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We report a method for fabricating inexpensive microfluidic platforms on paper using laser treatment. Any paper with a hydrophobic surface coating (e.g., parchment paper, wax paper, palette paper) can be used for this purpose. We were able to selectively modify the surface structure and property (hydrophobic to hydrophilic) of several such papers using a CO2laser. We created patterns down to a minimum feature size of 62 ± 1 µm. The modified surface exhibited a highly porous structure which helped to trap/localize chemical and biological aqueous reagents for analysis. The treated surfaces were stable over time and were used to self-assemble arrays of aqueous droplets. Furthermore, we selectively deposited silica microparticles on patterned areas to allow lateral diffusion from one end of a channel to the other. Finally, we demonstrated the applicability of this platform to perform chemical reactions using luminol-based hemoglobin detection. [ABSTRACT FROM AUTHOR]

Fungi are a diverse group of organisms that play an essential role in the biosphere. They have a unique ability to produce a vast array of secondary metabolites, including enzymes that have important applications in various industries. Fungal enzymes have been utilized in many fields, such as food processing, textile, paper, and pulp industries, to name a few. In recent years, there has been growing interest in the use of fungal enzymes in the synthesis of pharmaceutical compounds due to their scalability, high catalytic activity, relatively low cost, and ability to catalyze a wide range of chemical reactions under mild reaction conditions making the overall process greener and sustainable. Fungi produce a variety of enzymes such as oxidoreductases, transferases, and hydrolases which can be used in the synthesis of specific compounds with required chemo-, regio-, and stereoselectivity. This paper discusses the role of fungal enzymes in the synthesis of various drugs, active pharmaceutical ingredients (API), and drug intermediates and their applications in the pharmaceutical industry. [ABSTRACT FROM AUTHOR]

We proved that ice crystallized from water molecules within as-synthesized graphene oxide (GO) can be used as a spacer among individual GO sheets to form an expanded GO aerogel with a three-dimensional porous network structure. This designed specific structure can be retained during further processes to form graphene paper. Due to the fact that the as-fabricated graphene paper contains carbon defects and space in its infrastructure, this creates more electroactive surfaces and interfaces to significantly increase the Faradaic reaction efficiency. With the introduction of redox-electrolyte K3Fe(CN)6 into a KOH electrolyte, we can obtain a 95-fold increase in the specific capacitance compared with the value obtained in the traditional KOH electrolyte. The ice-crystallization formed graphene paper electrode showed high electroactivity because the specific porous structure can favor the fast transfer of electrolyte ions, such as Fe(CN)63- ions. The presented results prove that ice-crystallization formed GO can serve as a chemically tunable platform for electrochemical energy storage applications. [ABSTRACT FROM AUTHOR]

We report a robust and recyclable ‘dip-catalyst’ based on a gold nanoparticle (Au NP)-loaded filter paper composite, prepared by a simple dip-coating process using concentrated Au NP suspensions in toluene. While acting as catalysts, the composites display excellent surface enhanced Raman scattering (SERS) efficiency, allowing the real-time monitoring of chemical reactions. [ABSTRACT FROM AUTHOR]

Chiral Ph-dbfox (Ph-dbfox = (R,R)-4,6-dibenzofurandiyl-2,2′-bis(4-phenyloxazoline))/Zn(NTf2)2catalyzed enantioselective Friedel–Crafts reactions of β-CF3acrylates with pyrroles and indoles have been investigated, which afforded the corresponding chiral trifluoromethyl pyrrole and indole derivatives in high yields (90–99%) with a range of 66–99% ee values. With the aid of the chiral adduct of the asymmetric Friedel–Crafts reaction, the chiral trifluoromethylated heliotridane has been successfully constructed in good total yield. [ABSTRACT FROM AUTHOR]

Experiments were conducted to study the effects of reaction conditions on the hydrolysis of miscanthus dissolved in 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) catalyzed by H2SO4. It was determined that while there is a small co-inhibition effect associated with the simultaneous hydrolysis of the cellulosic and hemicellulosic portions of miscanthus, the largest rate decreases were observed for the hydrolysis of the hemicellulosic portion. This rate decrease was attributed to the chemical linkage between hemicellulose and lignin in miscanthus, which could be broken with chemical pretreatment. While chemical pretreatment increased the rate of the hydrolysis of the hemicellulosic component, delignification showed no further benefit. The rate of hydrolysis was determined to be first order in concentrations of β-1,4 glycosidic linkage and acid, and zero order in water concentration. The activation energy for the hydrolysis of the glycosidic linkages in the cellulosic and hemicellulosic components were determined to be 95 kJ mol−1and 114 kJ mol−1respectively. Progressive addition of water during the first hour of the reaction increased conversion and selectivity to saccharine products, while limiting dehydration of the sugars formed. The conversion of the cellulosic portion of miscanthus could be increased after the first hour of the reaction by increasing the reactor temperature. While miscanthus is only partially soluble in [Emim][Cl], it was found that the initial miscanthus loading could be increased to 9 wt% before significant yield decreases attributed to solubility limitations of the cellulosic component were observed. By proper adjustment of reaction conditions, it was possible to achieve yields of sugars approaching 84% from the cellulosic and hemicellulosic components of miscanthus, with minimal dehydration of the sugars to furans. [ABSTRACT FROM AUTHOR]

