Template Reagent Research Articles

Fabrication of lignosulfonate-derived porous carbon via pH-tunable self-assembly strategy for efficient atrazine removal

Herein, a straightforward protocol was developed for the one-pot synthesis of N-doped lignosulfonate-derived carbons (NLDCs) with a tunable porous structure using natural amino acids-templated self-assembly strategy. Specifically, histidine was employed as a template reagent, leading to the preparation of 10-NLDC-21 with remarkable characteristics, including the large specific surface area (SBET = 1844.5 m2/g), pore volume (Vmes = 1.22 cm3/g) and efficient adsorption for atrazine (ATZ) removal. The adsorption behavior of ATZ by NLDCs followed the Langmuir and pseudo-second-order models, suggesting a monolayer chemisorption nature of ATZ adsorption with the maximum adsorption capacity reached up to 265.77 mg/g. Furthermore, NLDCs exhibited excellent environmental adaptability and recycling performance. The robust affinity could be attributed to multi-interactions including pore filling, electrostatic attraction, hydrogen bonding and π-π stacking between the adsorbents and ATZ molecules. This approach offers a practical method for exploring innovative bio-carbon materials for sewage treatment.

Metal gel particles loaded with epidermal cell growth factor promote skin wound repair mechanism by regulating miRNA

Abstract Skin wounds are prone to fungal infections and may threaten patients’ lives in severe cases. However, conventional treatment protocols rarely promote skin wound repair by modulating microRNA (miRNA). A novel binuclear cobalt(ii) complex with the chemical formula [Co2(MBBA)2(HPT)2(H2O)2]·2H2O (1) was synthesized through the reaction of 2-(4-methylbenzoyl) benzoic acid and 3-(pyridin-2-yl)-1H-1,2,4-triazole in the presence of 3,4-pyridine dicarboxylic acid as the template reagent. With natural polysaccharide hyaluronic acid and carboxymethyl chitosan as raw material, based on the chemical synthesis of epidermal cell growth factor for the load of metal gel particles, the microstructure and skin wound healing effect were studied. Molecular docking simulation showed that neither the carboxyl nor triazole group formed binding interactions with the active sites on proteins. Instead, the carbonyl group interacted with the active sites through hydrogen bonding. This study not only provides an effective solution to promote skin wound repair by modulating miRNAs but also provides useful ideas for synthesizing organometallic ligand-based hydrogels and their applications in biomedical fields.

Tetraurea Macrocycles: Template-Directed One-Pot Synthesis and Anion Binding Properties

Given the significance of anion in life, study of anion recognition attracted great attentions in the past decades. Macrocyclic receptors display intriguing anion binding properties; however, the synthesis of macrocycles is challenging. Here, we reported a new strategy of making tetraurea in one-step. By using 1-butyl-3-methylimidazolium ([hmim][X], X = anion) as the solvent and template reagent, tetraurea macrocycle comprised of bis(urea) binding moiety and hexyl chain spacers is selectively formed with high yield. The obtained macrocycles displayed interesting anion binding properties as indicated by single crystal X-ray diffraction structures and computational modelling.

Regulating the Porosity of Uranyl Phosphonate Frameworks with Quaternary Ammonium: Structure, Characterization, and Fluorescent Temperature Sensors.

Regulating the porosity of metal phosphonate frameworks is still challenging, even though this is not an issue for carboxylate-based metal-organic frameworks (MOFs). Quaternary ammonium cations are common template reagents widely used for structure control. However, it is not successful for uranyl phosphonate frameworks (UPFs) because the large volume sizes of templates make it challenging to enter the channels constructed by phosphonate ligands with small pore sizes and low dimensions. In this work, three new porous three-dimensional UPFs were synthesized using the phosphonate ligand and template reagents with the same geometry, namely, (TEA)2(UO2)3(TppmH4)2·2H2O (UPF-106), (TPA)2(UO2)3(TppmH4)2 (UPF-107), and (TBA)2(UO2)5(TppmH2)2(H2O)2·4H2O (UPF-108). The porosity of the UPFs in this work showed a positive relation with the sizes of the template ammonium cations. Thermogravimetric analysis and infrared and ultraviolet spectroscopy were performed. The variable-temperature fluorescence spectra of the three compounds showed that the fluorescence intensity has an excellent relation to temperature with a potential application as fluorescence temperature sensors.

