Dual-function Reagent Research Articles

Ether chain-modified Alkanolguanidine for CO2 capture and subsequent conversion

Capturing CO2 and converting it into valuable chemicals has attracted considerable attention in recent years. Herein, a kind of ether chain-modified alkanolguanidines (ECMAs) was designed and synthesized as a dual functional reagent for carbon dioxide capture and conversion. Due to the presence of basic sites and CO2-philic ether chains, these ECMAs demonstrated almost equimolar CO2 capture at room temperature and atmospheric pressure through the synergy of physical and chemical absorption. Even for diluted CO2 (15 % CO2), 0.7 mol CO2 per mole capture reagent can still be achieved, showing their potential application in post-combustion capture. The synthesized ECMAs can also serve as catalyst in the cycloaddition reaction of CO2 with various epoxides, affording 75–99 % yield of corresponding cyclic carbonates under 3 MPa CO2 with tetrabutylammonium iodide (TBAI) as co-catalyst. Moreover, these ECMAs can be applied to the integrated CO2 capture and conversion, in which the ECMAs can react with CO2, forming the alkyl carbonate zwitterion as active CO2 species in the capture step. And in the subsequent cycloaddition reaction with propylene oxide, 52 % yield of propylene carbonate was obtained.

Elastin-like polypeptide-functionalized nanobody for column-free immunoaffinity purification of aflatoxin B1.

A column-free immunoaffinity purification (CFIP) technique for sample preparation of aflatoxin B1 (AFB1) was developed using an AFB1-specific nanobody (named G8) and an elastin-like polypeptide (ELP). The reversible phase transition between liquid and solid in response to temperature changes was exhibited by the ELP which was derived from human elastin. The G8 was tagged with ELPs of various lengths (20, 40, 60, and 80 repeat units) at the C-terminus using recursive directional ligation (RDL). Coding sequences were then subcloned into pET30a at the multiple cloning sites. Bioactive recombinant proteins were produced by expressing them as inclusion bodies in Escherichia coli BL21 (DE3), then dissolved and refolded. Analysis by indirect competitive enzyme-linked immunosorbent assay (icELISA) and transition temperature (Tt) measurement confirmed that the refolded G8-ELPs preserved the ability to recognize AFB1 as well as phase transition when the temperature rose above Tt. To establish the optimal conditions for cleaning AFB1, the effects of various parameters on recovery were investigated. The recovery in ELISA tests was 95 ± 3.67% under the optimized CFIP workflow. Furthermore, the CFIP-prepared samples were applied for high-performance liquid chromatography (HPLC) detection. The recovery in the CFIP-HPLC test ranged from 54 ± 1.86% to 98 ± 3.58% for maize, rice, soy sauce, and vegetable oil samples. To the best of our knowledge, this is the first report combining the function of both nanobody and ELP to develop a cleanup technique for small molecules in a complex matrix. The CFIP for the sample pretreatment was easy to use and inexpensive. In contrast to conventional immunosensitivity materials, the reagent utilized in the CFIP was entirely biosynthesized without any chemical coupling reactions. This suggests that the nanobody-ELP may serve as a useful dual-functional reagent for the development of sample cleaning or purification methods.

Dual role tertiary amines in photocatalytic cyclizations: towards sustainable syntheses of 1,3-dinitrogen heterocycles.

A novel photocatalytic cascade has been engineered for the transformation of diketimines into 1,3-dinitrogen heterocycles, ingeniously repurposing methylamine a typically utilized sacrificial additive as a dual-function reagent, serving simultaneously as an electron donor and a methyl source. This innovation champions atom economy and underscores a commitment to sustainable chemical synthesis.

Direct in situ photolithography of ultra-stable CsPbBr3 quantum dot arrays based on crosslinking polymerization.

CsPbX3 (X = Br, Cl, I) perovskite quantum dots (PQDs) are the rising star for various display applications owing to their excellent opto-electrical properties, such as an adjustable spectrum, narrow emission linewidth and high quantum yield. However, these PQDs are well known to suffer from intrinsic instability under atmospheric conditions. In this work, a novel photosensitive ligand, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (XBPO), was employed as a dual-functional reagent for PQD surface engineering. The XBPO ligand could cleave to produce phenylphosphinyl radicals and trimethylbenzoyl radicals under UV light irradiation. The phenylphosphinyl radicals with PO bonds could effectively passivate the PQD surface defects, leading to quantum yield improvement. The CsPbBr3 and CsPbI3 PQDs with XBPO modification could achieve a photoluminescence quantum yield (PLQY) of near unity and 92%, respectively. Additionally, the in situ encapsulation of the PQDs was achieved by the subsequent crosslinking polymerization, which significantly improved the stability of the PQDs against solvents and the environment. By combining a standard photolithography procedure, we demonstrated a micro-pattern of CsPbBr3 PQDs. These results establish a universal route for PQD patterning, compatible with the existing photolithography processes, which could facilitate the application of PQDs in next-generation display technology.