The ruthenium catalysed cross-metathesis of terpenoids with methyl acrylate and methyl methacrylate was used to prepare new terpenoids and to improve, to a large extent, the synthesis of known terpenoids. In particular, the cross-metathesis of mono-unsaturated terpenoids was very efficient whereas the transformation of terpenoids incorporating two double bonds was more difficult due to side reactions. The cross-metathesis reactions were carried out under environmentally friendly conditions either in dimethyl carbonate or under solvent-free conditions. [ABSTRACT FROM AUTHOR]

In the present work, for the first time, investigation of the initial fast step of reaction between 1,1,1-trichloro-3-methyl-3-phospholene (TCMP) and methanol was studied under a dry inert atmosphere by a newly constructed CSF apparatus by means of a further development in the configuration of the previous stopped-flow spectrophotometer (SFS). Hence, it was necessary to make many changes to the stopped-flow apparatus: replacement of the spectrophotometer amplifier with a conductance amplifier and the use of a conductivity cell to replace the optical one. The conductivity cell was made of polyethylene capillary tube (1 mm internal diameter; i.d.) and its inside dimensions were 1 mm i.d. × 3 mm long. Two tube electrodes which are made of stainless steel (0.8 mm i.d. × 14 mm long) were fixed at opposite ends of the observation cell and their outer surfaces were connected to the conductivity bridge amplifier by the two lead wires. The mixer was a 3-way Teflon valve and the distance between the mixer and the end of the observation cell was 30 mm. For each run, at least 24 µL of solution was required for a typical trace with a dead time of about 5 ms. Because of the extreme sensitivity of TCMP to moisture, the stopped-flow (CSF) apparatus was used inside a glove bag under a dry nitrogen atmosphere. Kinetic parameters for pseudo first-order reaction involving kobs= 30 s−1at 22 °C and activation energy Ea= 13.55 KJ mol−1were successfully calculated for the initial fast step of the reaction between TCMP and methanol at 22 °C. [ABSTRACT FROM AUTHOR]

Trialkyl imido niobium and tantalum complexes [MR3(NtBu)] (M = Nb, R = Me 2, CH2CMe33, CH2CMe2Ph 4, CH2SiMe35; M = Ta, R = Me 6, CH2CMe2Ph 7, CH2SiMe38) have been prepared by treatment of solutions containing [MCl3(NtBu)py2] (M = Nb 1a, Ta 1b) with three equivalents of magnesium reagent. By an unexpected hydrolysis reaction of the tris-trimethylsilylmethyl imido tantalum compound 8a, a μ-oxo derivative [(Me3SiCH2O)(Me3SiCH2)3Ta(μ-O)Ta(CH2SiMe3)2(NtBu)] (8a) was formed and its structure was studied by X-ray diffraction methods. Reactions of trialkyl imido compounds with two equivalents of isocyanide 2,6-Me2C6H3NC result in the migration of two alkyl groups, leading to the formation of a series of alkyl imido bisiminoacyl derivatives [MR(NtBu){C(R)NAr}2] (Ar = 2,6-Me2C6H3; M = Nb, R = Me 9, CH2CMe310, CH2CMe2Ph 11, CH2SiMe312, CH2Ph 13; M = Ta, R = CH2CMe314, CH2CMe2Ph 15, CH2SiMe316). All compounds were studied by IR and NMR (1H, 13C and 15N) spectroscopy. [ABSTRACT FROM AUTHOR]

Pseudooctahedral complexes [MCl3(NtBu)L2] (M = Nb, L = py 1, ½ tmeda 3; M = Ta, L = py 2, ½ tmeda 4) have been studied by spectroscopic methods. By a VT 1H NMR experiment a mutual exchange process between the pyaxand pyfreein the complexes 1–2was observed, whereas 13C and 15N NMR studies showed in the complexes 3–4a tmeda ligand with an axial/equatorial coordination mode. The reaction of 2with 3 equiv of Grignard reagent produces the methathesis products [TaR3(NtBu)] (R = CH2CMeCH25, CH2CHCHCH36) in which 2-methylallyl and 2-butenyl groups appear with a η3- and σ-coordination mode, respectively. When, toluene solutions of the compounds 5–6were treated with 2 equiv of 2,6-dimethylphenylisocyanide the imido bisiminoacyl compounds [TaR(NtBu){C(R)NAr-κ1C}2] (Ar = 2,6-Me2C6H3; R = CH2CMeCH27, CH2CHCHCH38) can be isolated, viaan imido iminoacyl intermediate [TaR2(NtBu){C(R)NAr-κ1C}] (Ar = 2,6-Me2C6H3; R = CH2CMeCH29) as we have observed in the treatment of 5with 1 equiv of isocyanide; however, the analogous reaction between 5and COPh2leads to the formation of the trisalkoxo imido compound [Ta(OCPh2R)3(NtBu)] (R = CH2CMeCH210). All new complexes were studied by IR and multinuclear NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Samarium metal and samarium diiodide have become important tools as selective cyclopropanating agents in organic synthesis due to their high chemo- and stereoselectivity. Therefore, Sm and SmI2are the ideal reagents to prepare cyclopropane derivatives. This tutorial reviewhighlights C–C multiple bond cyclopropanation processes promoted by samarium or samarium diiodide. [ABSTRACT FROM AUTHOR]