Regioselective Transition‐Metal‐Free Arene C−H Borylations: From Directing Groups to Borylation Template Reagents

AbstractThe latest developments in the field of electrophilic C−H borylation reactions of arenes and heteroarenes without transition metals are briefly overviewed, with a particular emphasis on the latest advances enabling the highly regioselective C−H borylations of indoles and indolines using borylation template reagents.

Regioselective Transition-Metal-Free Arene C-H Borylations: From Directing Groups to Borylation Template Reagents.

The latest developments in the field of electrophilic C-H borylation reactions of arenes and heteroarenes without transition metals are briefly overviewed, with a particular emphasis on the latest advances enabling the highly regioselective C-H borylations of indoles and indolines using borylation template reagents.

Cu–Mn–O nano-particle/nano-sheet spinel-type materials as catalysts in methanol steam reforming (MSR) and preferential oxidation (PROX) reaction for purified hydrogen production

Nanocomposite Cu–Mn–O nano-particle (CuMnNP) and nano-sheet (CuMnNS) catalyst were successfully prepared using a one-step hydrothermal method in the absence of any templating reagent. Materials were characterised applying various structural techniques. SEM images showed that composite Cu–Mn oxide sheets were tailor-made synthesised by a one-pot urea-abetted protocol. Conversely, upon replacing carbamate by Na2CO3, oxidised metal Cu–Mn particles could be obtained. The formation of bulk mixed Cu–Mn phases resulted in an enhanced crystal lattice oxygen reactivity in CuMnNS. XPS, XRD and TPR measurements confirmed the presence of the Cu+ and Cu2+ species in nano-catalysts, and CuMnNS nanomaterials possessed more surface defects, thus causing a higher O2 adsorption/storage capacity. CuMnNS presented a superior catalytic activity as opposed to CuMnNP in the preferential oxidation (PROX) pathway of CO. With both CO2 and H2O in feed, a decrease in CO turnover was observed, due to a competitive interface binding of CO, CO2 and H2O. Compared to CuMnNP, CuMnNS also demonstrated a high time-on-stream conversion of methanol for the reforming for all operating conditions.

Front Cover: Pyrrolyl‐Appended Zinc Porphodimethenes: Branched Oligopyrrole Products From the Templated One‐Pot Isoporphyrin Synthesis (Eur. J. Inorg. Chem. 32/2021)

The Front Cover shows the Ishihara test plate of a dimeric zinc tripyrrin complex. This compound is a side product of the Adler-Longo porphyrin synthesis, which has been overlooked for more than half a century. It has now been found to act as the key intermediate in the formation of branched oligopyrroles like porphodimethenes. The detection and isolation of the metalated tripyrrin and the unraveling of its special reactivity were only possible after attempting the use of zinc acetate as template reagent during the oxidation step. More information can be found in the Full Paper by M. Bröring and co-workers.

Zinc- and Cadmium meso-Aryl-Isoporphyrins: Non-Aromatic NIR Dyes with Distinct Conformational Features.

A series of pyrrolyl and dipyrrinyl isoporphyrins carrying different phenyl and thienyl groups is reported. The compounds are obtained by a one‐pot approach in the presence of a template reagent. Thienyl derivatives gave better yields, and were the only subclass to form with steric hindrance. The structural analyses carried out on compounds 1 and 14 revealed distinct conformational differences which are likely to result from an intramolecular NH…Cl hydrogen bridge of the pyrrolyl subclass. In addition, this hydrogen bridge strongly favors one of the two possible atropisomers. Hindered rotation of the meso‐aryl groups is observed only in the cases of methylbenzothienyl derivatives 10 and 15 and leads to the observation of several diastereomers. NIR absorptions up to 923 nm are found throughout. Electrochemical investigations into the 1e− and 2e− reduced species unravel axial ligand exchange dynamics for the zinc isoporphyrin radical, and the probable formation of a zinc phlorinate.

