Recent Advances in Cellulose Chemistry.

The current transition from fossil-based raw materials to biomass-based materials, and their application, has led to the innovation and development of sustainable chemical industries towards a circular economy [...

Copper phosphorylated cellulose nanofibers mediated azide-alkyne cycloaddition click reaction in water.

Heterogenous copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC) was performed by using the phosphorylated carbohydrate-based cellulose nanofibers loaded with copper(II) ions. The copper-containing phosphorylated cellulose nanofibers (here after noted Cu(II)-PCNFs) were prepared in two different morphologies, namely the paper and foam ones and characterized by different techniques, including Scanning Electronic Microscopy (SEM), Energy Dispersive X-ray (EDX), Brauner-Emmett-Teller (BET), FT-IR spectroscopy (FTIR), Thermal Gravimetric Analysis (TGA), X-ray Photoelectron spectroscopy (XPS) and Atomic Force Microscopy (AFM). Cu(II)-PCNFs showed high activity in the CuAAC reaction when applied to the ligation of various organic azides and terminal alkynes without any reducing agent, resulting in the regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles in water at room temperature.

Cellulose Acetate-Supported Copper as an Efficient Sustainable Heterogenous Catalyst for Azide-Alkyne Cycloaddition Click Reactions in Water.

A new sustainable heterogeneous catalyst for copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC) was investigated. The preparation of the sustainable catalyst was carried out through the complexation reaction between the polysaccharide cellulose acetate backbone (CA) and copper(II) ions. The resulting complex [Cu(II)-CA] was fully characterized by using different spectroscopic methods such as Fourier-transform infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDX), Ultraviolet-visible (UV-vis), and Inductively Coupled Plasma (ICP) analyses.

Recent Advances in Copper-Based Solid Heterogeneous Catalysts for Azide-Alkyne Cycloaddition Reactions.

The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is considered to be the most representative ligation process within the context of the "click chemistry" concept. This CuAAC reaction, which yields compounds containing a 1,2,3-triazole core, has become relevant in the construction of biologically complex systems, bioconjugation strategies, and supramolecular and material sciences. Although many CuAAC reactions are performed under homogenous conditions, heterogenous copper-based catalytic systems are gaining exponential interest, relying on the easy removal, recovery, and reusability of catalytically copper species.

An Overview on the Performance of 1,2,3-Triazole Derivatives as Corrosion Inhibitors for Metal Surfaces.

This review accounts for the most recent and significant research results from the literature on the design and synthesis of 1,2,3-triazole compounds and their usefulness as molecular well-defined corrosion inhibitors for steels, copper, iron, aluminum, and their alloys in several aggressive media. Of particular interest are the 1,4-disubstituted 1,2,3-triazole derivatives prepared in a regioselective manner under copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reactions. They are easily and straightforwardly prepared compounds, non-toxic, environmentally friendly, and stable products to the hydrolysis under acidic conditions.

Cu(ii)-alginate-based superporous hydrogel catalyst for click chemistry azide-alkyne cycloaddition type reactions in water.

A novel sustainable hydrogel catalyst based on the reaction of sodium alginate naturally extracted from brown algae residue with copper(ii) was prepared as spherical beads, namely Cu(ii)-alginate hydrogel (Cu(ii)-AHG). The morphology and structural characteristics of these beads were elucidated by different techniques such as SEM, EDX, BET, FTIR and TGA analysis. Cu(ii)-AHG and its dried form, namely Cu(ii)-alginate (Cu(ii)-AD), are relatively uniform with an average pore ranging from 200 nm to more than 20 μm.

In silico molecular investigations of pyridine N-Oxide compounds as potential inhibitors of SARS-CoV-2: 3D QSAR, molecular docking modeling, and ADMET screening.

The new coronavirus SARS-CoV-2 virus is causing a severe pneumonia in human, provoking the serious outbreak epidemic CoV-2. Since its appearance in Wuhan, China on December 2019, CoV-2 becomes the biggest challenge the world is facing today, including the discovery of antiviral drug for SARS-CoV-2. In this study, the potential inhibitory of a class of human SARS inhibitors, namely pyridine N-oxide derivatives, against CoV-2 was addressed by quantitative structure-activity relationship 3 D-QSAR.

Sustainable Construction of Heterocyclic 1,2,3-Triazoles by Strict Click [3+2] Cycloaddition Reactions Between Azides and Alkynes on Copper/Carbon in Water.

1,4-Disubstituted-1,2,3-triazoles, considered as an important and useful class of heterocycles with potential applications in material science and biology, have been prepared in an efficient and selective manner by copper on carbon-catalyzed [3+2] cycloaddition reactions of azides and alkynes (CuAAC) in water under strict click chemistry conditions. Copper(I) catalysts heterogenized onto commercially activated carbon materials (Cu-CC) and on another carbon material produced from vegetable biomass (Cu-CANS) were found to be versatile catalytic sources for sustainable CuAAC. These copper on carbon supports were prepared and fully characterized by using two types of activated carbons that exhibit different porosity and specific surface.

