Steric and electronic influence on Cu-Cu short contacts in ß-thioketiminato tricopper(I) clusters.

A series of ß-thioketiminate copper(I) complex trimers [LCuI]3 were synthesized by modifying the ligand framework with electron-withdrawing groups (F and Cl) or electron-donating groups (iPr and Me) at the N-aryl ring as well as with CF3 groups on the chelating backbone. This ligand modification significantly impacts the enhancement of Cu⋯Cu short contacts, which can be rationalized by using steric and electronic factors of the chelated ligand. We observed that this intramolecular cuprophilicity among [LCuI]3 complexes is primarily governed by the size of N-aryl ortho-substituents. These findings were well supported by X-ray crystallography, Raman spectroscopy, and Mayer bond order analysis. The electronic effects induced by the ligand modification on the LCuI fragment were investigated using CO and 2,4,6-CNC6H2Me3 as probe molecules. Corroborated by the FTIR and CV measurements, our results reveal that the ß-thioketiminate SN chelators induce more pronounced changes in the electronic character of the LCuI fragment due to the presence of CF3 groups on the chelating backbone in comparison with the F or Cl substituents on the N-aryl ring.

K2CO3-mediated annulation of 1,3-acetonedicarboxylates with 2-fluoro-1-nitroarenes: synthesis of indoles.

The K2CO3-mediated one-pot reaction of 1,3-acetonedicarboxylates with 2 equiv. of substituted 2-fluoro-1-nitrobenzenes has been developed to synthesize various 2,3-dicarboxylate indoles via a tandem annulation pathway. In the effective reaction, one carbon-carbon double bond, one carbon-carbon single bond and one carbon-nitrogen single bond are formed under open-vessel conditions. DFT calculations are used to rationalize the plausible mechanisms.

Unraveling the binding mechanisms of SARS-CoV-2 variants through molecular simulations.

The emergence of SARS-CoV-2 variants like Delta (AY.29) and Omicron (EG.5) poses continued challenges for vaccines and therapeutics. Mutations in the viral spike protein are key in altering infectivity and immune evasion. This study uses computational modeling to investigate the molecular binding mechanisms between spike protein variants and the ACE2 host receptor. Using the MARTNI force field, coarse-grained molecular dynamics (CGMD) simulations and nudged elastic band (NEB) calculations explore spike-ACE2 interactions for the wild type, Delta variant, and Omicron variant. The simulations reveal Omicron has the strongest binding affinity at -128.35 ± 10.91 kcal/mol, followed by Delta and wild type. Key mutations in Delta and Omicron, like Q493R and Q498R, optimize electrostatic contacts, enhancing ACE2 interactions. The wild-type spike has the highest transition state energy barrier at 17.87 kcal/mol, while Delta has the lowest barrier at 9.21 kcal/mol. Despite slightly higher dual barriers, Omicron's increased binding energy lowers its overall barrier to rapidly bind ACE2. These findings provide residue-level insights into mutation effects on SARS-CoV-2 infectivity. The computational modeling elucidates mechanisms underlying spike-ACE2 binding kinetics, aiding the development of vaccines and therapies targeting emerging viral strains.

Improvement of catalytic activity of aluminum complexes for the ring-opening polymerization of ε-caprolactone: aluminum thioamidate and thioureidate systems.

In this study, a series of Al complexes bearing amidates, thioamidates, ureidates, and thioureidates were synthesized and their catalytic activity for ε-caprolactone (CL) polymerization was evaluated. SPr-Al exhibited a higher catalytic activity than OPr-Al (3.2 times as high for CL polymerization; [CL] : [SPr-Al] : [BnOH] = 100 : 0.5 : 2; [SPr-Al] = 10 mM, conv. = 93% after 14 min at 25 °C), and USCl-Al exhibited a higher catalytic activity than UCl-Al (4.6 times as high for CL polymerization; [CL] : [USCl-Al] : [BnOH] = 100 : 0.5 : 2; [USCl-Al] = 10 mM, conv. = 90% after 15 min at 25 °C). Regardless of whether aluminum amidates or ureidates were present, thioligands improved the polymerization rate of aluminum catalysts. Density functional theory calculations revealed that the eight-membered ring [SPr-AlOMe2]2 decomposed into the four-membered ring SPr-AlOMe2. However, [OPr-AlOMe2]2 did not decompose because of its strong bridging Al-O bond. The overall activation energy required for CL polymerization was lower when using [SPr-AlOMe2]2 (18.1 kcal mol-1) as a catalyst than when using [OPr-AlOMe2]2 (23.9 kcal mol-1). This is because the TS2a transition state of SPr-AlOMe2 had a more open coordination geometry with a small N-Al-S angle (72.91°) than did TS3c of [OPr-AlOMe2]2, the crowded highest-energy transition state of [OPr-AlOMe2]2 with a larger N-Al-O angle (99.63°).

Ligand Degradation Study of Unsymmetrical ß-Diketiminato Copper Dioxygen Adducts: The Length Chelating Arm Effect.

An investigation on the reactivity of O2 binding to unsymmetrical ß-diketiminato copper(I) complexes by spectroscopic and titration analysis was performed. The length of chelating pyridyl arms (pyridylmethyl arm vs pyridylethyl arm) leads to the formation of mono- or di-nuclear copper-dioxygen species at -80 °C. The pyridylmethyl arm adduct (L1CuO2) forms mononuclear copper-oxygen species and shows ligand degradation, resulting in the formation of (2E,3Z)-N-(2,6-diisopropylphenyl)-4-(((E)-pyridin-2-ylmethylene)amino)pent-3-en-2-imine, which slowly converts to its cyclization isomer 1-(2,6-diisopropylphenyl)-4,6-dimethyl-2-(pyridin-2-yl)-1,2-dihydropyrimidine after addition of NH4OH at room temperature. On the other hand, the pyridylethyl arm adduct [(L2Cu)2(µ-O)2] forms dinuclear species at -80 °C and does not show any ligand degradation product. Instead, free ligand formation was observed after the addition of NH4OH. These experimental observations and product analysis results indicate that the chelating length of pyridyl arms governs the Cu/O2 binding ratio and the ligand degradation behavior.

DFT study on the catalytic decomposition of hydrogen peroxide by iron complexes of nitrilotriacetate.

The Fenton system in the presence of nitrilotriacetate (NTA) ligand is studied by DFT approach. The calculations show that complexation of Fe(II) with NTA significantly facilitates the H2 O2 activation. The ferric-hydroperoxo intermediate NTAFe(III)OOH predominantly decays via the disproportionation into NTAFe(II)OH2 and NTAFe(IV)O involving the formation of a µ-1,2-hydroperoxo-bridged biferric intermediate. In this mechanism, the bridged hydroperoxo is reduced by hydroperoxo ligand rather than by Fe(III). On the one hand, the NTAFe(III)OOH is sluggish to undergo hydrogen abstraction; on the other hand, it is a good nucleophile that may perform aldehyde deformylation. The present calculations suggest that both ˙OH and Fe(IV)O are generated in the NTA-assisted Fenton system. However, the polycarboxylate ligand provides a favorable environment for H2 O2 to accumulate around iron ion through hydrogen bonding. This promotes the quenching of Fe(IV)O by H2 O2 , rationalizing why the Fe(IV)O species is hardly detected in the NTA-assisted Fenton system.

Denticity governs the formation of ß-thioketiminato tri-copper(I) and mono-copper(I) complexes.

Two classes of ß-thioketiminate ligands, SN chelators (HL1 and HL2) and SNN chelators (HL3 and HL4), were prepared to understand their coordination behavior in copper(I) complex formation. The formation of these copper(I) complexes bearing ß-thioketiminate ligands and their corresponding adducts toward isocyanide, PPh3, and CO was investigated to address two important issues. First, whether the denticity governs the copper(I) thiolate species formation between SN chelators and SNN chelators. Second, how the length of the pendant pyridyl arm affects the coordination and reactivity behaviors of copper(I) complexes. Based on the characterization results, it was found that the denticity of SN chelators and SNN chelators led to different nuclearity of copper(I)-thiolate species. The coordination modes of the pendant pyridyl arm were confirmed by FTIR measurements, which allow us to conclude that the electron donating ability of the LCu fragment is in the order of SNN-chelator (SNN bound) > SNN-chelators (SN bound) > SN-chelator.

An investigation on catalytic nitrite reduction reaction by bioinspired CuII complexes.

Catalytic nitrite reductions by CuII complexes containing anionic Me2Tp, neutral Me2Tpm, or neutral iPrTIC ligands in the presence of L-ascorbic acid, which served as an electron donor and proton source, were investigated. The results showed that auxiliary ligands are important for copper-mediated catalytic nitrite reduction. Furthermore, the electronic effects of the ligand govern the nitrite reduction efficiency, which should be considered at two control points: one is the susceptibility of the LCuI-nitrite species to protonation and the other is the susceptibility of LCuII to reduction giving LCuI. In addition, an external strong acid leads to the production of nitrous acid, which may suggest that the reactivity of nitrous acid toward the LCuI species is a third control point.

Synthesis of Distorted Nitrogen-Doped Nanographenes by Partially Oxidative Cyclodehydrogenation Reaction.

A series of partially fused N-doped nanographenes (2-4) are synthesized via the oxidative cyclodehydrogenation of oligoaryl-substituted dibenzo[e,l]pyrene (1), and five, six, and seven new C-C bonds are formed, respectively, implying stepwise C-C bond fusion and extended π-conjugation. Single-crystal X-ray diffraction analysis of compound 4 a revealed that the presence of sterically demanding groups hindered the formation of planar and fully fused nanographene in the oxidative cyclodehydrogenation reaction step. Optical study of compounds 2 to 4 showed that extended π-conjugation leads to a regular stepwise bathochromic shift in the absorption and emission spectra. Furthermore, the HOMO-LUMO gaps of these compounds exhibit a decrease as C-C bond formation proceeds. Thus, the optoelectronic properties of nanographenes are highly dependent on the formation of new C-C bonds in the molecular skeleton.

Ring-Opening Polymerization of ε-Caprolactone by Using Aluminum Complexes Bearing Aryl Thioether Phenolates: Labile Thioether Chelation.

In this study, aluminum complexes bearing ferrocene-based and arylthiomethylphenolate ligands were synthesized, and their catalytic activity for ε-caprolactone (CL) polymerization was investigated. The catalytic activity of the reduced form of Al complexes was higher than that of the oxidized form. The CL polymerization rate of the reduced form fcO2AlMe (75 min, conversion = 100%) was higher than that of the oxidized form fcoxO2AlMe (4320 min, conversion = 45%), and the CL polymerization rate of fc(OAlMe2)2 (40 min, conversion = 100%) was higher than that of fcox(OAlMe2)2 (60 min, conversion = 97%). Electron deficiency substituents on phenolate decreased the catalytic activity of Al complexes bearing arylthiomethylphenolate ligands. Density functional theory calculations revealed that thioether coordination stabilized the transition state (TS1) and that the oxidized form fcox(OAlMe2)2 exhibited weaker thioether coordination and higher activation energy in TS1 compared with those of the reduced form fcO2AlMe. In addition, our study determined that the thioether group is a suitable chelating group for Al catalysts in CL polymerization due to its labile nature.

Responsive fluorescence enhancement for in vivo Cu(II) monitoring in zebrafish larvae.

Several neurodegenerative diseases are ascribed to disorders caused by the secretion of Cu ions. However, a majority of the current techniques for copper ion detection are restricted to in vivo monitoring and nonspecific interactions. Their methods are limited to the systematic analysis of Cu ions in living organisms. Thus, a synthetic molecular fluorophore, 5-amino 2,3-dihydroquinolinimine (NDQI), has been developed and successfully utilized in in vivo monitoring of the distribution of Cu(II) in zebrafish larvae. The reversible formation of the NDQI-Cu complex allows its use with high metal concentrations and in oxidative stress conditions. The NDQI-directed strategy developed here can quantitatively differentiate cells with different Cu(II) concentrations. Remarkably, dynamic distribution of Cu(II) in the intestine and liver can be observed.