Z-scheme photocatalyst based on porphyrin derivative decorated few-layer BiVO4 nanosheets for efficient visible-light-driven overall water splitting

It is highly desirable to simulate natural photosynthesis by using sunlight to drive the overall water splitting without using external bias and sacrificial agent. Herein, few-layer monoclinic BiVO4 nanosheets (BVNS) with a thickness of (∼)4.3 nm, exposed (010) facets and abundant oxygen vacancies are fabricated using graphene oxide dots as templating reagent. After decorating with asymmetric chromium porphyrin derivative bearing one benzoic acid and three phenyls as meso-position substituents (chromium-5-(4-carboxyphenyl)-10,15,20-triphenylporphrin, CrmTPP) and PtOx cocatalyst, the obtained two-dimensional (2D) hybrid nanocomposite (BVNS/CrmTPP/Pt) with an optimal component ratio delivers a robust overall water splitting performance with a relatively high apparent quantum yield (8.67%) at 400 nm monochromatic light. The ultrathin structure and widely distributed oxygen vacancies on the exposed (010) facets of BVNS not only endow strong and intimate contact with the decorated CrmTPP molecules to promote a two-step excitation Z-scheme charge transfer mechanism for preserving the high redox ability of the photogenerated charge carriers, but also alleviate their recombination, and thus causing the robust overall water splitting performance of the 2D hybrid nanocomposites. The present results provide a novel strategy to construct highly efficient artificial photosynthetic system for overall water splitting.

RETRACTED ARTICLE: Two Coordination Polymers: Protective Activity On Nerve Injury by Increasing miR-219 and Reducing Inflammatory Response

Two novel transition metal coordination polymers (CPs) of {Cu(tdc)(Hdmea)2 (1, Hdmea = N,N-dimethylethanolamine, tdc = 2,5-thiopenedicarboxylate) and [Co3(H2O)3(tdc)3(dioxane)]·2(dioxane) (2) were prepared via the reaction of Co(NO3)2·6H2O or Cu(NO3)2·3H2O and H2tdc with or without the template reagent Hdmea. The following experiments were carried out to determine the treatment activity for compounds against nerve injury. Firstly, the real time RT-PCR was carried out to determine the miR-219 relative expression in the nerve cells. Then the activation level of the AMPK signaling pathway in the nerve cells was measured with western blot. In addition to this, the ELISA detection was also used in this research, for the inflammatory cytokines’ evaluation. Finally, the inhibition of the compound 1 and compound 2 on the death of the nerve cells was determined with MTT assay.

Facile one-step synthesis of porous hybrid material fabricated by 2D nanosheets of molybdenum disulfide and reduced graphene oxide for efficient electrocatalytic hydrogen evolution

The electroreduction of water is a sustainable and environment-friendly way for sustainable hydrogen production. Herein 3D porous hybrid electrocatalysts, fabricated by ultrathin 2D nanosheets of molybdenum disulfide and reduced graphene oxide, have been prepared via a facile one-step hydrothermal route using hexamethylenetetramine as the template reagent. The as-prepared hybrids possess high specific surface areas and interconnected conductive graphene skeletons with vertically oriented MoS2 nanosheets. The hybrids exhibit excellent electrocatalytic activity for the hydrogen evolution reaction with a small overpotential of 97 mV at the current density of 10 mA cm–2 and a low Tafel slope of 70 mV dec−1, due to the synergetic effect of abundant active edge sites, efficient electron transfer, expedient hydrogen evolution routeway and convenient electrolyte diffusion.