Cellulose‑copper as bio-supported recyclable catalyst for the clickable azide-alkyne [3 + 2] cycloaddition reaction in water.

Naturally-occurring cellulose has been employed as a bio-support macromolecule for the immobilization of either copper(I) or copper(II) ions in order to click azide and alkyne derivatives in water. Under such a click regime, 1,4-disubstitued-1,2,3-triazoles were obtained regioselectively in excellent yields at room temperature. The reaction work-up is simple and the bio-heterogeneous catalyst that has been fully characterized by AAS, SEM, EDX and FT-IR can be easily separated and reused at least five times without any significant decrease in its activity and selectivity, particularly in the case of the very stable CuI-Cellulose.

Understanding the mechanism and regioselectivity of the copper(i) catalyzed [3 + 2] cycloaddition reaction between azide and alkyne: a systematic DFT study.

The copper(i) catalyzed azide-alkyne [3 + 2] cycloaddition (32CA) reaction and its uncatalyzed version have been studied for systematic understanding of this relevant organic transformation, using DFT calculations at the B3LYP/6-31G(d) (LANL2DZ for Cu) computational levels. In the absence of a copper(i) catalyst, two regioisomeric reaction paths were studied, indicating that the 32CA reaction takes place through an asynchronous one-step mechanism with a very low polar character. The two reactive channels leading to 1,4- and 1,5-regisomer present similar high activation energies of 18.

A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σ in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives.

The relationship between the electrophilicity ω index and the Hammett constant σ has been studied for the [2+3] cycloaddition reactions of a series of -substituted phenyl azides towards -substituted phenyl alkynes. The electrophilicity ω index-a reactivity density functional theory (DFT) descriptor evaluated at the ground state of the molecules-shows a good linear relationship with the Hammett substituent constants σ. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.

A Chiral, Photoluminescent, and Spin-Canted {Cu(I)Re(IV)2}n Branched Chain.

A new heteroleptic 1D Cu(I)-Re(IV) coordination polymer of the formula {Cu(I)Re(IV)Cl4(μ-Cl)(μ-pyz)[Re(IV)Cl4(μ-bpym)]}n·nMeNO2 (1; pyz = pyrazine, bpym = 2,2'-bipyrimidine) has been prepared through the Cu(I)-mediated self-assembly of two different Re(IV) metalloligands, namely, [ReCl5(pyz)](-) and [ReCl4(bpym)]. 1 consists of chiral branched chains with an overall rack-type architecture displaying photoemission and magnetic ordering. These results constitute a first step toward making new multifunctional magnetic materials based on mixed 3d-5d molecular systems.

Dicopper(II) metallacyclophanes as multifunctional magnetic devices: a joint experimental and computational study.

Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocalization through a molecular assembly in response to one or many input signals leads to the concept of developing a molecule-based spintronics that can be viewed as a potential alternative to the classical molecule-based electronics.

Bioinspired manganese(II) complexes with a clickable ligand for immobilisation on a solid support.

Clickable ligands like N,N'-bis((pyridin-2-yl)methyl)prop-2-yn-1-amine (L(1)) and N-((1-methyl-1H-imidazol-2-yl)methyl)-N-(pyridin-2-ylmethyl)prop-2-yn-1-amine (L(2)) have been used to synthesise a series of manganese(ii) complexes for grafting onto appropriate solid supports. These ligands mimic the 2-His-1-carboxylate facial chelation present in the active site of the manganese-dependent dioxygenase (MndD), while the alkyne side function allows grafting of the ligand onto an azido-functionalised support using "click chemistry" methodologies. Such synthetic analogues of the MndD crystallise in the solid state as double halide or pseudohalide-bridged dinuclear manganese(ii) complexes of the general formula [Mn2(μ-X)2X2L2] [L = L(1) with X = Cl (), Br (), and N3 (); L = L(2) with X = N3 ()].

Dicopper(II) metallacyclophanes with oligo(p-phenylene-ethynylene) spacers: experimental foundations and theoretical predictions on potential molecular magnetic wires.

Two novel double-stranded dicopper(II) metallacyclophanes of formula (nBu4N)4[Cu2(dpeba)2]·4MeOH·2Et2O (1) and (nBu4N)4[Cu2(tpeba)2]·12H2O (2) have been prepared by the Cu(II)-mediated self-assembly of the rigid ('rod-like') bridging ligands N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and N,N'-1,4-di(4-phenylethynyl)phenylenebis(oxamate) (tpeba), respectively. Single crystal X-ray diffraction analysis of 1 confirms the presence of a dicopper(II)tetraaza[3.3]4,4'-diphenylethynophane metallacyclic structure featuring a very long intermetallic distance between the two square planar Cu(II) ions [r = 14.

Reversible solvatomagnetic switching in a spongelike manganese(II)-copper(II) 3D open framework with a pillared square/octagonal layer architecture.

The concept of "molecular magnetic sponges" was introduced for the first time in 1999 by the creative imagination of the late Olivier Kahn. It refers to the exotic spongelike behavior of certain molecule-based materials that undergo a dramatic change of their magnetic properties upon reversible dehydration/rehydration processes. Here we report a unique example of a manganese(II)-copper(II) mixed-metal-organic framework of formula [Na(H(2)O)(4)](4)[Mn(4){Cu(2)(mpba)(2)(H(2)O)(4)}(3)]·56.

