Alkyl Bridge Research Articles

Alkyl-linked TiO2@COF heterostructure facilitating photocatalytic CO2 reduction by targeted electron transport

Targeted electron transfer to catalytically active site for CO2 reduction is promising for enhancing the efficiency of artificial photosynthesis. Here, we demonstrate a design of an alkyl-linked heterostructure composing of TiO2 and a Cu-porphyrin-based covalent organic framework (TiO2@CuPorTT-COF) for the photoreduction of CO2 with H2O. Through specific coordination effect, the alkyl chain bridges TiO2 and Cu moiety in COF. Upon light illumination, the photoinduced electrons in TiO2 can be directionally transported across the interface along the alkyl chain to the Cu active sites to reduce adsorbed CO2, while the left holes are consumed by the H2O oxidation, enhancing the spatial separation and utilization of electron-hole pairs. Accordingly, the TiO2@CuPorTT-COF enables remarkably superior catalytic activities over the counterpart without the alkyl bridge for electron transfer with 5 times of CO production rate. An apparent quantum efficiency of 0.455% at 380 nm was achieved. Moreover, a dynamic evolution of Cu active site for CO2 reduction is revealed, which can be promoted by the targeting electron transport approach. This work provides a targeted electron transport strategy for constructing photocatalysts.

Synergetic effects during co-pyrolysis of waste textiles and Ca/Fe-rich industrial sewage sludge: Reaction kinetics and product distribution

Co-pyrolysis is a promising technology for industrial organic waste to utilize their unique resource and energy properties for efficient conversion into valuable products. This study was the first time to characterize the co-pyrolysis of waste textiles with Ca-rich industrial sludge and Fe-rich industrial sludge on a laboratory-scale fixed bed. The properties, mechanisms, gas, oil and carbon production were investigated as a function of temperature and mixing type. Co-pyrolysis increased the total weight loss from 50.05 % to 69.81 % for Ca-rich industrial sludge mixed with 50 % waste textiles and from 49.13 % to 70.01 % for Fe-rich industrial sludge mixed with 50 % waste textiles. The activation energy of co-pyrolysis was approximately 50 % lower compared to the pyrolysis of waste textiles alone. The optimal reaction model for the different reaction stages for all samples was three diffusion (D3). Co-pyrolysis resulted in lower CO and CO2 emission temperatures of about 25–110 °C and produced more short-chain organic compounds (C < 10). Co-pyrolysis produced more aldehydes and ketones organics. Moreover, co-pyrolysis char exhibited an elevated level of fatty alkyl side chains and bridge branching, as well as higher degrees of aromatization and stability. This study offers valuable insights into the potential application of pyrolysis for the management of Ca/Fe-rich industrial sludge and waste textiles, thereby serving as a basis for future utilization endeavors.

Improving the Stability and Kinetic Inertness of Mn(II) Complexes by Increasing the Bridge Length in Bicyclic CDTA-Like Ligands.

Kinetic inertness of Mn(II)-based MRI contrast agents can be improved by increasing the rigidity of the polydentate ligand that tightly coordinate the metal ion. Taking inspiration from the remarkable increase in kinetic inertness of [Mn(CDTA)]2- compared to [Mn(EDTA)]2- due to the cyclohexyl backbone rigidity, we devised that bicyclic ligands would further improve the kinetic inertness of the Mn(II) complexes. The length of the alkyl bridge on the cyclohexane ring was varied from methylene (BCH-DTA), ethylene (BCO-DTA) to propylene (BCN-DTA) to evaluate the influence of the different trans-diaminotetraacetate ligands on relaxometric, thermodynamic and kinetic properties of the Mn(II) complexes. 1H and 17O NMR relaxometric studies showed a slight increase in relaxivity and a faster water exchange rate in these Mn(II)-complexes with respect to [Mn(CDTA)]2-. Solution studies revealed that the conditional stability (pMn) and dissociation half-life (t1/2) at pH 7.4 follow the order [Mn(BCH-DTA)]2-<[Mn(BCO-DTA)]2-<[Mn(BCN-DTA)]2- highlighting the effect of the bridge length on the overall stability of the Mn(II) complexes. Remarkably, [Mn(BCN-DTA)]2- shows an improved pMn value and a 7-times higher kinetic inertness than [Mn(CDTA)]2-. NMR studies on the Zn(II) analogues confirm the rigidity of the bicyclic complexes with an isomerization process at >313 K for the smaller bridged complex [Zn(BCH-DTA)]2-.