A continuous flow investigation of sulfonyl chloride synthesis using N-chloroamides: optimization, kinetics and mechanism

We develop a continuous flow protocol for the synthesis of sulfonyl chlorides from disulfides and thiols, using 1,3-dichloro-5,5-dimethylhydantoin (DCH) as a dual-function reagent for oxidative chlorination.

Dual Functional Hydrogen Peroxide Boosted One Step Solvothermal Synthesis of Highly Uniform Sulfur Quantum Dots at Elevated Temperature and Their Fluorescent Sensing

The dual functional hydrogen peroxide (H2O2) assisted strategy for preparation of homogeneously distributed sulfur quantum dots (SQDs) with tunable size and prominent photoluminescence (PL) property is originally proposed via a one-pot solvothermal method. The synthesis of SQDs was demonstrated by treating sublimated sulfur powder and polyethylene glycol-400 (PEG-400) in the presence of H2O2 at elevated temperature. The H2O2 acts as a dual-functional reagent which could suspend the sulfur powder and etching bulk sulfur to construct uniform SQDs. At elevated temperature, the sulfur powder are easily transformed to molten sulfur which simultaneously acts as solvent. The as obtained SQDs exhibit a uniform size distribution, excellent PL properties with quantum yields (QYs) up to 10.3 %, superior dispersibility, and eminent photo stability. Moreover, morphology and element characterization reveal that the surface of spherical SQDs equipped with abundant oxidized sulphur species, while the diversification in the PL and QYs of SQDs under different reaction time are derived from the difference in their particle size which is proposed by the etching-assemble-etching process. Finally, the resultant SQDs was utilized as a sensitive iron ions (Fe3+) sensor with limit of detection (LOD) up to 10.80 nM as well as their investigation for fluorescent cellular imaging.

Radical Carbosulfonylation of Propellane: Synthesis of Sulfonyl β-Keto-bicyclo[1,1,1]pentanes

AbstractThe construction of multiply functionalized bicyclo[1.1.1]pentanes (BCPs) is of high synthetic value, as they are frequently harnessed as bioisosteres of 1,3-disubstituted benzene rings, alkynes, and tert-butyl groups in medicinal chemistry. Herein, we disclose a practical radical-mediated carbosulfonylation of propellane for the synthesis of sulfonyl β-keto-substituted BCPs by using vinyl sulfonates as dual-function reagent. This protocol features broad functional group tolerance and excellent atom-economy, leading to a variety of valuable difunctionalized BCP derivatives under mild photochemical conditions.

Radical-Mediated Remote Functional Group Migration.

Alkenes are ubiquitous in natural products and are extensively used as synthetic feedstocks in multiple fields including organic synthesis, medicinal chemistry, and materials science. Radical-mediated difunctionalization of alkenes provides a powerful tactic for alkene utilization. Despite the considerable progress made in the past several decades, state-of-the-art methods are highly dependent upon activated alkenes in which a proximal group with a π-electron system (e.g., aryl, carbonyl, and heteroatom) is requisite to stabilize the nascent alkyl radical intermediate via p-π conjugation or p orbitals of the heteroatom. In contrast, the transformation of unactivated alkenes, such as aliphatic alkenes, remains challenging.To overcome this obstacle, we have recently disclosed the strategy of intramolecular distal functional group migration (FGM), which has been efficiently applied in radical difunctionalization of unactivated alkenes. A portfolio of functional groups, such as cyano, heteroaryl, oximino, formyl, and alkynyl groups, showcase the excellent migratory aptitude. Mechanistically, after the addition of an extrinsic radical to the alkene, the newly formed active alkyl radical is rapidly captured by the intramolecular migratory group to generate a cyclic intermediate. Subsequent cleavage of the cyclic C-C bond of the intermediate leads to the functionalized product through the FGM process. Based on the strategy of FGM, a set of elusive difunctionalizations of unactivated alkenes have been accomplished (Part A).Alongside this research, an upgraded highly efficient synthetic strategy, "dock-migration," is created for intermolecular difunctionalization of alkenes. A diversity of sulfone-based dual-function reagents are developed. The intermolecular transformation is initiated by docking the dual-function reagent to the alkene, followed by intramolecular migration of the functional group. Compared to the original FGM protocol, the scope of alkenes is significantly extended from the strategically placed tertiary alcohol-substituted alkenes to general alkenes. Both activated and unactivated alkenes are well tolerated. By this approach, radical-mediated fluoroalkylheteroarylation, fluoroalkylalkynylation, and alkylation of alkenes have been achieved (Part B).Direct elaboration of C-H bonds into the targeted functional groups represents one of the most ideal and straightforward methods for molecular functionalization. The FGM strategy proves to be an ingenious tool for radical-mediated functionalization of remote unactivated C(sp3)-H bonds. Based on the FGM process, we have accomplished: (a) remote C(sp3)-H heteroarylation and cyanation of unprotected alcohols via the cascade of alkoxy radical-enabled hydrogen atom transfer (HAT) and intramolecular functional group (e.g., heteroaryl, cyano) migration, and (b) distal C(sp3)-H vinylation of propargylic alcohols through consecutive alkenyl radical-promoted HAT process and subsequent alkenyl migration (Part C).

