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As COVID-19 spreads over the world, the treatment of acute lung injury (ALI) has attracted much attention. Considering ubiquitin-specific protease (USP) 25 has been relevant to inflammation, this article focused on its role in ALI and its regulatory mechanism. Lipopolysaccharide (LPS) was applied to separately stimulate mice and human lung epithelial cells to establish in vivo and in vitro ALI models. To discover the effects of USP25 overexpression on mouse, lung pathology, inflammatory factor levels, edema, number of inflammatory cells, and downstream protein levels were evaluated. USP25 overexpression in mice could alleviate LPS-induced lung tissue lesions and edema, and reduce inflammatory factors and inflammatory cells. It also inhibited the levels of downstream TRAF6, MAPK pathway-related proteins, and Fos Proto-Oncogene (FOS) in vivo. Furthermore, BEAS-2B cells were transfected with TNF receptor-associated factor 6 (TRAF6) plasmids to study the role of TRAF6 in the regulatory mechanism of USP25. TRAF6 overexpression was found to reverse the functions of USP25 overexpression on cells. In conclusion, USP25 reduced ALI and inhibited inflammation in lung epithelial cells via regulating TRAF6/MAPK/FOS signaling.

Bacterial infection and oxidative stress are serious complications in emergency burn patients, as the increase of oxygen free radicals in burn wounds can aggravate vascular endothelial cell injury, make the wounds ischemic and hypoxic, and delay wound healing. Traditional dressings cannot meet the first-aid needs of burn patients. In this study, polycaprolactone/chitosan (PCL/CS) was used as an electrospun nanofiber matrix, and curcumin (CUR), a molecule with excellent anti-inflammatory and antioxidant properties, was introduced to construct polycaprolactone/ chitosan graft copolymer-zein-curcumin electrospun nanofibers (PCL/CS-ZE-CUR). The results of clinical experiments suggest that compared with traditional dressings, based on the excellent mechanical properties and antibacterial activity of PCL/CS, the new dressing can exhibit oxygen free radical-scavenging abilities of CUR to accelerate wound healing and is expected to provide a beneficial upgrade for wound emergency care.

A simple and effective approach to remove pesticide residues on vegetables is necessary for food safety. Ozone microbubbles treatment as an eco-friendly washing technique was investigated for three vegetables (celery, pakchoi and cowpea) collected from the field applied with five pesticides. The removal rates of five pesticide residues on cowpea by ozone microbubbles treatment were 15 %-47 % higher than that by ozone macrobubbles. Moreover, compared with the other four systemic pesticides, emamectin benzoate had a preferable removal rate (65 %-94 %) as a non-systemic pesticide with high water solubility. Through Mass Spectrometry (MS), the double-bonded structure of emamectin benzoate made it more possible to be removed chemically, carrying a degradation rate of 88 % at 25 min in water. Additionally, cowpea showed low removal (28 %-65 %) owing to its stomata and rough surface with SEM. Conclusively, this study demonstrated the potential of the ozone microbubble treatment on pesticide residues removal to enhance food safety.