One-pot Syntheses of Benzo- and Benzofuran-fused Iridaoxabenzenes via CH Bond Activations of Alkyl-bridged Diphenol Derivatives.

One-pot syntheses of new π-extended metallaaromatic compounds have been developed by utilizing Ir-mediated CH bond activation of ethylene- or ethylidene-bridged diphenol derivatives. Depending on the bridging alkyl groups, two types of iridaoxabenzenes, both of which are doubly fused with benzo and benzofuran units, have been obtained. Studies on their structures and electronic characters indicate that both complexes have an aromatic character on the iridaoxacycles, and their π-conjugated systems are fully delocalized over the whole molecular skeletons. These novel metallaaromatic complexes exhibited some reactivities which are distinct from those reported for the non-fused metallaaromatic compounds.

Magnetic poly(1,8-diaminonaphthalene)-nickel nanocatalyst for the synthesis of antioxidant and antibacterial isoxazole-5(4H)-ones derivatives

A magnetic poly (1,8-diaminonaphthalene)-nickel (PDAN-Ni@Fe3O4) composite as a multifunctional nanocatalyst was prepared in several steps including (I) synthesis of poly (1,8-diaminonaphthalene) (PDAN), (II) modification of PDAN with NiSO4 (PDAN-Ni) and (III) preparation of magnetic nanocatalyst by iron (I and II) salts in the existence of PDAN-Ni complex (PDAN-Ni@Fe3O4). Fourier-transform infrared spectroscopy (FTIR), elemental analysis (CHNSO), vibrating-sample magnetometer (VSM), X-ray diffraction (XRD), energy-dispersive X-ray (EDX), field emission scanning electron microscope (FESEM), ultraviolet–visible (UV–vis), and thermogravimetric analysis (TGA) were applied to characterize the prepared nanocatalyst. The PDAN-Ni@Fe3O4 was applied as an environmentally friendly nanocatalyst for the isoxazole-5(4H)-ones synthesis via a one-pot reaction between aryl/heteroaryl aldehyde, hydroxylamine hydrochloride, and β-ketoester. The nanocomposite was also used for the synthesis of some new alkylene bridging bis 4-benzylidene-3-methyl isoxazole-5(4H)-ones. The catalyst's reusability, and the antioxidant and antibacterial activities of both catalyst and products, were studied. Results showed that the nanocatalyst and isoxazole-5(4H)-ones have antioxidant activity of 75% and 92%, respectively. In addition, the antibacterial test showed that the nanocatalyst and isoxazole-5(4H)-ones have highly active versus Staphylococcus aureus and Escherichia coli bacteria. The reusability and stability of the nanocatalyst, a medium to higher product yield and conversion, a faster reaction time, and the use of green solvents were a few benefits of this study.

Modulating the Differentiation of Kinetically Controlled Supramolecular Polymerizations through the Alkyl Bridge Length.

The synthesis and self-assembling features of N-annulated perylenebisimides (N-PBIs) 2-4 are reported and compared with the complex self-assembly of N-PBI 1. The studies presented herein demonstrate that increasing the length of the alkyl spacer separating the central aromatic core of the dye and the peripheral side chains cancels the differentiation on the corresponding supramolecular polymerization. Thus, only 2 is able to form two different supramolecular polymorphs. The formation of kinetically trapped monomeric species is observed for all the N-PBIs 2-4. These metastable species, constituted by intramolecularly H-bonded pseudocycles of 7, 8, 9, or 10 members for compounds 1, 2, 3, and 4, respectively, provoke kinetically controlled supramolecular polymerizations that can be accelerated by the addition of seeds. The results presented herein shed light on the intricate process of differentiation in self-assembly.

Modulating the Differentiation of Kinetically Controlled Supramolecular Polymerizations through the Alkyl Bridge Length

AbstractThe synthesis and self‐assembling features of N‐annulated perylenebisimides (N‐PBIs) 2–4 are reported and compared with the complex self‐assembly of N‐PBI 1. The studies presented herein demonstrate that increasing the length of the alkyl spacer separating the central aromatic core of the dye and the peripheral side chains cancels the differentiation on the corresponding supramolecular polymerization. Thus, only 2 is able to form two different supramolecular polymorphs. The formation of kinetically trapped monomeric species is observed for all the N‐PBIs 2–4. These metastable species, constituted by intramolecularly H‐bonded pseudocycles of 7, 8, 9, or 10 members for compounds 1, 2, 3, and 4, respectively, provoke kinetically controlled supramolecular polymerizations that can be accelerated by the addition of seeds. The results presented herein shed light on the intricate process of differentiation in self‐assembly.