A simple strategy to improve the sensitivity of probe molecules on SERS substrates

In this work, we report a simple strategy to improve the detection sensitivity as well as the spectral quality of probe molecules on surface-enhanced Raman scattering (SERS) substrates. On normal SERS substrates, due to the decreased absorption capacity and changes in the molecule orientations, SERS signals disappear when the analyte molecule concentrations reach a limit value. To solve this problem, the molecular template reagent (MTR) technique, a simple strategy based on SERS surface selection rules, is considered. By choosing the best MTR according to different samples, the effect of adjusting the molecular orientations of samples can be studied. In this process, 1-butanethiol, 1-hexanethiol, 1-octanethiol, 1-decanethiol, and 1-dodecanethiol, which are MTRs, are used to adjust the orientations of probe molecules under optimized conditions. The use of the MTR technique indicated that the limit of detection (LOD) of the probe molecules of p-aminobenzenethiol and 4-mercaptobenzoic acid on noble metal substrates showed an increase of one order of magnitude over the LOD of the pure probing molecule systems. Hence, the proposed method introduces a way to detect the molecules with an improved sensitivity at extremely low concentrations. The study corresponds to a proof-of-concept study of MTR-assisted SERS for SERS-based applications in ultrasensitive analyses.

Etherification of 5‐Hydroxymethylfurfural to Biofuel Additive Catalyzed by Aquivion® PFSA Modified Mesoporous Silica

Catalytic etherification of 5‐hydroxymethylfurfural (HMF) with isobutene (IB) to a biodiesel additive, that is, 5‐(tert‐butoxymethyl)‐furfural (tBMF), is studied on the Aquivion® perfluorosulfonic acid resin (PFSA) modified mesoporous silica (Aquivion®/m‐SiO2) solid acid. Mesoporous silica, composed of amorphous silica‐particle aggregates, is synthesized by the sol–gel method using the amphiphilic Aquivion® PFSA as both the acidic and the template reagent. The silica surface is then modified by the Aquivion® resin, leading to the hybrid Aquivion®/m‐SiO2 solid acid bearing highly accessible sulfonic acid sites and adequate porous structure. The catalytic properties, including composition, thermal stability, acidity, porosity, and morphology, are characterized by FTIR spectroscopy, Raman spectroscopy, solid‐state NMR spectroscopy, XPS, TGA/DTG, elemental analysis, potentiometric titration, N2 physisorption, SEM, and TEM. The influence of different reaction parameters, such as catalyst dosage, reaction time and temperature, reactants composition, and solvent, is investigated. The optimal Aquivion®/m‐SiO2 catalyst (10 wt.‐%), with an accessible acidity of 45 µmolH+ gcatal.–1 demonstrates 78 % conversion of HMF and 66 % yield of tBMF, in the presence of THF, after 3 h at 90 °C, whereas the yield of byproduct 5,5′‐[oxy‐bis(methylene)]bis‐2‐furfural (OBMF), generated by the oligomerization of HMF, is lowered to 4 %. The developed catalyst demonstrates good stability after regeneration for five consecutive cycles.

Influence of Catalysts with Different Templates on Direct Decomposition of NO in Cement Kiln Exhaust

The influence of catalysts with different templates on direct decomposition of NO in cement kiln exhaust was studied in this paper. The NO direct decomposition rate of porous catalyst materials with different templates was determined by infrared spectrometer. And pore structure and the microstructure of the catalysts were characterized by BET surface area, nitrogen adsorption-desorption. The results show that the catalytic performance of porous catalyst without any template is better than catalysts with other templates at low temperature. When the temperature reached 550 °C, NO decomposition rate of porous catalyst with CTAB could reach to more than 80%. And meanwhile, the catalysts with organic template reagent have higher BET surface area than those with inorganic template agent. With the increasing of the reaction time, the NO decomposition rate decreases. After reaction for 3 hours, the decomposition rate decreases from 80% to 40%.

Bi2Te3 Nanorods: Preparation, Reaction Mechanism and Electrochemical Property

A rapid chemical method has been developed for the synthesis of the Bi2Te3 nanorods with hexagonal crystalline phase. The method is based on the template-engaged synthesis in which the Te nanowires were used as template reagents. On the basis of a series of experiments and characterizations, the effect factors and the formation mechanism of the Bi2Te3 nanorods were discussed. Furthermore, the electrochemical property of the Bi2Te3 nanorods was determined by the voltammetric technique.