DFT mechanistic study on the formation of 8-oxoguanine and spiroiminodihydantoin mediated by iron Fenton reactions.

Fenton reactions unavoidably take place in the human body and have been demonstrated to cause oxidative DNA damage. However, the molecular-level understanding of DNA damage mediated by Fenton reactions is limited. Herein, density functional theory (DFT) calculations were made to investigate the counterion effects on aqueous Fenton reactions and the detailed mechanisms of chemical modifications to guanine induced by Fenton reactions. Our calculations show that the activation energy of the Fenton reaction catalyzed by a pure aquo complex [FeII(H2O)6]2+ is too high to agree with experiments, whereas complexation with counteranions reduces the activation energy to a reasonable range. This result suggests that FeII-counteranion complexes are the real catalyst for fast aqueous Fenton reactions. In addition, we found that the Fenton oxidation mediated by FeII bonded to the N7 atom of guanine can result in the formation of 8-oxoguanine and spiroiminodihydantoin through multiple reaction pathways, including the electrophilic addition of ˙OH, H-abstraction by ˙OH, and oxygen atom transfer of oxoiron(iv) species. The activation of hydrogen peroxide by ferrous iron is the rate-determining step. The guanine N7-bound iron ion and the coordinated counteranion were found to play an important role in the Fenton oxidation of guanine.

Synergistic Catalysis by Brønsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-Like Reactivity.

Carbodicarbene (CDC), unique carbenic entities bearing two lone pairs of electrons are well-known for their strong Lewis basicity. We demonstrate herein, upon introducing a weak Brønsted acid benzyl alcohol (BnOH) as a co-modulator, CDC is remolded into a Frustrated Lewis Pair (FLP)-like reactivity. DFT calculation and experimental evidence show BnOH loosely interacting with the binding pocket of CDC via H-bonding and π-π stacking. Four distinct reactions in nature were deployed to demonstrate the viability of proof-of-concept as synergistic FLP/Modulator (CDC/BnOH), demonstrating enhanced catalytic reactivity in cyclotrimerization of isocyanate, polymerization process for L-lactide (LA), methyl methacrylate (MMA) and dehydrosilylation of alcohols. Importantly, the catalytic reactivity of carbodicarbene is uniquely distinct from conventional NHC which relies on only single chemical feature of nucleophilicity. This finding also provides a new spin in diversifying FLP reactivity with co-modulator or co-catalyst.

Near-IR Charge-Transfer Emission at 77 K and Density Functional Theory Modeling of Ruthenium(II)-Dipyrrinato Chromophores: High Phosphorescence Efficiency of the Emitting State Related to Spin-Orbit Coupling Mediation of Intensity from Numerous Low-Energy Singlet Excited States.

Efficient charge-transfer (CT) phosphorescence in the near-IR (NIR) spectral region is reported for four substituted Ru-(R-dipyrrinato) complexes, [Ru(bpy)2(R-dipy)](PF6), where bpy is 2,2'-bipyridine and the substituent R is phenyl (ph), 2,4,6-trimethylphenyl, 4-carboxyphenyl (HOOC-ph), or 4-pyridinyl. The experimentally determined phosphorescence efficiency, ιem(p) = kRAD(p)/(νem(p))3 (where kRAD(p) and νem(p) are the phosphorescence rate constant and the phosphorescence frequency, respectively), of the [Ru(bpy)2(R-dipy)]+ complexes was approximately double that of [Ru(bpy)(Am)4]2+ complexes (Am = ammine ligand) in the NIR region. Density functional theory (DFT) modeling indicated two strikingly different electronic configurations of the triplet emitting state (Te) in the two types of complexes. The Te of [Ru(bpy)2(R-dipy)]+ complexes shows a CT-type corresponding to the metal-to-ligand charge transfer (MLCT)-(Ru-(R-dipy)) and the ππ*-(R-dipy) moiety configurations, and the Te state in the [Ru(bpy)(Am)4]2+ complexes corresponds to an approximately MLCT excited state consisting of mostly MLCT-(Ru-bpy) with a minimal ππ*(bpy) contribution. DFT modeling also indicated that the low-energy singlet excited states in the Te geometry (Sn(T)) of the [Ru(bpy)2(ph-dipy)]+ complex consist of numerous CT-Sn(T)-type states of the Ru-dipy and Ru-bpy moieties, whereas the [Ru(bpy)(Am)4]2+ ions show quite simple MLCT-Sn(T)-type states of the Ru-bpy moiety. Based on experimental observations, DFT modeling, and the plain spin-orbit coupling (SOC) principle, we conclude that the remarkably high ιem(p) amplitudes of the [Ru(bpy)2(R-dipy)]+ complexes relative to those of [Ru(bpy)(Am)4]2+ complexes can be attributed to the relatively substantial contribution of intrinsic SOC-mediated intensity stealing from the numerous low-energy CT-type Sn(T) states.

In vivo monitoring of carbonic anhydrase expression during the growth of larval zebrafish: a new environment-sensitive fluorophore for responsive turn-on fluorescence.

This study monitors the dynamic progress of a newly developed background-free, target responsive strategy; 2,3-dihydroquinolin-4-imine (DQI) that can instantly respond to environmental changes with fluorescence enhancement, revealing a comprehensive platform for in vivo fluorescence bioimaging of mebrane-bound carbonic anhydrase II in HeLa cells and its expression during the growth of larval zebrafish.

The Mechanical Behaviors of Polyethylene/Silver Nanoparticle Composites: an Insight from Molecular Dynamics study.

This research uses molecular dynamics simulation (MD) to study the mechanical properties of pristine polyethylene (PE) and its composites which include silver nanoparticles (PE/AgNPs) at two AgNP weight fractions of 1.05 wt% and 3.10 wt%. The stress-strain distribution of the tensile process shows that the embedded AgNPs can significantly improve the Young's modulus and tensile strength of the pristine PE, due to improvements in the local density and strength of the PE near the AgNP surface in the range of 12 Å. Regarding the effect of temperature on the mechanical properties of pristine PE and PE/AgNP composites, the Young's modulus and the strength of the pristine PE and PE/AgNP composites decreased significantly at 350 K and 450 K, respectively, consistent with predicted melting temperature of pristine PE, which lies at around 360 K. At such temperatures as these, PE material has stronger ductility and a higher mobility of AgNPs in the PE matrix than those at 300 K. With the increase of tensile strain, AgNPs tend to be close, and the fracture of PE leads to a similarity between both the Young's modulus and ultimate strength found for the pristine PE and those found for the PE/AgNP composites at 350 K and 450 K, respectively.

CuBr2-Mediated One-Pot Synthesis of Sulfonyl 9-Fluorenylidenes.

In this article, a high-yield method for the synthesis of sulfonyl 9-fluorenylidenes is described, which consists of a one-pot straightforward three-step synthetic route, including (i) CuBr2-mediated α-bromination of o-arylacetophenone, (ii) sequential nucleophilic substitution of the resulting α-bromo o-arylacetophenone with sodium sulfinate (RSO2Na), and (iii) the CuBr2-mediated intramolecular Friedel-Crafts cyclizative dehydration. A plausible mechanism is proposed and discussed. This protocol provides a highly effective regio- and stereoselective annulation via the formation of one carbon-carbon (C-C) bond and one carbon-sulfur (C-S) bond.

Construction of Sulfonyl Dihydrobenzo[c]xanthen-7-ones Core via NH4OAc/PdCl2/CuCl2-Mediated Double Cyclocondensation of α-Sulfonyl o-Hydroxyacetophenones with 2-Allylbenzaldehydes.