Spectroscopic and computational study of the interaction of Pt(II) pyrrole-imine chelates with human serum albumin.

Three bis(pyrrolide-imine) Pt(II) chelates were synthesised and characterized with different bridging alkyl groups, specifically 2-hydroxypropyl (1), 2,2-dimethylpropyl (2), and 1,2-(S,S)-(+)-cyclohexyl (3). Novel compounds 1 and 2 were analysed by single-crystal X-ray diffraction (space group P1̄). The asymmetric unit of 1 comprises three independent molecules linked by hydrogen bonds involving the OH groups, forming a trimeric supramolecular structure. The Pt(II) chelates were reacted with human serum albumin (HSA) to investigate how the ligand bound to the Pt(II) ion influences the compound's affinity for HSA. Fluorescence quenching data obtained for native HSA and HSA bound to site-specific probes (warfarin, subdomain IIA; ibuprofen, subdomain IIIA) indicated that the three Pt(II) chelates bind close enough (within ∼30 Å) to Trp-214 to quench its intrinsic fluorescence. The bimolecular quenching constant (kq) was 103-104 -fold higher than the maximum diffusion-controlled collision constant in water (1010 M s-1) at 310 K, while the affinity constants, Ka, ranged from ∼5 × 103 to ∼5 × 105 at 310 K, and followed the order 1 > 3 > 2. The reactions of 1 and 3 with HSA were enthalpically driven, while that for 2 was entropically driven. Macromolecular docking simulations (Glide XP) and binding site specificity assays employing site-specific probes and UV-vis CD spectroscopy indicated that 1 and 2 target Sudlow's site II in subdomain IIIA, minimally perturbing the tertiary structure of the protein. Well-resolved induced CD signals from 1 and 2 bound to HSA in subdomain IIIA were adequately simulated by hybrid QM:MM TD-DFT methods. We conclude that the structure of the bis(pyrrolide-imine) Pt(II) chelate measurably affects its uptake by HSA without detectable decomposition or demetallation. Such compounds could thus serve as metallodrug candidates capable of utilising an HSA-mediated cellular uptake pathway.

Gas-phase Förster resonance energy transfer in mass-selected and trapped ions.

Förster Resonance Energy transfer (FRET) is a nonradiative process that may occur from an electronically excited donor to an acceptor when the emission spectrum of the donor overlaps with the absorption spectrum of the acceptor. FRET experiments have been done in the gas phase based on specially designed mass-spectroscopy setups with the goal to obtain structural information on biomolecular ions labeled with a FRET pair (i.e., donor and acceptor dyes) and to shed light on the energy-transfer process itself. Ions are accumulated in a radio-frequency ion trap or a Penning trap where mass selection of those of interest takes place, followed by photoexcitation. Gas-phase FRET is identified from detection of emitted light either from the donor, the acceptor, or both, or from a fragmentation channel that is specific to the acceptor when electronically excited. The challenge associated with the first approach is the collection and detection of photons emitted from a thin ion cloud that is not easily accessible while the second approach relies both on the photophysical and chemical behavior of the acceptor. In this review, we present the different instrumentation used for gas-phase FRET, including a discussion of advantages and disadvantages, and examples on how the technique has provided important structural information that is not easily obtainable otherwise. Furthermore, we describe how the spectroscopic properties of the dyes are affected by nearby electric fields, which is readily discernable from experiments on simple model systems with alkyl or π-conjugated bridges. Such spectral changes can have a significant effect on the FRET efficiency. Ideas for new directions are presented at the end with special focus on cold-ion spectroscopy.

Tuning the Charge Transport in Nickel Salicylaldimine Polymers by the Ligand Structure.

The conductivity of the polymeric energy storage materials is the key factor limiting their performance. Conductivity of polymeric NiSalen materials, a prospective class of energy storage materials, was found to depend strongly on the length of the bridge between the nitrogen atoms of the ligand. Polymers obtained from the complexes containing C3 alkyl and hydroxyalkyl bridges showed an electrical conductivity one order of magnitude lower than those derived from more common complexes with C2 alkyl bridges. The observed difference was studied by means of cyclic voltammetry on interdigitated electrodes and operando spectroelectrochemistry, combined with density functional theory (DFT) calculations.