The immobilization of N-sulfonyl-(Ra)-binam-d-prolinamide using polystyrene as a support allows the recovery of an efficient catalytic system for the enantioselective direct aldol reaction between different ketones and aldehydes under solvent-free or aqueous conditions. The polystyrene-supported N-sulfonyl-(Ra)-binam-d-prolinamide catalyst in combination with benzoic acid showed similar results to those obtained with unsupported N-tosyl-binam-derived prolinamide under similar reaction conditions. The aldol products were obtained at room temperature and using only 2 equivalents of the ketone with high yields, regio-, diastereo- and enantioselectivities. The aldol reaction between aldehydes can also be performed under these reaction conditions with moderate results. The recovered catalyst can be reused up to six times without having a detrimental effect on the achieved results. [ABSTRACT FROM AUTHOR]

Two {Co3+–Zn2+} heterobimetallic coordination networks have been synthesized utilizing Co3+complex as the building blocks. The structural studies reveal 2D sheet-like networks where the Co3+containing building blocks are connected through Zn2+ions. Two different building blocks generate two unique networks as evidenced by the crystallographic studies and other properties. These networks are shown to catalyze Lewis metal ion assisted Strecker reaction in heterogeneous manner. [ABSTRACT FROM AUTHOR]

Covering: up to the end of 2009 [ABSTRACT FROM AUTHOR]

The biological synthesis of metal nanoparticles from ions has recently emerged as a novel technique for an environmentally benign recovery of heavy metals. Bacteria are known to recover palladium(0) in the form of nanoparticles that are catalytically active. However, the extent of the reactions that can be catalysed by bio-recovered palladium has not been investigated. This study demonstrates that the Suzuki–Miyaura and Mizoroki–Heck reactions can be catalysed by bio-generated palladium nanoparticles formed on the surface of Gram-negative bacteria. The results suggest that the range of applications of this catalyst can be extended to the realm of carbon–carbon bond formation in synthetic organic chemistry. [ABSTRACT FROM AUTHOR]

Selective oxidation of tetralin by molecular oxygen over mesoporous CrMCM-41 molecular sieve catalyst using supercritical carbon dioxide (scCO2) solvent has been investigated. CrMCM-41 catalyst gave high selectivity (96.2%) and good yield (63.4%) of 1-tetralone. The presence of scCO2medium improves 1-tetralone selectivity and suppresses leaching of chromium from the CrMCM-41. The activity over recycled CrMCM-41 remains nearly the same under the present experimental conditions. The effect of the reaction parameters on CrMCM-41 was also studied in detail along with comparison of its catalytic activities with other mesoporous catalysts, viz.MnMCM-41, CoMCM-41, microporous CrAPO-5, CoMFI, and macroporous Cr/SiO2catalyst, respectively. In addition this catalytic system was also applied for the oxidation of other benzylic compounds such as indane, fluorene, acenaphthene and diphenylmethane. [ABSTRACT FROM AUTHOR]

Protein phosphorylation is one of the most biologically relevant and ubiquitous post-translational modifications. The analysis of protein phosphorylation is very challenging due to its highly dynamic nature and low stoichiometry. In this article, recent techniques developed for phosphoproteome analysis are reviewed with an emphasis on the new developments in this field in China. To improve the performance of phosphoproteome analysis, many novel methods, either by application of new separation mechanisms or by adoption of new separation materials, were developed to specifically enrich phosphopeptides from complex protein digests. A series of new materials, including nanostructure materials, magnetic materials, and monolithic materials, were applied to prepare immobilized affinity chromatography or metal oxide affinity chromatography to improve the performance of phosphopeptide enrichment. Besides, new software tools were also developed to validate phosphopeptide identification and predict kinase specific phosphorylation sites. [ABSTRACT FROM AUTHOR]

In view of the growing demand for synthetic molecules or materials by researchers from both the core sciences and interdisciplinary sectors, the field of organic synthesis needs to be strategically more powerful to produce more molecules in a shorter time. Ensuring a reduction in the use of solvents, catalysts, reagents, time, effort, and waste is essential during green chemical syntheses. Keeping those criteria in mind, the integration of chemical reactions is very much needed. Integrated organic synthesis can be considered the ideal replacement for stepwise synthesis to fulfill demand while maintaining green parameters. The electrochemical cascade process satisfies the essential criteria of greener integrated synthesis to a great extent, providing a modern strategic tool in the arsenal of synthetic chemists. The strategy is applied extensively by researchers, as evidenced by the growing number of publications, amounting to more than a hundred papers on the development of synthesis methods using electrochemical cascade reactions. A thorough understanding of the process is needed to implement the strategy further in targeted synthesis and methodology development for cutting-edge research. To grow the concept among researchers, a concise account of published articles on the topic, depicting the mechanisms, prospects, and problems of the developed methods, is highly desirable. Quenching the thirst herein, we present a concise review of electrochemical cascade processes reported in the literature since 2015. The precedent reactions developed earlier are also discussed in this context. Electrochemical multicomponent reactions involving the cascade process are also covered, expanding the scope of the review. The sections are classified based on the types of functionalization. The mechanistic details of each category of reactions are thoroughly covered to present a clear idea of the redox behavior of different reagents under electrochemical conditions. The prospects and problems associated with the methods are also discussed. [ABSTRACT FROM AUTHOR]