Preparation of high surface area mesoporous nickel oxides and catalytic oxidation of toluene and formaldehyde

Mesoporous nickel oxide (NiO) nanoparticles were synthesized by the thermal decomposition reaction of Ni(NO3)2·9H2O using oxalic acid dihydrate as the mesoporous template reagent. The pore structure of nanocrystals could be controlled by the precursor to oxalic acid dihydrate molar ratio, thermal decomposition temperature and thermal decomposition time. The structural characteristic and textural properties of resultant nickel oxide nanocrytals were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption–desorption isotherm and temperature programmed reduction. The results showed that the most excellently mesoporous nickel oxide particles (m-Ni-1-4) with developed wormlike pores were prepared under the conditions of the mixed equimolar precursor and oxalic acid and calcined for 4 h at 400 °C. The specific surface area and pore volume of m-Ni-1-4 are 236 m2 g−1 and 0.42 cm3 g−1, respectively. Over m-Ni-1-4 at space velocity = 20,000 mL g−1 h−1, the conversions of toluene and formaldehyde achieved 90 % at 242 and 160 °C, respectively. It is concluded that the reactant thermal decomposition with oxalic acid assist is a key step to improve the mesoporous quality of the nickel oxide materials, the developed mesoporous architecture, high surface area, low temperature reducibility and coexistence of multiple oxidation state nickel species for the excellent catalytic performance of m-Ni-1-4.

Unique 1D Co3O4 crystallized nanofibers with (220) oriented facets as high-performance lithium ion battery anode material.

A novel one-step hydrothermal and calcination strategy was developed to synthesize the unique 1D oriented Co3O4 crystal nanofibers with (220) facets on the carbon matrix derived from the natural, abundant and low cost wool fibers acting as both carbon precursor and template reagent. The resultant W2@Co3O4 nanocomposite exhibited very high specific capacity and favorable high-rate capability when used as anode material of lithium ion battery. The high reversible Li+ ion storage capacity of 986 mAh g−1 was obtained at 100 mA g−1 after 150 cycles, higher than the theoretical capacity of Co3O4 (890 mAh g−1). Even at the higher current density of 1 A g−1, the electrode could still deliver a remarkable discharge capacity of 720 mAh g−1 over 150 cycles.

Allele polymorphism analysis of hemostasis and folate metabolism genes by real-time microchip PCR

Genetic diagnostics is widely used for detection of risk factors of hereditary thrombophilias caused by molecular defects in the coagulation system. The hereditary thrombophilias are frequently associated with higher incidences of point mutations in hemostasis (F2 20210G>A, F5 1691G>A) and folate metabolism (MTHFR 677C>T, MTHFR 1298A>C) genes. Combinations of gene abnormalities in F2 and/or MTHFR with Leiden mutation (F5 1691G>A) significantly increase risk of thrombosis. Thus, simultaneous analysis of allele polymorphism of these genes is of clinical importance. This study has demonstrated high efficiency of microchip-based multiplex real time PCR for analysis of allele specific polymorphism in hemostasis and folate metabolism genes. Using this test it is possible to analyze polymorphism of the three genes (four point mutations) in a short time; it requires a minimal quantity of DNA template and PCR reagents including DNA polymerase, and thus can be recommended for clinical laboratory diagnostics.

Preparation of mesopourous Fe3O4 nanoparticle with template reagent: Tannic acid and the catalytic performance

We report a one-pot hydrothermal method for novel mesoporous Fe3O4 nanoparticles (NPs) preparation based on the reduction of ferric chloride with bifunctional agent: tannic acid (TA). TA acted both as template agent to obtain the mesoporous structure and functional agent to modify Fe3O4 NPs. The facile controlled process resulted in a relatively high surface area (99.5 m2 g−1) and good monodispersity with average diameter ∼200 nm of the synthetic nanoparticles. The high saturation magnetization (54.7 emu g−1) of the nanoparticles made it can be separated quickly from solution media via a magnet. The unique mesoporous structure of the Fe3O4 nanoparticles possessed high active site, and this was proved by studying the catalytic properties through Fenton catalytic degradation with hydrogen peroxide as a model reaction system. As a result, the tannic acid templated mesoporous Fe3O4 NPs (TA–Fe3O4 NPs) showed the very efficient catalytic properties for the degradation of methylene blue (MB) accelerated by the functionalization of TA.