Very long-distance magnetic coupling in a dicopper(II) metallacyclophane with extended π-conjugated diphenylethyne bridges.

Self-assembly of the rigid rodlike ligand N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and Cu(2+) ions affords a novel dinuclear copper(II) metallacyclophane (nBu(4)N)(4)[Cu(2)(dpeba)(2)]·4MeOH·2Et(2)O (1) featuring a very long intermetallic distance (r = 15.0 Å). Magnetic susceptibility measurements for 1 reveal a moderately weak but nonnegligible intramolecular antiferromagnetic coupling between the two metal centers across the double para-substituted diphenylethynediamidate bridge (J = -3.

Efficient ultraviolet-light energy dissipation by an aromatic ketone.

Experimental evidence on the efficiency of 2,2',4,4'-tetramethoxybenzil for UV-light energy dissipation is provided. This non-phenolic aromatic ketone has a low energy triplet which quickly decays to the ketone ground state, thus avoiding the generation of undesirable reactive species.

Hyperbranched polyglycerols: from the controlled synthesis of biocompatible polyether polyols to multipurpose applications.

Dendritic macromolecules with random branch-on-branch topology, termed hyperbranched polymers in the late 1980s, have a decided advantage over symmetrical dendrimers by virtue of typically being accessible in a one-step synthesis. Saving this synthetic effort once had an unfortunate consequence, though: hyperbranching polymerization used to result in a broad distribution of molecular weights (that is, very high polydispersities, often M(w)/M(n) > 5). By contrast, a typical dendrimer synthesis yields a single molecule (in other words, M(w)/M(n) = 1.

Photocatalysis within hyperbranched polyethers with a benzophenone core.

Quenching and product studies have been performed to demonstrate the suitability of hyperbranched polyethers with a tetrafunctionalized benzophenone core as photocatalysts. The triplet photosensitized transformation of an unsaturated diazo compound has been used as the model reaction. The polymer with highest molecular weight led to a similar product distribution even after several catalytic cycles, which evidences its excellent photostability under prolonged irradiation time.

Ligand effects on the structures and magnetic properties of tricyanomethanide-containing copper(II) complexes.

The preparation, crystal structure and magnetic properties of four heteroleptic copper(II) complexes with the tricyanomethanide (tcm(-)) and the heterocyclic nitrogen donors 3,6-bis(2-pyridyl)pyridazine (dppn), 2,5-bis(2-pyridyl)pyrazine (2,5-dpp), 2,3-bis(2-pyridyl)pyrazine (2,3-dpp) and 2,3-bis(2-pyridyl)quinoxaline (2,3-dpq) are reported, {[Cu(2)(dppn)(OH)(tcm)(2)] x tcm}(n) (1), {[Cu(2,5-dpp)(tcm)] x tcm}(n) (2), {[Cu(2)(2,3-dpp)(2)(tcm)(3)(H(2)O)(0.5)] x tcm x 0.5H(2)O}(n) (3) and [Cu(2,3-dpq)(tcm)(2)](n) (4).

Pyrene-benzoylthiophene exciplexes as selective catalysts for the [2+2] cycloaddition between cyclohexadiene and styrenes.

Efficient intramolecular fluorescence quenching in pyrene-benzoylthiophene systems leads to formation of exciplexes. These species interact with 1,3-cyclohexadiene (or styrenes), leading to reactive excited triplexes. The overall process affords [2+2] cross-cycloadducts with an average yield of 57%.

A tetramethoxybenzophenone as efficient triplet photocatalyst for the transformation of diazo compounds.

The aromatic ketone 2,2',4,4'-tetramethoxybenzophenone has a strong absorption band between 300 and 375 nm, and its pi,pi* triplet excited-state is selectively populated in methanol. Both facts make this aromatic ketone a versatile and efficient triplet photocatalyst for the transformation of alpha-diazo carbonyl compounds into mainly the cyclopropanation product.

Positive photocatalysis of a Diels-Alder reaction by quenching of excited naphthalene-indole charge-transfer complex with cyclohexadiene.

[reaction: see text] Naphthalene photo-catalyzes formation of cyclohexadiene-indole cycloadducts in a wavelength-dependent process. Steady-state irradiation and time-resolved fluorescence studies agree well with NP-InH ground-state charge transfer (CT) complexes as the key species responsible for the photo-catalyzed process.

Mechanism of triplet photosensitized Diels-Alder Reaction between indoles and cyclohexadienes: theoretical support for an adiabatic pathway.

Diels-Alder reactions between indoles (InHs) and 1,3-cyclohexadienes (CHDs) were achieved by using aromatic ketones as photosensitizers. For instance, irradiation of deaerated dichloromethane solutions containing benzoylthiophene (BT, 1 mM), indole (20 mM), and phellandrene (40 mM), in the presence of an acylating agent, led to the N-acetylated Diels-Alder cycloadduct in 46% yield (endo:exo ratio of 1.8:1).