Lawsone (2-hydroxy-1,4-naphthoquinone) reacts with latent fingermark deposits on paper surfaces to yield purple-brown impressions of ridge details which are also photoluminescent; this compound represents the first in a completely new class of fingermark detection reagents. [ABSTRACT FROM AUTHOR]

The present paper reviews 47 Life Cycle Assessments (LCA) applied to chemical reactions. The selection of the evaluated articles was conducted with a systematic literature review methodology. The review arises from the need to define the best methods for developing LCAs of chemical processes at industrial scale. The authors go through the stages defined in ISO 14040 and 14044, identifying both the gaps and the best techniques used in all the reviewed papers. The main difficulty observed when developing LCAs of chemical reactions is the lack of data due to confidentiality issues in chemical companies. In addition, this data is commonly only available at the laboratory scale. Laboratory data is sometimes directly upscaled without further consideration. Even though, simulation software, advanced calculations benchmarks, pinch analysis and retrosynthetic analysis are the best methods to estimate and scale up the mass and energy balances in the Life Cycle Inventory (LCI) stage. The article discusses these upscale procedures, makes a deep analysis of each single LCA stage, and assesses how chemical process information is managed, which is a novelty regarding previous reviews of chemical reaction LCA. From the Life Cycle Impact Assessment (LCIA) methodologies, they should be standardized to enable the comparability between LCAs of the same product. Both the European Commission and the Life Cycle Initiative are making progress in this regard. Eventually, the ReCiPe is the most used methodology among the reviewed papers. Finally, the article proposes different analyses to be performed in the interpretation phase: i.e., projecting the energy mix foreseen for the years 2030 and 2050 in energy-intensive processes or including other sustainability vectors (economic and social) in cross-cutting projects. [ABSTRACT FROM AUTHOR]

The free-radical hydrothiolation of alkynes (thiol-ynecoupling, TYC) unites two thiol fragments across the carbon-carbon triple bond to give a dithioether derivative with exclusive 1,2-addition; this reaction can be used for modification of peptides and proteins allowing glycoconjugation and fluorescent labeling. These results have implications not only as a flexible strategy for attaching two modifications at a single site in proteins but also for unanticipated side-reactions of reagents (such as cycloalkynes) used in other protein coupling reactions. [ABSTRACT FROM AUTHOR]

The Staudinger reaction of unprotected azido-peptides with silylated phosphinic acids and esters on the solid support offers a straightforward acid-free entry to different phosphonamidate peptide esters or acids under mild conditions in high purity and yield. [ABSTRACT FROM AUTHOR]

The palladium-catalysed carbonylation of vinyl aziridines can give either the trans- or cis-β-lactam preferentially or even the δ-lactam simply by adjusting the reaction parameters ([Pd], [CO], temperature). [ABSTRACT FROM AUTHOR]

A homodinuclear Ni2-Schiff base 1complex (0.1–1 mol%) promoted the direct catalytic asymmetric aldol reaction of β-keto esters with formaldehyde, giving hydroxymethylated adducts in 94–66% ee. [ABSTRACT FROM AUTHOR]

Heteroleptic complexes, formed selectively by using a 1 : 1 combination of a σ-donor and a π-acceptor ligand, are involved in Rh- and Pd-catalysed reactions. [ABSTRACT FROM AUTHOR]

Reaction of LSrN(SiMe3)2(thf) 1(L = CH(CMe-2,6-i-Pr2C6H3N)2) with Me3SnF and LAlCl(Me), respectively, gave the first example of a strontium mono fluoride complex [LSr(thf)(μ-F)2Sr(thf)2L] 2and the corresponding chloride derivative [LSr(thf)(μ-Cl)2Sr(thf)2L] 3. [ABSTRACT FROM AUTHOR]

The combination of ligands based on two quinoline units acting as primary coordinating sites connected by tetra- or penta-ethyleneoxy fragments behaving as secondary interaction sites leads spontaneously in a one-pot reaction to the formation of tri- and terta-nuclear metalla-organic knots in the presence of silver cation. [ABSTRACT FROM AUTHOR]

Dihydrosilanes undergo double trans-hydrosilylation with 1,4-diarylbuta-1,3-diynes in the presence of a cationic ruthenium catalyst to afford 2,5-diarylsiloles: in particular, 9-silafluorene is a good hydrosilylating agent to produce spiro-type siloles in good yield. [ABSTRACT FROM AUTHOR]

The intramolecular [2 + 2]-photocycloaddition of the 1,3-divinyl-2-cyclopentyl tetronates 1 was performed under various conditions to give perfect diastereoselectivity and a regioselectivity of up to 85/15 in the presence of γ-cyclodextrin by differentiating the two chemically very similar double bonds of 1. [ABSTRACT FROM AUTHOR]