Pesticides such as insecticides, fungicides, and herbicides play an important role in the global agricultural industry as they reduce the occurrence of crop diseases, kill pests, and remove weeds. On the other hand, these pesticides are a double-edged sword because they have both acute effects and chronic adverse effects on human health. The widespread use of pesticides has led to their persistence in soil, water, and agricultural products, thus posing a serious threat to public health. Therefore, the removal and analysis of pesticides are critical to protecting human safety and health. When removing pesticides from the environment, it is imperative to ensure high removal efficiency while preventing secondary pollution to the environment. Because of the low concentrations of pesticide residue in the environment, complex matrix, and large throughput of pesticide residue analysis, a low-cost fast pre-treatment technique that has strong selectivity and an enrichment effect on the target pesticide residue, with little environmental impact, is required. Plant biomass-derived biochar is obtained from wheat straw, corn cob, rice husk, etc. This material has a large specific surface area, high pore capacity, tunable surface functional groups, and good environmental compatibility, which make it an inexpensive and efficient adsorbent. Hence, there is a need to systematically review the knowledge regarding the application of plant-based biochar on pesticide removal and pesticide residue analysis. This paper reviews the application progress of plant biomass-derived biochar in the above mentioned two areas over the last decade. The pesticide removal applications include reducing the mobility of pesticides in soil, eliminating the pollution caused by chiral pesticides, loading pesticide-degrading bacteria, and releasing fertilizers sustainably when removing pesticide. As mentioned above, plant biomass-derived biochar has a large specific surface area, a high number of functional groups on the surface, and good environmental compatibility. Therefore, it can effectively remove pesticides or their metabolites from the environment without causing any secondary pollution. During pre-treatment, plan biomass-derived biochar is used as an adsorbent for dispersive solid-phase extraction, solid-phase microextraction, and magnetic solid-phase extraction to selectively adsorb organophosphorus and triazole pesticides in fruits and vegetables, as well as organochlorine pesticides in the aquatic environment. This paper also introduces the adsorption mechanism of plant biomass-derived biochar, where studies based on computational simulations such as the density functional theory, molecular dynamics simulation, and giant canonical Monte Carlo simulation are carefully discussed. The benefits of adopting computational simulations are also mentioned. Finally, this paper summarizes the advantages and disadvantages of using plant biomass-derived biochar in pesticide removal and pre-treatment, as well as the future research trends in this area.

In this study, poplar wood biochar modified with Fe

Background Pesticide residues in fruits and vegetables threaten food safety. Cleaning before eating is a usual way to remove pesticide residues, so it is very important to find the most efficient cleaning conditions for public health. However, many previous cleaning studies only focused on a single variable which required a large amount of time manpower and material resources. Plackett-Burman design (PBD) and response surface methodology can avoid the earlier-mentioned problems and have potential in studying the influence and interaction of multiple factors. In this study, the effect of five factors on the removal of triadimefon and boscalid from rape by ultrasonic washing was evaluated through PBD: pH of water, ultrasonic cleaning time, water temperature, initial residual concentration and volume of water. Results Temperature had a significant effect on the rate of triadimefon removal while the other four factors impacted boscalid removal greatly. A higher temperature was better for the removal rate of triadimefon. Under alkaline environment, when initial residual concentration and cleaning time increased with decreasing water volume, the removal rate of boscalid increased. Furthermore, the interactions among factors were obtained. The regression coefficients of fitting equations about triadimefon and boscalid were 0.9657 and 0.9738, respectively. Conclusion Changing pH of water, cleaning time, water volume and temperature during the washing process of rape through PBD designed experiments represents a valid strategy for improving the removal rate of two pesticides residue. This study provides a reference for ultrasonic cleaning conditions by a sink dishwasher, which has a positive effect on food safety. © 2021 Society of Chemical Industry.

The maximum residue limit (MRL) of emamectin benzoate in mango had not been legislated in China and no work had been done to determine the emamectin benzoate residue in mango. The aim of this study...

The solubility of 9 sparingly soluble pesticide active ingredients (PAIs) was predicted in 133 deep eutectic solvents (DESs) based on 7 hydrogen bond acceptors and 19 hydrogen bond donors, using a COSMO-RS model. 13 DESs with superior solubility of water-insoluble PAIs were screened out and verified with experiments. The actual measurement results agree well with the forecasting results. When compared with the solubility in pure water, some PAIs can even be mutually dissolvable with tetraethylammonium chloride: decanoic acid (1:2), tetrabutylammonium chloride: decanoic acid (1:3), and tetrabutylammonium chloride: phenol (1:5), such as butachlor, acetochlor, and metolachlor. IR and 1H NMR spectra suggested that hydrogen bonding between DESs and PAIs molecules played a crucial role in solvation. Crucially, the study indicated that it’s feasible to replace toxic organic solvents with DESs in emulsifiable concentrates formulations. The effects of different concentrations of tetraethylammonium chloride: decanoic acid (1:2) on the growth of wheat seedlings were also explored. The results showed that it did not affect the germination rate of wheat seeds, but with the increase of concentration, the growth indexes such as the lengths of shoots and roots grew shorter, the fresh weight of aboveground and underground decreased. This study not only provides COSMO-RS as a useful and reliable tool to screen DESs but also highlights that DESs can be an alternative to replace toxic and harmful organic solvents in emulsifiable concentrates (EC) formulations, which provide ideas and a basis for designing new green pesticide formulations.

The study developed a novel purification procedure with ion column-solid-phase extraction (IC-SPE) for analysis of fluroxypyr-meptyl and fluroxypyr in wheat samples by liquid chromatography tandem mass spectrometry. During the sample preparation, IC-SPE method was carried out with the column containing the selection of adsorbent materials and with the help of syringes to pull and push extract through adsorbents. Based on a modified quick, easy, cheap, effective, rugged, and safe sample preparation, the ratio of water (containing 0.1% formic acid) to extraction solvent, cleanup adsorbents, and IC-SPE cycle times was studied for analyzing the residues in wheat grain, seedling, straw, and soil. The mean recoveries ranged from 82 to 107% with relative standard deviations below 10% for all matrices. Good linearity was obtained at the range of 0.005~1.0 mg L−1 for the analytes in the selected matrices. The limit of quantification for target analytes was between 0.05 and 0.1 mg kg−1. A field trial including dissipation kinetics and terminal residue study was conducted under open field conditions at three sites during the year of 2015–2016 to monitor the residue level of fluroxypyr-meptyl and fluroxypyr in wheat and soil samples. The results suggested that the developed method was successfully applied to the routine monitoring of fluroxypyr-meptyl or fluroxypyr residues in practical samples.

1-decyl-3-methyl imidazolium bromide ([C10mim][Br]) aqueous solution was studied as an alternative to aromatic compounds of clethodim emulsifiable concentrate (EC). The solubility of clethodim in [C10mim][Br] aqueous solution (1253.19 g·L− 1) has been greatly improved compared with that in pure water (5.45 g·L− 1) when the mass fraction of [C10mim][Br] was 35%. The electrical conductivity, viscosity and average diameter of [C10mim][Br] aqueous solution were measured. The thermodynamic parameters of electrical conductivity indicate that [C10mim][Br] in aqueous solution can spontaneously occur micelle formation and micellization is an entropy-driven process. The result of the average diameter of [C10mim][Br] can proved the presence of the micelle. And a higher fluidity is more suitable for pesticide dissolution, but not too high. After storage stability test, clethodim formulation water-based with [C10mim][Br] aqueous solution was stable under three different temperatures. The result of bioassay of clethodim formulation water-based with [C10mim][Br] aqueous solution indicates that the new formulation has high herbicidal activity (df = 6, F = 5.871, P = 0.001).

In this work, quaternary ammonium based ionic liquids (ILs) are proven to be good candidates to act as green solvents/solubilizers for pesticide formulations. The surface activity of six ionic liquids ([M3CnN]X; M = CH3; n = 10, 12, 14; X = Cl, Br) was tested, along with the corresponding critical aggregation concentration (CAC), lowest surface tension (γCAC), maximum surface excess concentration (Γmax), minimum area per molecule (Amin) and higher adsorption efficiency (pC20), which were measured using several methods, including surface tension measurements, electrical conductivity measurements, steady-state fluorescence measurements and 1H NMR. The thermodynamic parameters of micellization, the viscosities and the activation energies of the six ILs in 30% aqueous solutions, over the temperature range of 288–308 K, were determined and calculated. The results indicated that the solubilities of representative pesticides (metolachlor, acetochlor, clethodim, thiamethoxam, prochloraz, acetamiprid and fosthiazate) in different concentrations of these ILs were significantly higher than in pure water, especially for prochloraz (e.g., 137.2 g L−1 in 30% C10Br, 4035 times higher than in pure water). The microenvironment existing between the pesticide and micelle was investigated using 1H NMR techniques, revealing that micelle localization of pesticide molecules and a change in micelle conformation occurred in the dissolving process.

In this study, a rapid, sensitive, and selective method was established for the detection of oxathiapiprolin and the metabolite IN-E8S72, as well as its glucose conjugate IN-SXS67 in cucumber using modified QuEChERS procedure combined with HPLC-MS/MS. The LOQs for all compounds were 0.02 mg kg-1, and the average recoveries were 77.4-111.3% with RSDs of 1.0-8.5%. Under the optimized conditions, the established method was successfully used to determine field samples in dissipation and terminal residue studies. The dissipation study results showed that oxathiapiprolin dissipated rapidly in cucumber with half-lives of 2.4-4.0 days. On the basis of the terminal residue results, the risk assessment was conducted, and both the international estimated daily intake (IEDI) or national estimated daily intake (NEDI) of oxathiapiprolin were much less than 100% which indicate a low health risk to consumers. This work provides guidance for establishing MRL of oxathiapiprolin in China and is of great significance for evaluating its dietary risk in cucumber.

The control and removal of pesticide residues from possible pollution source by using improved methods without secondary pollution is essential for reducing its potential hazards to humans. In this work, a method of combining adsorption and degradation for the removal of pesticide residue was investigated based on the biodegradable microporous starch immobilized laccase (LA–MPS). Biosorbent of microporous starch (MPS) were prepared from maize starch by treating with glucoamylase and α -amylase to increase the specific surface area. Then, laccase with natural biological activity was immobilized on the surface of MPS, the prepared LA-MSP was characterized by SEM, FT-IR, activity assay and stability test. Moreover, LA–MPS coupled with mediators were applied to remove two typical triazine herbicides, atrazine and prometryn, in paddy field water sample. The physical action force between the LA–MPS and pesticide molecules resulted in the good adsorption of LA–MPS to the two pesticides. The apparent rate constants of laccase interaction with pesticide molecules were greatly improved by the adsorption process. Compared with natural degradation, the removal efficiency of atrazine and prometryn were increased by 61% in 7 days, which contributed by 43 ∼ 52% of degradation and 10 ∼ 38% of adsorption. These results indicated that the application of LA–MPS prepared by MPS sorbent was a feasible and green approach for the removal of pesticide residues in paddy field water sample.

Mixed ionic liquids (ILs) of 1-butyl-3-methylimidazolium bromide ([C4mim][Br], A) and 1-decyl-3-methylimidazolium bromide ([C10mim][Br], B) were used as solubilizers for six water-insoluble pesticides (i.e., metolachlor, acetamiprid, acetochlor, clethodim, thiamethoxam, and prochloraz). The solubilities of six pesticides were improved by increasing the B content of the mixed ILs. The aggregation behavior of the mixed IL systems was investigated by means of surface tension, conductivity, and fluorescence measurements. Enhancements in solubility were related to the surface activities of the mixed ILs, as indicated by measurements of their surface active and thermodynamic parameters. This work can reduce the cost and toxicity of using ILs, and the data shown in this paper provide valuable information for choosing a proper mixing proportion of suitable ILs for application to agriculture.

In line with the requirements of green chemistry, the preparation of eco-friendly pesticide formulations has become an inevitable development trend. In this work, we explored the feasibility of four new ionic liquids (ILs, [Octyl trimethyl ammonium] anions, anions = proline, valine, leucine, tartaric acid) as environmentally-friendly solvents for pesticide emulsifiable concentrates, and also as alternatives to traditional imidazole-based ILs since they do not contain the imidazole ring and the anions are natural substances. The results showed that the solubility of pesticides (clethodim, metolachlor, acetochlor, prochloraz, thiamethoxam, glyphosate, acetamiprid) in water with 25%w/v ILs was significantly improved, especially for acetamiprid, where the solubility was increased 19-fold, while it only increased about 4 to 5-fold after adding imidazole-based ILs in our previous work. In addition, the solubilization mechanism was explored by many methods and found that the solubilization effect does not completely depend on the critical micelle concentration (CMC) value but has a great relationship with the hydrophilicity of the ILs which may affect the size of micelles and release behavior to pesticides. Finally, 1H NMR was used to investigate the solubilization sites of ILs for glyphosate, and the interaction between pesticides and anions was explored by the quantum chemical method.

Biosorbents prepared with peanut shell and wheat straw were act as supports for the immobilization of Aspergillus laccase, and the redox mediator syringaldehyde (SA) was used to improve laccase-catalyzed degradation of nine pesticide residues, including isoproturon, atrazine, prometryn, mefenacet, penoxsulam, nitenpyram, prochloraz, pyrazosulfuron-ethyl and bensulfuron-methyl. Pesticides in water and soil samples were effectively removed via biosorbent concentration and subsequent immobilized laccase degradation on peanut shell or wheat straw supports. The Langmuir equation and Freundlich equation described the biosorption isotherms of the nine pesticides. Parameters that affect the degradation was also investigated. With concentration of pesticides and SA of 6.0 mg L−1 and 1 mmol L−1, over 54.5% and 65.9% of pesticides were removed in water in 3 days with a biosorbent immobilized laccase dose of 25 g L−1 for peanut shell immobilized laccase and wheat straw immobilized laccase, respectively. In the treatment of pesticide in soil with a biosorbent dose of 50 g (kg soil)−1, with the maximum degradation rates ranged from 20.9 to 92.9% and 14.7–92.0% in 7 days for peanut shell immobilized laccase and wheat straw immobilized laccase, respectively. Therefore, laccase immobilized on biomass materials has a strong potential for the effective removal of pesticide pollutants from water and soil by biosorption coupled with degradation.

Among eight ionic liquids (ILs) examined, 1-n-butyl-4-methyl-pyridinium bromide (BMPyBr, 5) was used in this study as an appropriate alternative to benzene homologs and derivatives to be used in 10 wt% water-insoluble difenoconazole emulsifiable concentrate (EC). Moreover, 10 wt% difenoconazole EC with BMPyBr (5) exhibited the same efficacy as 10 wt% difenoconazole wettable powder (WP) against powdery mildew on cucumbers under field conditions. The results revealed that difenoconazole EC with BMPyBr (5) had excellent stability at 268 K and 327 K after 14 days through high-performance liquid chromatography (HPLC). Therefore, ILs can be considered as promising environment-friendly adjuvants for pesticides that are commercially processed as EC formulation.

Ionic liquids may be considered as "environment-friendly solvents" for sparingly soluble pesticides. In this study, a series of aqueous ionic liquids (ILs) with different cations and different anions was used as environment-friendly alternative to harmful organic solvents sparingly dissolved in soluble pesticides (metolachlor, acetochlor, clethodim, thiamethoxam, and prochloraz). The aggregation behavior of aqueous ILs was investigated through surface tension measurement. Minimum area per IL molecule (Amin) values from the surface tension measurement showed that alkyl chain length and the halide anions strongly affect the aggregation behavior of ILs and the solubilization of pesticides. The solubility of metolachlor, acetochlor, clethodim, thiamethoxam, nitenpyram, and prochloraz in aqueous ILs increased. More importantly, the solubility of prochloraz in [C10mim][I] became 5771-fold higher than that in pure water. The substantially enhanced solubility of the above pesticides proved that aqueous ILs are promising environment-friendly solvents for pesticides that are commercially processed in emulsifiable concentrate (EC) formulation.

In this study, the ultrasonic dishwasher was used to remove five pesticides known to be frequently used on rape and grape. As compared with normal water washing, washing with the ultrasonic dishwasher was demonstrated to be more effective for pesticides removal, achieving removal rates between 14.7% and 59.8% on rape, and between 72.1% and 100% on grape. However, there were significant differences in order of the removal rate of five pesticides on rape and grape. From the adsorption experiments and analysis via Freundlich equation, the adsorption index (n, 0.551–1.056 on rape and 0.362–1.478 on grape) and adsorption coefficient (KF, 10−2.47–10−1.65 and 10−3.64–10−1.56 (mg·dm−2)/(mg·L−1)−n on rape and grape) were obtained. Taken together with the observation of the matrix surface by scanning electron microscopy and the evaluation of the physicochemical properties of pesticides, the different pesticides removal may be related to surface structure of the matrix.

Maquindox, 3-methyl-2-acetylquinoxaline-1,4-dioxide, is a quinoxaline-N,N-dioxide used in veterinary medicine as a feed additive. 1-Desoxymaquindox and 4-desoxymaquindox, two novel deoxidized metabolites of maquindox are synthesized from their parent drug. This study deals with the structural and spectral properties of the maquindox metabolites by employing experimental and theoretical methods. The investigation, using ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry, shows independent proof of the structures. Gauge-including atomic orbital NMR chemical shifts are calculated for isomeric quinoxaline metabolite pairs and several different parameters (correlation coefficient, mean absolute error, and corrected mean absolute error) are investigated. Comparison of the experimental and calculated 1 H and 13 C NMR chemical shifts allows the reliable assignment of the isomeric quinoxaline compound pairs.

A series of (o-alkylaminophenyl)diphenylphosphine ligands (P–N ligands) containing different alkyl carbon numbers or amino groups have been synthesized and characterized by IR and NMR (1H, 13C, 31P). The rhodium complexes ligated with P–N ligands in the hydroformylation of 1-hexene showed a considerable enhancement with the addition of water. NMR characterization studies suggested that the addition of water would engage in hydrogen bonding to the nitrogen atom of the coordinated P–N ligand, inhibiting the internal Rh–N interaction and generating more of the active unsaturated Rh-species that could react with 1-hexene to start the hydroformylation.

An amorphous Co-B catalyst was prepared by chemical reduction method and characterized by isothermal N2 adsorption/desorption, XRD, ICP-AES and HR-TEM. The catalytic activity of the Co-B catalyst in the hydroformylation of 1-octene was evaluated in a 100 mL stainless autoclave. Fresh amorphous Co-B catalyst showed a relatively high activity in the hydroformylation of 1-octene. The thermal stability of fresh Co-B catalyst was also examined. When fresh Co-B catalyst was thermally treated in N2 or H2 atmosphere at 200–500 °C for 2 h, the specific surface area and the catalytic activity of the Co-B catalyst decreased. When Co-B was supported on SiO2, the activity of the catalyst increased obviously. Compared with conventional supported Co/SiO2 catalyst, Co-B/SiO2 showed much higher activity than Co/SiO2. The influences of solvents and reaction conditions on the catalytic activity of the amorphous Co-B catalyst were also studied. The recycle test of the amorphous Co-B catalyst was done.

The catalyst Co-Ph3PO/PDMS/SiO2, Co-Ph3PO complex immobilized on polydimethylsiloxane (PDMS) functionalized SiO2, was prepared by sol-gel method. The characterizations of the catalysts were made by FT-IR, ICP-AES and N2 adsorption/desorption. The BET surface area, pore diameter and pore volume of the catalyst Co-Ph3PO/PDMS/SiO2 were smaller than that of pure SiO2 · ICP-AES showed that the content of cobalt of Co-Ph3PO/SiO2 was almost the same as that of Co-Ph3PO/PDMS/SiO2. The conversion of mixed octenes catalyzed by Co-Ph3PO/PDMS/SiO2 was 24.6 % (cobalt leaching was only 0.014% after the first run), which was two times about that of Co-Ph3PO/SiO2 (the conversion was only 11.6 , 25% cobalt leaching was observed after the first run). The immobilized catalyst Co-Ph3PO/PDMS/SiO2 could be reused six times without reducing the activity and selectivity.

A biphasic catalysis system composed of ionic liquid and rhodium complexes with water-soluble or amphiphilic phosphine ligands bearing water-soluble groups of sodium sulfonate have been employed for hydroformylation of 1-hexene. The experimental results show that the activity is almost independent of the hydrotropicity of the phosphine ligands in BMI·BF4. In this system, the extraction of phosphine species by the organics from the IL phase was quite low but larger than that of rhodium species and showed rather good stability of catalytic activity. A slight decrease in the aldehyde n/i ratio during the catalyst reuse could be recovered, in part, by replenishing certain amount of ligand into the used catalyst system.

Three surface active ionic liquids (ILs) containing organic anions but no halides were used as solubilizers for water insoluble pesticides and as well as alternates for similar ILs with halide anions, which have been increasingly popular in the agricultural practice. The solubilities of five pesticides (fluazifop-P, clethodim, pyrethrin, fosthiazate, and prochloraz) in three aqueous micellar systems, each containing 1-octyl-3-methylimidazolium--tartrate ([OMIM][Tart]), 1-octyl-3-methylimidazolium- l -proline ([OMIM][Prol]), 1-octyl-3-methylimidazolium- l -lactate ([OMIM][lact]), respectively, were measured. The solubilities of all five pesticides were found to increase with the increasing concentrations of ILs solubilzers The enhancements in solubilities were related to surface activities of these SAILs, as indicated in the results of the measurements of their corresponding critical aggregation concentration (CAC), lowest surface tension (γcac), maximum surface excess concentration (Γmax) and minimum area per molecule (Amin) of aqueous solutions of ILs. When comparing with similar ILs with halides as counter anions, we found that these ILs with organic counterions are at least comparable, often more effective solubilizers for all of the five very different pesticides we tested. We conclude that these novel SAILs with organic counterions would serve as at least similarly effective and more environmentally–friendly solubilizers over the more traditional ones with halides.

Two triphenylphosphine analogs, (4- tert -butylphenyl)diphenylphosphine ( 1 ) and bis-(4- tert -butylphenyl)phenylphosphine ( 2 ), have been synthesized for the preparation of Rh–P complexes with a formula of Rh(CO)Cl( L ) 2 ( L stands for the ligands 1 and 2 , respectively). Such Rh–P complexes were then attached to amino-group functionalized MCM-41 and MCM-48 for the hydroformylation of 1-hexene in the liquid phase. The supports and the heterogeneous catalysts were characterized by means of XRD, nitrogen adsorption–desorption, FT-IR, HRTEM and AAS. The heterogenized catalysts showed catalytic activity and normal heptanal selectivity comparable to the corresponding homogeneous ones; the advantage in the product selectivity towards the normal heptanal due to the larger cone angle of the ligands over Rh–PPh 3 in the homogeneous systems was also observed in the heterogeneous ones. Considerable interactions occurred between the surface amino-groups and the active rhodium species during the immobilization, resulting in highly dispersed active Rh-moieties and a significant modification in the catalytic stability.

The catalytic performances of rhodium complexes with three new amphiphilic phosphine ligands, bis-(3-sodium sulfonatophenyl)-(4-tert-butylphenyl)-phosphine (3), phenyl-(3-sodium sulfonatophenyl)-(4-tert-butyl-phenyl)-phosphine (4) and bis-(4-tert-butylphenyl)-(3-sodium sulfonatophenyl) phosphine (5), in hydroformylation of 1-hexene, 1-octene and 1-dodecene have been studied. The steric attributes of free ligands are investigated by Tolman's cone angle method through geometric optimizations. The results reveal that the new phosphines are surface-active as the typical surfactants and the corresponding rhodium complexes show significant enhancements in the reaction rate and higher selectivities toward the normal aldehydes in comparison with those obtained by triphenylphosphine trisulfonate (TPPTS)- and triphenylphosphine disulfonate (TPPDS) rhodium complexes under identical conditions.

Both interstitially Ag-doped Bi1.6Pb0.4Sr2Ca2Cu30y + x(wt%) Ag with x = 0.5, 1.0, 5.0, 10.0, 15.0, and substitutionally doped Bi1.6Pb0.4Sr2Ca2(Cu1-xAgx)0y with x = 0.025, 0.05, 0.10, 0.20, 0.40 systems were studied. Magnetic susceptibility Measurements indicate that both the interstitial and substitutional Ag-doping yield auch higher diaiagnetic signal for ZFC in a field of 60 0e at 5 K. At 80 K, -4πH/H was also enhanced by Ag-doping for H≤ 0.2. Possible explanation was discussed.