RAGE-binding peptide-conjugated polyethylenimine as a dual-functional carrier: A RAGE-mediated gene carrier and an anti-angiogenic reagent

Receptor for advanced glycation end-products (RAGE) is overexpressed in various cancer cells. In this study, a RAGE-binding peptide (RBP) was conjugated to polyethylenimine (25kDa, PEI). RBP-conjugated PEI (PEI-RBP) was characterized as a dual-functional reagent, a RAGE-mediated gene carrier and an anti-angiogenic reagent. As a gene carrier, PEI-RBP had higher transfection efficiency to the C6 glioblastoma cells than PEI. As an anti-angiogenic reagent, the pEmpty/PEI-RBP complex reduced RAGE expression on the surface of the C6 glioblastoma cells. Also, the complex reduced the VEGF expression and tube formation of endothelial cells. Therefore, PEI-RBP may be useful for development of glioblastoma therapy.

Photoluminescent Cationic Carbon Dots as efficient Non-Viral Delivery of Plasmid SOX9 and Chondrogenesis of Fibroblasts

With the increasing demand for higher gene carrier performance, a multifunctional vector could immensely simplify gene delivery for disease treatment; nevertheless, the current non- viral vectors lack self-tracking ability. Here, a type of novel, dual-functional cationic carbon dots (CDs), produced through one-step, microwave-assisted pyrolysis of arginine and glucose, have been utilized as both a self-imaging agent and a non-viral gene vector for chondrogenesis from fibroblasts. The cationic CDs could condense the model gene plasmid SOX9 (pSOX9) to form ultra-small (10–30 nm) nanoparticles which possessed several favorable properties, including high solubility, tunable fluorescence, high yield, low cytotoxicity and outstanding biocompatibility. The MTT assay indicated that CDs/pSOX9 nanoparticles had little cytotoxicity against mouse embryonic fibroblasts (MEFs) compared to Lipofectamine2000 and PEI (25 kDa). Importantly, the CDs/pSOX9 nanoparticles with tunable fluorescence not only enabled the intracellular tracking of the nanoparticles, but also could successfully deliver the pSOX9 into MEFs with significantly high efficiency. Furthermore, the CDs/pSOX9 nanoparticles-mediated transfection of MEFs showed obvious chondrogenic differentiation. Altogether, these findings demonstrated that the CDs prepared in this study could serve as a paradigmatic example of the dual-functional reagent for both self-imaging and effective non-viral gene delivery.

Effect of energy input on flocculation process and flotation performance of fine scheelite using sodium oleate

We have investigated the effect of energy input on the flocculation process and flotation behavior of fine scheelite of less than 10µm size. Sodium oleate was used as a dual-function reagent, acting as flocculant and collector. Energy input in shear flocculation was controlled in a four-baffle cylindrical tank with a four-blade impeller by changing the agitation speed. The flocculation process was investigated by measuring continuous transformations in size distribution and observing floc shape. The results show that with increasing energy input, the size distribution of fine scheelite transforms from unimodal to bimodal. The flocs produced tend to possess more branches with low energy input and tends to become globule-like with high energy input. A parameter termed the flocculation degree was introduced to quantify the flocculation process as a function of energy input. The flocculation degree with increasing energy input reveals the aggregation order of different size fractions (all less than 10µm) when forming flocs. The flotation rate of flocs formed with different energy input was studied. The results demonstrate that the flotation rate is closely related to energy input and also, exhibits an intimate correlation with flocculation degree. These results could potentially be used to routinely monitor the flotation performance of fine particles in operating plants when shear flocculation is used.

Preparation of polyhedral oligomeric silsesquioxane based cross-linked inorganic-organic nanohybrid as adsorbent for selective removal of acidic dyes from aqueous solution.

A cross-linked polyhedral oligomeric silsesquioxane (POSS) nanohybrid is synthesized through Schiff base chemistry by using octa-amino POSS as building blocks and glutaraldehyde as dual functional reagent. The obtained nanohybrid is characterized by FT-IR, solid-state 29Si NMR, SEM, TEM, TGA and N2 adsorption-desorption isotherm, and the results demonstrate the successful cross-linkage between POSS molecules, forming block-like irregular nanoparticles with a specific surface area of 42.8m2g-1. As a novel solid-phase adsorbent, cross-linked POSS nanohybrid exhibits selective adsorption properties for acidic dyes, i.e., methyl orange (MO) in the present case. The strong electrostatic interactions between MO species and the nanohybrid are the main driving forces for MO adsorption. The kinetic data are well described by the pseudo-second-order kinetic model. The adsorption isotherm studies demonstrate that the data are well fit with Langmuir model at 293K and a maximum adsorption capacity of 237.5mgg-1 is obtained. Thermodynamic studies indicate that the adsorption of MO is spontaneous and exothermal, along with reduced randomness. The adsorbed MO species could be effectively recovered by using methanol/NaOH (9/1, v/v, 0.1molL-1 NaOH) as eluent. The practical application for textile wastewater treatment demonstrates that cross-linked POSS nanohybrid appears to be a promising material in dye removal field.

Quantitative structure–activity relationship for the apparent rate constants of aromatic contaminants oxidized by ferrate (VI)

Hexavalent ferrate, Fe(VI), is a promising oxidation–coagulation dual–functional reagent for removing aromatic contaminants (ACs) in water engineering systems. Recognizing that an increasing number of ACs are being used and introduced to the engineered waters, experimental measurements of the Fe(VI) oxidation kinetics, especially apparent second–order rate constants (kapp) are relatively expensive for these numerous organic compounds. Therefore, reliable models are highly demanded for predicting kapp of Fe(VI) oxidation of ACs with wide structural diversity and reactivity. In the present study, a quantitative structure–activity relationship (QSAR) model was developed for the kapp predication at pH=7 using stepwise multiple linear regression analysis (MLR) with the training set (n=26). The standardized QSAR model was obtained: lnkapp=34.7−4.80×IP, where IP is the ionization potential. The internal (QLOO2=0.81, n=26) and external validation (Qext2=0.82, n=8) indicates a robust prediction for kapp. Further, we compared the predicted kapp with experimental k values for Fe(VI) oxidation of phenolic compounds, and demonstrated that possible first step reaction pathways depends on different electron donating/withdrawing abilities of the functional groups, corroborating the mechanistic meaning of IP in the QSAR model. The QSAR model developed is helpful in understanding the degradation mechanisms of ACs by Fe(VI), and the predicted kapp values provide a basis to optimize the Fe(VI) oxidation of ACs during wastewater treatment processes.

Effective treatment of cadmium–cyanide complex by a reagent with combined function of oxidation and coagulation

The treatment of heavy metal–cyanide complex in industrial wastewater generally involves various processing units, such as chemical oxidation, hydrolysis precipitation and coagulation. A novel dual function reagent (PACC), which contains high content of active chlorine and Al13 polymer, shows a promising potential to shorten the process and heighten the treatment efficiency for cadmium–cyanide complex ([Cd(CN)4]2−). The results indicated that PACC is able to simultaneously achieve the complete oxidation of cyanide (CN−) by active chlorine and the subsequent coagulation of cadmium ion (Cd2+) by Al13 polymer. Two stages were carried out for complete CN− oxidation and effective Cd2+ coagulation. The first stage involves the conversion of CN− to cyanate (CNO−), and the second stage involves the conversion of CNO− to nitrogen and the coagulation of the liberated Cd2+. The optimum pH values for the first stage and the second stage are pH 11 and pH 8.5, respectively. The two stages for effective treatment of [Cd(CN)4]2− at the optimal pH condition totally need about 43 min at active chlorine dosage 130% of the theoretical requirement for CN− decomposition. Under the optimal conditions for [Cd(CN)4]2− treatment, the stoichiometric weight ratio of Cl2/Al in PACC is 2. This study presents a novel reagent and method to remove heavy metal–cyanide complexes from wastewater.

Derivatization following hollow-fiber microextraction with tetramethylammonium acetate as a dual-function reagent for the determination of benzoic acid and sorbic acid by GC

Derivatization at the injection port following hollow-fiber-based liquid-liquid-liquid microextraction with tetramethylammonium acetate as a dual-function reagent, i.e. an acceptor and derivatization reagent, for the determination of benzoic acid (BA) and sorbic acid (SA) in real samples by GC was developed. BA and SA were extracted from aqueous samples to an organic phase impregnated into the pores of the hollow fiber wall, and then back-extracted to the acceptor solution located inside the lumen of the hollow fiber. Upon injection, the extracted analytes were quantitatively derivatized to their methyl esters with tetramethylammonium acetate in the GC injection port. Several parameters related to the derivatization and extraction efficiency were optimized. The linearity was satisfactory over a concentration range of 0.1-50 mg/L with r > 0.993 for both analytes. The LODs were 2.0 μg/L for SA and 20 μg/L for BA. The recoveries (83-116%) and precisions (RSDs of 1.2-11.4% (n = 3)) were examined by analyzing real spiked samples. The enrichment factors of BA and SA were 300 and 425. The results demonstrated that this is a simple, rapid, accurate, and sensitive method for the determination of BA and SA in various samples.

Facile decoration of Au nanoparticles on reduced graphene oxide surfaces via a one-step chemical functionalization approach

A facile way to fabricate functionalized and reduced graphene oxide (RGO) was reported by introducing the dual-function reagent N1-(3-trimethoxysilylpropyl) diethylenetriamine (TSPD), in which (i) the amine functional groups of the organosilane can effectively restore the π bonds of the GO; and (ii) the silanol parts react with the hydroxyl groups of GO and subsequently cross-link to form a monolayer on the graphene surface. The exposed amine groups of the functionalized GO could effectively template the Au nanoparticles (AuNPs) assembly on the graphene surface with high density and good dispersity. TEM images indicate that AuNPs retained their original size and were well-anchored on the graphene surfaces with an average inter-particle distance of 15 nm. The resultant graphene sheets decorated by AuNPs has the capability of sensing single molecules on its surface, e.g., Rhodamine 6G (Rh6G), through the surface-enhanced Raman spectroscopy (SERS).

Dual C–H activations of electron-deficient heteroarenes: palladium-catalyzed oxidative cross coupling of thiazoles with azine N-oxides

The palladium-catalyzed, copper-promoted cross-dehydrogenative-coupling (CDC) of electron-deficient thiazoles with azine N-oxides through dual C–H activations was developed. It was found that copper(II) pivalate was an efficient dual-function reagent for the oxidative cross-coupling reactions, playing the roles of both an oxidant and a C–H bond activation promoter. This methodology provides a simple way to construct 2-thiazolyl pyridine moiety.

As(III) Oxidation by Active Chlorine and Subsequent Removal of As(V) by Al13 Polymer Coagulation Using a Novel Dual Function Reagent

An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.

Temperature sensitive polymers as efficient and selective flotation collectors

This study investigates both the efficacy and selectivity temperature responsive of poly(N-isopropylacrylamide) PNIPAM as a flotation collector. The results of this study showed that charged poly(N-isopropylacrylamide) polymers selectively increased both the probability particle/bubble attachment as well as the floatability of coarse alumina and quartz particles respectively. These results provide a basis for considering PNIPAM as both an effective and selective collector in a flotation system. Coupled with previous studies that demonstrate the efficacy of PNIPAM as a flocculant in mineral suspensions, these results clearly demonstrate the potential use of PNIPAM as a dual function reagent which acts as both selective flotation collector and flocculant in the flotation of ultrafine particles.

Classification of bacteria by simultaneous methylation–solid phase microextraction and gas chromatography/mass spectrometry analysis of fatty acid methyl esters

Direct methylation and solid-phase microextraction (SPME) were used as a sample preparation technique for classification of bacteria based on fatty acid methyl ester (FAME) profiles. Methanolic tetramethylammonium hydroxide was applied as a dual-function reagent to saponify and derivatize whole-cell bacterial fatty acids into FAMEs in one step, and SPME was used to extract the bacterial FAMEs from the headspace. Compared with traditional alkaline saponification and sample preparation using liquid-liquid extraction, the method presented in this work avoids using comparatively large amounts of inorganic and organic solvents and greatly decreases the sample preparation time as well. Characteristic gas chromatography/mass spectrometry (GC/MS) of FAME profiles was achieved for six bacterial species. The difference between Gram-positive and Gram-negative bacteria was clearly visualized with the application of principal component analysis of the GC/MS data of bacterial FAMEs. A cross-validation study using ten bootstrap Latin partitions and the fuzzy rule building expert system demonstrated 87 +/- 3% correct classification efficiency.