Conversion of low temperature coal tar into high value-added chemicals based on the coupling process of fast pyrolysis and catalytic cracking

To convert the Xinjiang low temperature coal tar (XJ-CT) into high value-added chemicals, the coupling process of fast pyrolysis and catalytic cracking (FP-CC process) is proposed, and the related fundamental data is collected in this research. First, the composition of XJ-CT is analyzed by GC-GC/MS, and the result shows that the relative contents of alkanes, alkenes, aromatics, and the oxygen compound are 13.16%, 4.85%, 48.38%, and 29.29%, respectively. Then, the performance of XJ-CT fast pyrolysis is evaluated under different reaction temperature. The results show that aromatics is predominant among the pyrolysis vapor, whereas the yield of aliphatic products enhances with the increase of temperature. And the aliphatic products are mainly formed from the deep cleavage of long-chain aliphatics and alkyl side chains (alkyl bridge chain) of aromatics. Meanwhile, the relative content of oxygen-containing compounds decrease with the increase of temperature. Furthermore, molecular distributions of the major groups in pyrolysis vapor with different temperatures are summarized to gain insight into the pyrolysis process. Finally, the ZSM-5 (40), ZSM-5 (200), and USY zeolite are used to catalyze the pyrolysis vapor. It is demonstrated that the maximum light olefin yield of 31.79% is obtained over ZSM-5 (40), while converting XJ-CT to liquid fuels can be realized on USY zeolite.

Hybridization of amantadine with gardenamide A enhances NMDA antagonism and in vivo anti-PD effects

Eight hybrids of amantadine (ATD) with a natural modulator gardenamide A (GA) via an alkylene carbonyl bridge or alkylene bridge have been designed and synthesized. Evaluated by electrophysiological assay, compound 5b was confirmed an enhanced NMDAR antagonist compared to ATD with IC50 value of 10.2 ± 1.2 μM. 5b has been demonstrated to reverse the damages of behavioral performance, the loss of dopaminergic neurons, the reduction of TH positive, and the increase of α-synuclein in both MPTP-treated mice and zebrafish models. In both ethological and ecological experiments, the activity of 5b was confirmed better than ATD or ATD/GA combination, and was almost equal to the positive selegiline. In vivo and in vitro, 5b is shown to reverse the ascend of NR1 and i-NOS levels. This candidate was also demonstrated the activity to down-regulated MPTP-increased Ca2+ influx in SH-SY5Y cells in a steep and sharp mode. It is displayed that 5b exerts neuroprotective effect partly by activating the PI3K/Akt signaling pathway. Taken all together, our data support that 5b is a more promising agent against PD than ATD.

Poly(aniline-co-melamine)@MnFe2O4 nanocatalyst for the synthesis of 4,4'-(arylmethylene) bis (1H-pyrazole-5-ol) derivatives, and 1,4- dihydropyrano[2,3-c]pyrazoles and evaluation of their antioxidant, and anticancer activities.

In this work, magnetic poly(aniline-co-melamine) nanocomposite as an efficient heterogeneous polymer-based nanocatalyst was fabricated in two steps. First, poly(aniline-co-melamine) was synthesized through the chemical oxidation by ammonium persulfate, then the magnetic nanocatalyst was successfully prepared from the in-situ coprecipitation method in the presence of poly(aniline-co-melamine). The resulting poly(aniline-co-melamine)@MnFe2O4 was characterized by FTIR, FESEM, XRD, VSM, EDX, TGA, and UV-vis analyses. The catalytic activity of poly(aniline-co-melamine)@MnFe2O4 was investigated in the synthesis of 4,4'-(arylmethylene)bis(1H-pyrazole-5-ol) derivatives, and new alkylene bridging bis 4,4'-(arylmethylene)bis(1H-pyrazole-5-ol) derivatives in excellent yields. The yield of 1,4-dihydropyrano[2,3-c]pyrazoles, 4,4'-(arylmethylene)bis(1H-pyrazol-5-ol), yields, and new alkylene bridging bis 4,4'-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives were obtained 89%-96%, 90%-96%, and 92%-96%, respectively. The poly(aniline-co-melamine)@MnFe2O4 nanocatalyst can be recycled without pre-activation and reloaded up to five consecutive runs without a significant decrease in its efficiency. In addition, the antioxidant activity of some derivatives was evaluated by DPPH assay. Results showed that the maximum antioxidant activity of 4,4'-(arylmethylene)bis(1H-pyrazole-5-ol) derivatives and 1,4-dihydropyrano[2,3-c]pyrazoles were 75% and 90%, respectively. Furthermore, 4,4'-(arylmethylene)bis(1H-pyrazole-5-ol) derivatives and 1,4-dihydropyrano[2,3-c]pyrazoles showed good potential for destroying colon cancer cell lines. Consequently, the poly(aniline-co-melamine)@MnFe2O4 nanocomposite is an excellent catalyst for green chemical processes owing to its high catalytic activity, stability, and reusability.