NH4OAc/PdCl2/CuCl2 mediated domino double cyclocondensation of α-sulfonyl o-hydroxyacetophenones and 2-allylbenzaldehydes provides tetracyclic sulfonyl dihydrobenzo[c]xanthen-7-one core with good to excellent yields in MeOH. The intermediates contain a 3-sulfonyl flavanone motif. Only water is generated as a byproduct. The use of various catalysts and reaction conditions is studied for the facile-operational conversion.

Low-Temperature Spectra and Density Functional Theory Modeling of Ru(II)-Bipyridine Complexes with Cyclometalated Ancillary Ligands: The Excited State Spin-Orbit Coupling Origin of Variations in Emission Efficiencies.

The 77 K emission spectra of cyclometalated ruthenium(II)-2,2'-bipyridine (CM-Ru-bpy) chromophores are very similar to those of related Ru-bpy complexes with am(m)ine or diimmine ancillary ligands, and density functional theory (DFT) modeling confirms that the lowest energy triplet metal to ligand charge transfer (3MLCT) excited states of CM-Ru-bpy and related Ru-bpy complexes have very similar electronic configurations. However, the phosphorescence decay efficiencies of CM-Ru-bpy excited states are about twice those of the conventional Ru-bpy analogues. In contrast to the similar 3MLCT excited state electronic configurations of the two classes of complexes, the CM-Ru-bpy chromophores have much broader visible region MLCT absorptions resulting from several overlapping transitions, even at 87 K. The emitting excited-state emission efficiencies depend on spin-orbit coupling (SOC) mediated intensity stealing from singlet excited states, and this work explores the relationship between the phosphorescence efficiency and visible region absorption spectra of Ru-bpy 3MLCT excited states in the weak SOC limit. The intrinsic 3MLCT emission efficiency, ιem, depends on mixing with singlet excited states whose RuIII-dπ-orbital angular momenta differ from that of the emitting state. DFT modeling of the 1MLCT excited-state electronic configurations that contribute significantly to the lowest energy absorption bands have RuIII-dπ orbitals that differ from those of their emitting 3MLCT excited states. This leads to a very close relationship between ιem and the lowest energy MLCT band absorptivities in Ru-bpy chromophores. Thus, the larger number of 1MLCT transitions that contribute to the lowest energy absorption bands accounts for the enhanced phosphorescence efficiency of Ru-bpy complexes with cyclometalated ancillary ligands.

Why the Reactive Oxygen Species of the Fenton Reaction Switches from Oxoiron(IV) Species to Hydroxyl Radical in Phosphate Buffer Solutions? A Computational Rationale.

It has been shown that the major reactive oxygen species (ROS) generated by the aqueous reaction of Fe(II) and H2O2 (i.e., the Fenton reaction) are high-valent oxoiron(IV) species, whereas the hydroxyl radical plays a role only in very acidic conditions. Nevertheless, when the Fenton reaction is conducted in phosphate buffer solutions, the resulting ROS turns into hydroxyl radical even in neutral pH conditions. The present density functional theory (DFT) study discloses the underlying principle for this phenomenon. Static and dynamic DFT calculations indicate that in phosphate buffer solutions, the iron ion is highly coordinated by phosphoric acid anions. Such a coordination environment substantially raises the pK a of coordinated water on Fe(III). As a consequence, the Fe(III)-OH intermediate, resulting from the reductive decomposition of H2O2 by ferrous ion is relatively unstable and will be readily protonated by phosphoric acid ligand or by free proton in solution. These proton-transfer reactions, which become energetically favorable when the number of phosphate coordination goes up to three, prevent the Fe(III)-OH from hydrogen abstraction by nascent •OH to form Fe(IV)=O species. On the basis of this finding, a ligand design strategy toward controlling the nature of ROS produced in the Fenton reaction is put forth. In addition, it is found that while phosphate buffers facilitate •OH radical generation in the Fenton reaction, phosphoric acid anions can act as •OH radical scavengers through hydrogen atom transfer reactions.