Reactions and purifications, including carbon–carbon bond forming reactions, can be carried out on a cellulose support on which the substrates are non-covalently absorbed. [ABSTRACT FROM AUTHOR]

Single-electron reduction of a carbonyl by photoredox catalysis enables the generation of ketyl radicals, providing a benign procedure for constructing C–C bonds. However, external photocatalysts are required. In this paper, photoinduced generation of ketyl radicals and application in C–C coupling are reported, which require no use of any external photocatalyst. Irradiation of carbonyl with purple light in the presence of a tertiary amine generates highly reactive ketyl radicals, enabling a series of important reactions in synthetic chemistry, such as the reductive coupling of aldehydes, ketones, and imines, the allylation of aldehydes, the Barbier reaction, reductive arylation, and aldehyde–aniline coupling. We also present evidence to support the ketyl radicals being formed via photoinduced intermolecular electron transfer from the tertiary amine to aryl aldehydes. [ABSTRACT FROM AUTHOR]

A liquid marble is a liquid droplet coated with a shell of microparticles. Liquid marbles have served as a unique microreactor for chemical reactions and cell culture. Mixing is an essential task for liquid marbles as a microreactor. However, the potential of liquid marble-based microreactors is significantly limited due to the lack of effective mixing strategies. Most mixing strategies used manual and contact-based actuation schemes. This paper reports the development of a manipulation scheme that induces fluid motion into a liquid marble, leading to enhanced mixing. By inducing rotation on a horizontal axis, we significantly increased the mixing rate by 27.6 times compared to a non-actuated liquid marble and reduced the reaction time by more than 10 times. The proposed method provides a simple, continuous, precise, and controllable high-performance mixing strategy on a liquid marble platform. [ABSTRACT FROM AUTHOR]

Lignin is one of the most abundant biopolymers on Earth and is considered as the primary resource of aromatic compounds. Recently, lignin has attracted attention from scientists and industrialists due to its inherent potential arising from its unique structure, which leads to its possible use in many applications. Many efforts have been made to ameliorate the reactivity and compatibility of lignin in different areas. Although methods have been proposed for endowing lignin with different properties, there continues to be a considerable demand for discovering new and effective ways of unraveling the beneficial uses of this aromatic polymer. Considering the structure of lignin, different grafting modifications can occur on the aliphatic and/or aromatic groups of lignin. To date, there has been a lack of fundamental understanding of the modification pathways of lignin for generating lignin-based products. In this review paper, we discuss comprehensively the chemical reactions that were introduced in the literature for preparing lignin with different features via modifying its phenolic and aliphatic hydroxy groups for altered uses. This review paper critically and comprehensively elaborates on the recent progress in lignin reactions as well as the challenges, advantages and disadvantages associated with the reaction procedures and the product development processes. Furthermore, the research gap in reaction strategies and product development are described throughout this study. [ABSTRACT FROM AUTHOR]

The voltammogram features of TMPD2+/TMPD, N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), reflect the intensive instability of TMPD2+ in aqueous solutions. The instability of TMPD2+ strongly restricts its application in electrochemical syntheses. The striking feature of this paper is the stabilization of this redox-active species via amine functionalization. The procedure started with the chemical reaction of TMPD with sodium nitrite to produce N-(2-nitro-4-(dimethylamino)phenyl)-N-methylnitramide (NDPM). The nitro functional group of NDPM was reduced electrochemically to the corresponding amine derivative, N-(2-amino-4-(dimethylamino)phenyl)-N-methylnitramide (ADPM). Unlike TMPD2+/TMPD, the voltammetric results of ADPM presented a reversible redox process at low redox potentials. The phenomenon introduces ADPM as an effective compound for the electrochemical synthesis of p-phenylenediamine derivatives in green conditions. To examine the hypothesis, we have developed a paired electrochemical synthesis method via the reduction of NDPM at the surface of the cathode followed by oxidation at the anode surface in the presence of arylsulfinic acids as typical nucleophiles. The electrochemical synthesis was successfully performed under green conditions in the absence of redox mediators. [ABSTRACT FROM AUTHOR]

The reaction of alkynes with bis-cyclopentadienyl hydride complexes of niobium has aroused substantial concern due to their important roles in catalytic hydrogenation processes. In this paper, the reaction mechanisms of Cp2NbH3 (Cp = η5-C5H5) with substituted alkynes RC≡CR (R = COOMe (1) and Me (2)) were investigated and compared based on density functional theory (DFT) calculations. The calculated results demonstrate that the reaction mechanisms and products of the title reactions are regulated by the characteristics of the alkyne substituent. For alkynes that feature the electron-withdrawing substituent COOMe, the corresponding fumaric ester complex, namely, Cp2NbH(trans-MeO2CCH＝CHCO2Me), can be obtained at ambient temperature through an insertion process. For alkynes that feature the electron-donating substituent Me, the products are hydride niobocene Cp2NbH(MeC≡CMe) and H2, which are obtained via the elimination of hydrogen molecules, and they can only be obtained with irradiation by UV light. Our studies provide reasonable explanations for experimental observations and predict new chemical reactions in this domain. [ABSTRACT FROM AUTHOR]

The emphasis of this mini review is on the representation of dynamic NMR methods to obtain kinetic and mechanistic information on the equilibria of metal complexes in aqueous solution. A brief discussion of the basic aspects of NMR relaxation and the effect of chemical exchange on that providing information on the dynamics of equilibrium is given. The experimental and computational tools for extracting kinetics from dynamic data are also described, underlining the importance of a multinuclear approach. It reviews some theoretical background citing useful books and papers on the chemical applications of the most often used dynamic NMR methods. It focuses on the use of these methods for elucidating reaction pathways, and mechanisms and for determination of kinetic parameters, through examples, rather than on the technical and theoretical details or on an exhaustive survey of the present literature. The usefulness of the multinuclear NMR approach in this context is illustrated quoting cases when it has been applied. Most of the concrete experimental data refer to the authors own work on the kinetics of lanthanide, uranium and thallium complexes; however, the general aspects are always emphasized. The aim of this paper is to encourage coordination chemists to employ NMR and discover that the dynamic aspects of this very powerful technology are exactly made for coordination chemistry. [ABSTRACT FROM AUTHOR]

Reactive distillation is a process intensification technology that combines a chemical reaction with distillation in a device. Enzymatic Reactive Distillation (ERD)—the application of immobilized enzyme catalysts instead of traditional acid–base catalysts in reactive distillation has attracted much attention due to its high selectivity and mild process conditions. However, to apply ERD to industrial processes, it is critical to address constraints such as the cost and stability of immobilized enzyme catalysts. Herein, in this paper, Candida antarctica lipase B (CALB) was immobilized in a commercial resin "NKA" by a hydrophobic interaction, and the immobilized enzyme was PEGylated by a series reaction. Both the stability and catalytic performance of the prepared NKA-CALB-PEGylated are significantly improved. The catalytic efficiency of NKA-CALB-PEGylated (80.1%) in the transesterification reaction system is slightly higher than those of NKA-CALB (71.7%) and Novozyme435 (69.3%), and significantly higher than that of Sol gel-CALB (60%) published in our previous literature. Additionally, NKA-CALB-PEGylated retained an initial activity of 92.4% after repeated use six times, which was significantly higher than those of Novozyme435 (60.2%) and NKA-CALB (78.6%). Therefore, the prepared stable and economical enzyme catalyst has great prospects for applications in the ERD industry. [ABSTRACT FROM AUTHOR]

Amongst the most popular methods for the production of metal oxide nanostructures is hydrothermal synthesis. For producing ZnO nanostructures, a nitrate-based precursor reaction with equimolar amounts of hexamethylenetetramine (HMTA) is commonly used. In these reactions, zinc nitrate provides the source of Zn2+ ions, and HMTA produces the desired amount of OH− ions. The growth process occurs due to a dissolution-secondary precipitation mechanism. ZnO nanostructures are characterized by anisotropic growth with different growth rates of the individual faces, where (v(0001) > v(101¯0) > v(101¯1¯) > v(101¯1) > v(0001¯)). Therefore, considering the principle of energy minimization, the most favorable is vertical growth perpendicular to the (0001) plane, which ensures the formation of characteristic rod-like nanostruchtures of ZnO. The mentioned process takes place when chemical reactions are in equilibrium. Shifting from the equilibrium conditions by varying the parameters of reaction, or using capping agents, makes it possible to change the growth rate of individual crystallographic planes and, as result, affect the morphology of the obtained nanostructure. In this paper the influence of concentration and composition of the reagents, growth time and temperature, pH of the solution, and the presence of different capping agents on the growth process of nanostructured ZnO were investigated. Optimal synthesis parameters for obtaining nine independent ZnO morphologies have been determined. The distinctive feature of these experiments is the fact that the samples were obtained as durable, homogeneous, epitaxial coatings on hard surfaces. This can be especially interesting for the development of sensors and other fields where surface area is crucial, and it opens up more possibilities than use of the nanostructured ZnO powders. [ABSTRACT FROM AUTHOR]

Droplet-based microfluidics has permeated many areas of life sciences including biochemistry, biology and medicine. Water-in-oil droplets act as independent femto- to nano-liter reservoirs, enabling the parallelization of (bio)chemical reactions with a minimum sample input. Among the range of applications spanned by droplet microfluidics, digital detection of biomolecules, using Poissonian isolation of single molecules in compartments, has gained considerable attention due to the high accuracy, sensitivity and robustness of these methods. However, while the droplet throughput can be very high, the sample throughput of these methods is poor in comparison to well plate-based assays. This limitation comes from the necessity to convert independently each sample into a monodisperse emulsion. In this paper, we report a versatile device that performs the quick sequential partitioning of up to 15 samples using a single microfluidic chip. A 3D printed sample rotor is loaded with all samples and connected to a pressure source. Simple magnetic actuation is then used to inject the samples in the microfluidic chip without pressure disruption. This procedure generates monodisperse droplets with high sample-to-sample consistency. We also describe a fluorescent barcoding strategy that allows all samples to be collected, incubated, imaged and analyzed simultaneously, thus decreasing significantly the time of the assay. As an example of application, we perform a droplet digital PCR assay for the quantification of a DNA amplicon from 8 samples in less than 2 hours. We further validate our approach demonstrating the parallel quantification of 11 microRNAs from a human sample using an isothermal nucleic acid amplification chemistry. As an off-chip device, the sample changer can be connected to a variety of microfluidic geometries and therefore, used for a wide range of applications. [ABSTRACT FROM AUTHOR]

Mechanochemistry refers to a chemical reaction induced by mechanical energy involving solids. This method provides several advantages over solution-phase synthesis, such as minimizing the need for large volumes of solvents in chemical reactions and greener and more efficient synthetic solutions. In this paper we obtain, via mechanochemistry, a hybrid salt, named MEFAS, derived from two antimalarial molecules – mefloquine and artesunate. We demonstrate, using a simple experimental procedure, how the catalytic amount of liquid present during mechanochemical reactions is decisive to obtain MEFAS. Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) data indicate that liquid-assisted mechanochemical reactions are promising in the formation of the hybrid salt, which is formed via a hydrogen interaction of the carboxylate group of the artesunate molecule with the piperidine group of mefloquine. [ABSTRACT FROM AUTHOR]

In this paper, we report three-dimensional (3-D) liquid metal manipulation using electromagnets, which can be applied to electrical switching applications. The liquid metal droplet was coated with iron (Fe) particles by chemical reaction with hydrochloric acid (HCl), and thus it became responsive to the magnetic field, becoming a magnetic liquid metal marble. Using electromagnets, the magnetic field was turned on and off on-demand. We investigated an average velocity and the maximum working distance of the horizontal and vertical electromagnetic field-driven manipulation of the magnetic liquid metal marble. Linear (1-D) and plane (2-D) manipulation of the marble was successfully demonstrated and 3-D manipulation was verified for electrical switching. [ABSTRACT FROM AUTHOR]

This paper presents a microfluidic chemical reaction using an electrowetting-on-dielectric (EWOD) digital microfluidic device. Despite a number of chemical/biological applications using EWOD digital microfluidic devices, their applications to organic reactions have been seriously limited because most of the common solvents used in synthetic organic chemistry are not compatible with EWOD devices. To address this unsolved issue, we first introduce a novel technique using an "engine-and-cargo" system that enables the use of non-movable fluids (e.g., organic solvents) on an EWOD device. With esterification as the model reaction, on-chip chemical reactions were successfully demonstrated. Conversion data obtained from on-chip reactions were used to characterize and optimize the reaction with regard to reaction kinetics, solvent screening, and catalyst loading. As the first step toward on-chip combinatorial synthesis, parallel esterification of three different alcohols was demonstrated. Results from this study clearly show that an EWOD digital microfluidic platform is a promising candidate for microscale chemical reactions. [ABSTRACT FROM AUTHOR]

Four principal intra-particle phenomena occur in a highly concerted manner during the pyrolysis of lignocellulosic materials: heat transfer, mass transfer, chemical reactions, and phase changes. Achieving a holistic understanding of these processes has been challenged by their intricate coupling, high temperatures, and rapid rates at which they occur. Heat and mass transfer have been well studied at the single-particle level but their coupling with chemical reactions and phase change within single particle models remains problematic. Equally challenging is the multiscale coupling of reactor- and single particle-scale models. Too little attention has been given to phase change. Similarly, the presence of oligomeric compounds (constituting up to 20% of the oil) has not been fully accounted for in chemical reaction schemes and physical models developed for pyrolysis. Recent studies have shown that a multiscale approach is key to predictive modelling across a variety of reactor systems. Historical and recent developments are outlined in this pyrolysis review paper regarding these four intra-particle phenomena, as well as modelling efforts to capture their effect on product yields and composition. It is critical for the design of future biomass pyrolysis systems to appropriately account for all four intra-particle phenomena and their inter-connectivities in order to predict, achieve, and maintain optimal operation. [ABSTRACT FROM AUTHOR]

LaMnO3 and LaCoO3 perovskite nanoparticles have sprung up as the platinum group-metal (PGM)-free catalysts of NO oxidation to reduce NOX in the exhaust. In this paper, we present mesoporous LaMnO3 and LaCoO3 with rhombohedral structures prepared by a facile molten-salt synthesis method. LaMnO3 and LaCoO3 achieved NO oxidation performance with the highest NO conversions of 85% and 94% at 300 °C, which may be improved by K and Na introduced via flux. [ABSTRACT FROM AUTHOR]

An unprecedented twofold interpenetrating (3,4)-connected topology of the Cu3L4-type metal–organic framework was prepared using N,N′,N″-tris(4-pyridinyl)-1,3,5-benzenetricarboxamide (L) as a trigonal three-connection node and the copper(ii) ion as a square planar four-connection node, where the framework contains remarkably large 1-D solvent channels. [ABSTRACT FROM AUTHOR]