Cover Feature: Flexible Alkylene Bridges as a Tool To Engineer Crystal Distyrylbenzene Structures Enabling Highly Fluorescent Monomeric Emission (Chem. Eur. J. 52/2022)

Cover Feature: Flexible Alkylene Bridges as a Tool To Engineer Crystal Distyrylbenzene Structures Enabling Highly Fluorescent Monomeric Emission (Chem. Eur. J. 52/2022)

Flexible Alkylene Bridges as a Tool To Engineer Crystal Distyrylbenzene Structures Enabling Highly Fluorescent Monomeric Emission.

To design ultrabright fluorescent solid dyes, a crystal engineering strategy that enables monomeric emission by blocking intermolecular electronic interactions is required. We introduced propylene moieties to distyrylbenzene (DSB) as bridges between the phenyl rings either side of its C=C bonds. The bridged DSB derivatives formed compact crystals that emit colors similar to those of the same molecules in dilute solution, with high quantum yields. The introduction of flexible seven‐membered rings to the DSB core produced moderate distortion and steric hindrance in the DSB π‐plane. However, owing to this strategy, it was possible to control the molecular arrangement with almost no decrease in the crystal density, and intermolecular electronic interactions were suppressed. The bridged DSB crystal structure differs from other DSB derivative structures; thus, bridging affords access to novel crystalline systems. This design strategy has important implications in many fields and is more effective than the conventional photofunctional molecular crystal design strategies.

Synthesis of Polyhydroquinolines and 2-Amino-4H-Chromenes and their Alkylene Bridging Derivatives using Sulfonic acid Functionalized Heterogeneous Nanocatalyst Based on Modified Poly (Styrene-alt-Maleic Anhydride)

: A highly efficient heterogeneous nanocatalyst based on modified poly (styrene-altmaleic anhydride) (MPSAMA) in three steps was fabricated. Then, the MPSAMA surface was modified using chlorosulfonic acid (CAS) to achieve a sulfonated MPSAMA (SMPSAMA) with high acidity and efficiency. FT-IR spectroscopy, CHNS analysis, FESEM, and TGA were employed to characterize the prepared nanocatalyst. The catalytic activity of the SMPSAMA was examined for the formation of the polyhydroquinoline derivatives through Hantzsch condensation and the synthesis of 2-amino-4H-chromene derivatives. This new heterogeneous nanocatalyst has been efficiently used for the synthesis of bifunctional bis polyhydroquinoline, and new alkylene bridging bis 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-benzo[b]pyran derivatives.

Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage.

Invited for the cover of this issue are Kentaro Tanaka at Nagoya University and co-workers. The image depicts the importance of the flexibility of bridging alkyl chains in a molecular conjugate to pack the components closely to generate efficient molecular communication. Read the full text of the article at 10.1002/chem.202200819.

Front Cover: Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage (Chem. Eur. J. 37/2022)

The flexibility of the bridging alkyl chains is important for proximity in the stacking of porphyrin and phthalocyanine conjugated through a fourfold rotaxane linkage. This picture shows a chochin, a Japanese lantern made with paper and thin strips of bamboo that can be expanded and contracted flexibly. This foldability recalls the induced molecular interaction in the flexible molecular conjugate. More information can be found in the Research Article by K. Tanaka et al. (DOI: 10.1002/chem.202200819).

A New Structural Model of Enzymatic Lignin with Multiring Aromatic Clusters.

Lignin is a natural aromatic compound in plants. Several lignin structural models have been proposed in the past years, but all the models cannot be converted to benzene carboxylic acids (BCAs) for all aromatic rings connected to oxygen. This inspired us to explore the structures of lignin. Based on the yields of BCAs, the results of 13C NMR and ethanolysis residues, and gas chromatography–mass spectrometry and electrospray ionization mass spectrometry of ethanolysis of lignin, we have constructed a structural model of lignin with a formula C6407H6736O2590N147S3. The model not only satisfies the results of analyses, but also explains the generation of BCAs from lignin oxidation and the ethanolysis products. Importantly, double-ring and triple-ring aromatic clusters are found in lignin, and some of them are connected by alkyl bridges, which results in conventional low conversions of lignin. Our findings in the structures of lignin may significantly influence the structures and applications of lignin.

Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage.

Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10 ) chains was estimated to be 4.03 Å and showed a unique physical character arising from short-distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains.