herein, by introducing chitosan (CS) as a starting substrate into benzoxazine-isocyanide chemistry (BIC)/sol-gel reaction system, a novel polyamide (PA)/SiO2/CS covalent hybrid (PA-Si-CS) was successfully prepared in-situ at 30 °C. PA-Si-CS's chemical structure and elementary properties were characterized here. The introduction of CS combining with the presence of diverse N, O-containing segments (amide, phenol -OH, Si-OH, etc.) in PA-Si-CS provided its synergistic adsorption for Hg2+ and anionic dye Congo red (CR). The capture of PA-Si-CS for Hg2+ was rationally applied to the "enrichment"-type electrochemical probing of Hg2+. Relevant detection range, detection limit, interference, and probing mechanism were systematically analyzed. Compared with the experimental results of control electrodes, the electrode modified with PA-Si-CS (PA-Si-CS/GCE) showed a significantly enhanced electrochemical response to Hg2+, with a detection limit up to ~2.2 × 10-8 mol/L. In addition, PA-Si-CS also exhibited the specific adsorption for CR. Systematic analyses of dye adsorption selectivity, kinetics, isothermal models, thermodynamics, and adsorption mechanism told that PA-Si-CS can be used as an efficient CR adsorbent, with a maximum adsorption capacity of ~348 mg/g.

Preparation of benzenesulfonyl hydrazone modified guar gum and its adsorption properties for dyes and phytotoxicity assays.

Herein, a novel environmentally friendly benzenesulfonyl hydrazone modified guar gum (DGH) that carries excellent adsorption performance towards dyes was facilely prepared through oxidation and condensation. The structure, morphology, and physics-chemical of DGH were fully characterized by multiple analysis techniques. The as-prepared adsorbent yielded highly efficient separating performance towards multiple anionic and cation dyes, including CR, MG, and ST with the maximum adsorption capacity of 1065.3839 ± 10.5695, 1256.4467 ± 2.9425, and 1043.8140 ± 0.9789 mg/g at 298.15 K, respectively. The adsorption process well fitted the Langmuir isotherm models and the pseudo-second-order kinetic models. The adsorption thermodynamics revealed that the adsorption of dyes onto DGH was spontaneous and endothermic. The adsorption mechanism indicated that the hydrogen bonding and electrostatic interaction participated in the fast and efficient removal of dyes. Furthermore, the removal efficiency of DGH still remained above 90 % after six adsorption-desorption cycles, and the presence of Na+, Ca2+, and Mg2+ have weakly impacted the removal efficiency of DGH. The phytotoxicity assay was conducted via the germination of mung bean seeds, which confirmed the adsorbent can effectivity decreased the toxicity of dyes. Overall, the modified gum-based multifunctional material has good promising applications for wastewater treatment.

A "Turn-On" fluorescent probe for detection and removal of Zn2+ in aqueous and its application in living cells.

Using 3-hydroxy-2-naphthoic acid hydrazine and 4-(diethylamino) salicylaldehyde. as raw materials, compound L with an acylhydrazones structure was synthesized. The structure of compound L was characterized by nuclear magnetic resonance spectroscopy, X-ray single crystal diffraction, Fourier transform infrared spectroscopy, and mass spectrometry. The results show that Compound L can quickly and selectively recognize zinc ions in the H2O/DMSO (V:V = 3:7) solvent system. After that, the spectral performance of probe L was studied by fluorescence spectroscopy and UV-vis spectroscopy. The results show that the combination with Zn2+ can significantly enhance the fluorescence intensity of probe L while being almost unaffected by other coexisting ions. After that, Job's curve method, nuclear magnetic titration analysis, and mass spectrometry were used to study the binding mechanism of probe L and Zn2+. The results showed that probe L coordinated with Zn2+ is 1:1. The linear equations of different concentrations of Zn2+ and fluorescence intensity were obtained by fitting, and the detection limit of probe L for Zn2+ was determined to be 6.75 × 10-9 mol/L. The experimental study of standard addition and recovery showed that probe L could be used for the quantitative detection of Zn2+ in natural water samples. After that, we prepared L-doped sodium alginate hydrogel (SAL). The research results show that SAL has obvious adsorption capacity for Zn2+ in solution, and the color change before and after adsorption can be easily distinguished by the naked eye under ultraviolet light. SEM-EDS study showed that the microscopic morphology and composition of SAL changed significantly before and after adsorption. This fluorescent probe can be used for detection and removal of Zn2+ in aqueous solution. Also, probe L is effective for sensing for zinc (II) in living tumor cells. Overall, this work allows us to obtain a great potential to be applied to detect and remove Zn2+.

Highly efficient and selective adsorption of heavy metal ions by hydrazide-modified sodium alginate.

In the present study, a new potential adsorbent for the separation and removal of heavy metal ions was prepared using hydrazide modification. Characterization of structural and chemical properties of the absorbent indicated the dialdehyde sodium alginate (DSA) grafted adipic acid dihydrazide (AAD) plays a crucial role. The adsorption process correlated well with Freundlich isotherm and pseudo-second-order kinetics models. Additionally, the adsorption capacities for Hg2+, Pb2+, Cd2+, and Cu2+ were 7.833, 2.036, 4.766, and 3.937 mmol g-1, respectively. The thermodynamic parameter for the sorption demonstrated the process is endothermic and spontaneous. FT-IR and XPS analysis revealed the combination of chelation interactions and ion exchange between nitrogen, oxygen atoms and heavy metal ions. Moreover, after 10 times adsorption-desorption recycles, the adsorption efficiency of the adsorbent was slightly decreased. In conclusion, the as-prepared adsorbent has great potential in practical water pollution purification.

Effective removal of metal ions and cationic dyes from aqueous solution using different hydrazine-dopamine modified sodium alginate.

In this paper, DSA-AAD-DA and DSA-TPDH-DA were prepared to effectively remove metal ions and cationic dyes from aqueous solution. The hydrazone structure was prepared by hydrazide-modified SA which captured metal ions selectively, and the remaining functional groups were used as active adsorption sites for cationic dyes. The thermodynamic parameter for the sorption demonstrated the process is endothermic and spontaneous. In single process, the adsorption of metal ions by DSA-AAD-DA and DSA-TPDH-DA correlated well with the Freundlich model through the hydrazone structure coordination and ion exchange which was mainly chemical adsorption, and cationic dyes adsorption correlated well with the Langmuir model which was shown monolayer adsorption was dominant by hydrogen bonding, electrostatic interaction, and π-π interaction. In binary system, the mixed adsorption shown significant antagonism effect in high concentration, but cationic dyes and metal ions in low concentration were efficiently and simultaneously removed, the adsorption ability of DSA-TPDH-DA was much better than DSA-AAD-DA. Moreover, adsorption efficiency can still maintain more than 80% after five times adsorption-desorption recycle. Therefore, DSA-AAD-DA and DSA-TPDH-DA possessed great potential for wastewater treatment.

[Effects of exogenous melatonin on antioxidant capacity and nutrient uptake of Lolium perenne and Medicago sativa under drought stress]. / å¤–æºè¤ªé»‘ç´ å¯¹å¹²æ—±èƒè¿«ä¸‹é»‘éº¦è‰å’Œè‹œè“¿æŠ—æ°§åŒ–èƒ½åŠ›åŠå »åˆ†å¸æ”¶çš„å½±å“.

To explore the effects of exogenous melatonin on antioxidant capacity and nutrient uptake of plants under drought stress, we used Lolium perenne and Medicago sativa potted seedlings for foliar spraying and root application of 100 µmol·L-1 melatonin, respectively. We measured the biomass, malondialdehyde (MDA) content, relative conductivity, superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT) activities, as well as nutrient contents (organic carbon, total nitrogen, total phosphorus) under drought stress. The results showed that the biomass of L. perenne and M. sativa decreased significantly under drought stress, and that external melatonin application could effectively alleviate the inhibitory effect of drought stress on L. perenne and M. sativa. Foliar spray and root application of melatonin under drought stress enhanced L. perenne biomass by 14.5% and 29.6%, and that of M. sativa by 36.6% and 49.1%, respectively. The SOD and POD activities in L. perenne and SOD activity in M. sativa significantly decreased under drought stress, and exogenous melatonin significantly increased SOD, POD and CAT activities in L. perenne and M. sativa, reduced the accumulation of MDA in leaves, caused a significant decrease in the relative conductivity of leaves, and significantly increased antioxidant capacity. Drought stress and exogenous melatonin did not affect organic carbon content of L. perenne and M. sativa. Under drought stress, the contents of N and P in L. perenne leaves and roots and the content of N in M. sativa roots decreased, while the application of melatonin increased the contents of N and P in roots and leaves of L. perenne and M. sativa, indicating that melatonin could regulate the nutrient absorption of L. perenne and M. sativa under drought stress. In conclusion, the melatonin application not only improved the antioxidant capacity of plants, but also regulated nutrient uptake to enhance plant resilience to drought stress. Foliar spraying of melatonin was more effective than root application.

Highly Efficient Adsorption of Heavy Metals and Cationic Dyes by Smart Functionalized Sodium Alginate Hydrogels.

In this paper, functionalized sodium alginate hydrogel (FSAH) was prepared to efficiently adsorb heavy metals and dyes. Hydrazide-functionalized sodium alginate (SA) prepared hydrazone groups to selectively capture heavy metals (Pb2+, Cd2+, and Cu2+), and another functional group (dopamine grafting), serves as sites for adsorption methylene blue (MB), malachite green (MG), crystal violet (CV). Thermodynamic parameters of adsorption indicated that the adsorption process is endothermic and spontaneous. The heavy metals adsorption by FSAH was physical adsorption mainly due to ΔHθ < 40 kJ/mol, and the adsorption of cationic dyes fitted with the Langmuir models, which indicated that the monolayer adsorption is dominated by hydrogen bonds, electrostatic interactions, and π-π interactions. Moreover, the adsorption efficiency maintained above 70% after five adsorption-desorption cycles. To sum up, FSAH has great application prospect.

Interfacial engineered RDX/TATB energetic co-particles for enhanced safety performance and thermal stability.

1,3,5-Trinitro-1,3,5-triazinane (RDX) has attracted considerable attention in energy-related fields. However, the safety performance of RDX needs to be improved in terms of various external stimuli. Herein, such issues of RDX could be well balanced through hydrothermal assembly with the assistance of insensitive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) in a low content of 10 wt% (named RT co-particles). The TATB spread outside and were embedded inside of the resultant RT co-particles, which were examined via X-ray computed tomography and a three-dimensional laser scanning confocal microscope. As a result, the impact safety performance of RT co-particles could be drastically enhanced to 17.5 J by the TATB lubricant effect, demonstrating over twice the value of that of raw RDX (6 J) and mixtures (7 J). Moreover, an interfacial reconstruction between RDX and TATB was witnessed due to the strong interfacial interaction, as examined by theoretical simulation. Inspired by this, a delayed exothermic decomposition temperature of RT co-particles (244.4 °C) has been achieved when compared with that of RDX (241.4 °C). As demonstrated, an energetic co-particle strategy may provide an effective pathway toward remarkably improved mechanical and thermal safety performance, shedding light on other energetic materials.

Functionalized polymethyl methacrylate-modified dialdehyde guar gum containing hydrazide groups for effective removal and enrichment of dyes, ion, and oil/water separation.

In the study, a novel polymethacryloyl hydrazone modified guar gum adsorption material (GSA) was prepared via condensation between polyhydrazide and dialdehyde guar gum. GSA exhibited an abundant porous structure, higher selectivity for cationic pollutants in high-concentration wastewater like methylene blue (MB), malachite green (MG) dyes, and Cu2+. Under optimized experimental conditions, the maximum equilibrium adsorption capacity of MB, MG, and Cu2+ were 1418.36 mg/g, 1375.58 mg/g, and 196 mg/g, respectively. Adsorption isotherms and kinetics were well fitted with the Langmuir isotherm model and pseudo-second-order kinetic model. The thermodynamic analysis demonstrated that the adsorption process was endothermic, feasible, and spontaneous. Correspondently, the adsorption mechanism was explored by FTIR, SEM-EDS and XPS. The adsorbent was employed in disposing of local sewage water. Additionally, GSA successfully achieves efficient water/oil separation in different salt concentrations with a separation efficiency exceeding 99%.

Bifunctional cyclomatrix polyphosphazene-based hybrid with abundant decorating groups: Synthesis and application as efficient electrochemical Pb(II) probe and methylene blue absorbent.

HYPOTHESIS: The construction of novel functional cyclomatrix polyphosphazenes (CPPs) hybrid, which with diverse decorating groups, is a challenging task due to the structural limitation of available reaction substrates (phenols and amines). EXPERIMENTS: Herein, a phenolic hydroxyl (OH) modified ployamide derivative (P2) was successfully prepared via novel benzoxazine-isocyanide chemistry (BIC). A kind of CPP hybrid (P3), which with abundant functional groups (amide, tertiary amine, benzoxazine and phenolic hydroxyl) was prepared subsequently by the condensation between P2 and hexachlorocyclotriphosphazene (HCCP). Chemical structure, elemental composition, morphology, porous properties and crystallinity of P3 were systematically analyzed here. The electrochemical detection of lead ion (Pb2+) was realized by using P3-modified glassy carbon electrode (GCE/Nafion/P3) as the working electrode. Besides this, given the unique chemical structure and morphology of P3, the selective adsorption of methylene blue (MB) by P3 was also studied here. FINDINGS: Experimental results indicated that that P3 can act as bifunctional hybrid material to solve environmental issues.

A novel activation-hydrochar via hydrothermal carbonization and KOH activation of sewage sludge and coconut shell for biomass wastes: Preparation, characterization and adsorption properties.

A two-stage method of hydrothermal carbonization and chemical activation technology was applied to prepare a novel, large surface area and rich-pore structure activation-hydrochar from sludge sewage and coconut shell due to its mild, low-cost, and well-developed merits. The pore-making mechanism of activation-hydrochar was discussed by FT-IR, XPS, SEM, TG, TG-MS, XRD, and BET characterization. These results illustrated that the first stage of hydrothermal carbonization achieved the rich-pore structure hydrochar via dehydration, decarboxylation, deamination, and rearrangement reactions. The subsequent KOH activation was conducive to the pore-forming process. Specifically, the pore structure of activation-hydrochar was ameliorated and abundant active adsorption sites were obtained by the modification. The adsorption properties of activation-hydrochar on Methylene Blue (MB) and Congo Red (CR) were systematically investigated, and the max adsorption capacities of those were obtained with 623.37 mg/g and 228.25 mg/g, respectively. The pseudo-second-order kinetics and Langmuir models were both fit to elucidate the adsorption process for both dyes. Thermodynamics revealed adsorption performance accompanied by the spontaneous and endothermic processes. In general, the research clearly indicated the synthesis route for activation-hydrochar, and its further adsorption performance, capacity, and mechanism on MB and CR. This research demonstrated that activation-hydrochar with the abundant surface area and rich-pore structure made it a candidate for the production of effective adsorption material. It is prospective to achieve the utilization of wastes and its further application in wastewater treatment.

Magnetic cross-linked chitosan for efficient removing anionic and cationic dyes from aqueous solution.

Herein, a novel magnetic cross-linked chitosan CS-BA@Fe3O4 was rationally synthesized by cross-linked with epichlorohydrin and coated with Fe3O4 to the acylated chitosan, which was prepared by the reaction of chitosan with benzenetricarboxylic anhydride. The as-obtained absorbent was characterized by FTIR, XRD, VSM, TGA, TEM, BET, SEM and EDS. The results showed that the maximum adsorption capacities of CR and CV were 471.46 ± 16.97 mg/g and 515.91 ± 25.12 mg/g at 318.15 K, respectively. The main adsorption mechanisms were H-bonding and electrostatic interaction. The kinetic data were in good agreement with the pseudo-second-order model and closed to adsorption equilibrium at 30 min. Thermodynamic studies showed that the adsorption on CS-BA@Fe3O4 were spontaneous and endothermic. More importantly, the adsorbent exhibited excellent regeneration properties after 6 cycles and remarkable stability under harsh environments including strong acid, strong alkali, multi-salt and mixed dyes conditions. Therefore, abundant efforts revealed a broad application prospect of CS-BA@Fe3O4 in water remediation.

A new highly selective fluorescent turn-on chemosensor for cyanide anion.

A new simple molecule, 2-((2-phenyl-2H-1,2,3-triazol-4-yl)methylene)malononitrile (M1), was synthesized successfully by the Knoevenagel condensation reaction between 2-phenyl-1,2,3-triazole-4-carboxaldehyde and malononitrile. The receptor M1 is highly sensitive and selective to cyanide anion due to the nucleophilic addition of cyanide anion with M1. Distinct changes on UV-vis and fluorescence spectra can be detected with the addition of cyanide anion to the DMSO solution of M1. Optical properties of M1 were scarcely affected by the addition of other common background anions (F(-), Cl(-), Br(-), I(-), SCN(-), OH(-), CO4(2-), H2PO4(-), SO4(2-), HSO4(-), AcO(-), and NO3(-)) under the same condition. The detection limit of CN(-) reaches ~1.43 µM by M1 and the presence of background anions brought very slight interference for the detection of CN(-).

Tandem addition/cyclization reaction of organozinc reagents to 2-alkynyl aldehydes: highly efficient regio- and enantioselective synthesis of 1,3-dihydroisobenzofurans and tetrasubstituted furans.

The enantioselective addition of organozinc reagents to some 2-alkynyl benzaldehydes and the subsequent regioselective cyclization step was performed in one pot to form chiral 1,3-dihydroisobenzofurans with good product yields and excellent regio- and enantioselectivities. In the case of 2-alkynylcycloalkene aldehydes, tetrasubstituted furans were obtained in good product yields through a 1, 5-hydride shift of the preformed cyclization product.