Cofacial assemblies of metalloporphyrinoids represent a fascinating platform for the fabrication of novel functional molecular assemblies based on π–π, d–d, and d–π interactions between components. In this paper, we present a novel synthetic strategy for the programmable arrangement of different metal ions inside a cofacially stacked trimer of porphyrinoids. A combination of two different assemblies was utilized for our purpose: a tetracationic fourfold rotaxane heterodimer between a porphyrin with four alkylammonium chains and a phthalocyanine bearing four peripheral crown ethers, and a stacked assembly between the fourfold rotaxane heterodimer and an additional tetraanionic porphyrin. Three metal ions, namely Cu(ii), Ag(ii), and Au(iii), were arranged inside the cofacially stacked assembly of three porphyrinoids. Moreover, paramagnetic Cu(ii) ions were arranged inside a cofacially stacked heterotrimer of porphyrinoids and were precisely programmed, affording the desired spin–spin communications as readable information. These results indicated that the developed strategy is effective for arranging various metal ions in cofacially stacked assemblies of porphyrinoids toward the creation of molecular tags or bar codes. [ABSTRACT FROM AUTHOR]

This paper presents a series of six examples of 1,1-difluoro-3-aryl(heteroaryl)-1H-pyrido[1,2-c][1,3,5,2]oxadiazaborinin-9-ium-1-uides (2)―in which aryl(heteroaryl) = phenyl, 4-MeC6H4, 4-N(CH3)2C6H4, 4-NO2C6H4, 2-naphthyl, and 2-thienyl―as pyridine-based boron heterocycles with variable ligand structures. The heterocycles 2 were easily synthesized at yields of 51–70% from reactions―at room temperature for 24 h―of simple N-(pyridin-2-yl)benzamides (1) with BF3·Et2O, and they were fully characterized by 1H-, 13C-, 19F-, and 11B-NMR spectroscopy, GC-MS, and X-ray diffractometry. The optical and electrochemical properties of 2 (UV-vis spectra, fluorescence spectra, quantum yield calculations, Stokes’ shifts, redox potentials, and DFT calculations) were determined and discussed. BSA-binding experiments and molecular docking studies of new complexes 2 were performed and correlated between each other. [ABSTRACT FROM AUTHOR]

Despite the increasing importance of positron emission tomography (PET) imaging in research and clinical management of disease, access to myriad new radioactive tracers is severely limited due to their short half-lives (which requires daily production) and the high cost and complexity of tracer production. The application of droplet microfluidics based on electrowetting-on-dielectric (EWOD) to the field of radiochemistry can significantly reduce the amount of radiation shielding necessary for safety and the amount of precursor and other reagents needed for the synthesis. Furthermore, significant improvements in the molar activity of the tracers have been observed. However, widespread use of this technology is currently hindered in part by the high cost of prototype chips and the operating complexity. To address these issues, we developed a novel microfluidic device based on patterned wettability for multi-step radiochemical reactions in microliter droplets and implemented automated systems for reagent loading and collection of the crude product after synthesis. In this paper, we describe a simple and inexpensive method for fabricating the chips, demonstrate the feasibility of prototype chips for performing multi-step radiochemical reactions to produce the PET tracers [18F]fallypride and [18F]FDG, and further show that synthesized [18F]fallypride can be used for in vivo mouse imaging. [ABSTRACT FROM AUTHOR]

Co-encapsulation of two distinct particles within microfluidic droplets provides the means to achieve various high-throughput single-cell assays, such as biochemical reactions and cell–cell interactions in small isolated volumes. However, limited by the Poisson statistics, the co-encapsulation rate of the conventional co-flow approach is low even under optimal conditions. Only up to 13.5% of droplets precisely contain a pair of two distinct particles, while the rest, either being empty or encapsulating unpaired particles become wastes. Thus, the low co-encapsulation efficiency makes droplet-based assays impractical in biological applications involving low abundant bioparticles. In this paper, we present a highly promising droplet merging strategy to increase the co-encapsulation efficiency. Our method first enriches droplets exactly encapsulating a single particle via fluorescence or scattering-light activated sorting. Then, two droplets, each with a distinct particle, are precisely one-to-one paired and merged in a novel microwell device. This deterministic approach overcomes the Poisson statistics limitation facing conventional stochastic methods, yielding an up to 90% post-sorting particle capture rate and an overall 88.1% co-encapsulation rate. With its superior single-particle pairing performance, our system provides a promising technological platform to enable highly efficient microdroplet assays. [ABSTRACT FROM AUTHOR]

Based on the recent results obtained in papers it has become possible to create an original theory for the quantitative detection/description of different electrode states in electrochemical measurements. This new approach allows for the taking into account of the influence of the apparatus function and for the quantitative comparison of two similar electrodes used for measurements of the same substance. The new approach does need unjustified suppositions and a specific model for the description of measured curves; the desired curves (reduced to an ideal experiment after the elimination of the apparatus function) are expressed quantitatively in terms of the so-called intermediate model. The fitting parameters of the intermediate model coincide with the fragment of the Fourier series used as the fitting function. Besides, the distribution of measurements has a universal distribution and can be expressed in terms of the fitting parameters associated with a beta distribution function. The new approach opens new perspectives for conventional electrochemistry and can be used as an accurate tool for the description of reproducible data, the detection of “traces” and the selection of the “best fit” model among competitive hypotheses suggested by theoretical electrochemistry. [ABSTRACT FROM AUTHOR]