Search Results (22)

In bipolar membrane electrodialysis (BPED), proton transport through the anion-exchange membrane (AEM) is a major factor that reduces overall process efficiency. In this study, we propose a composite AEM incorporating a proton-blocking layer that combines strongly basic and weakly basic functional groups on top of a strongly basic AEM, providing proton-blocking capability while minimizing degradation of membrane conductivity. The proton-blocking layer is prepared by reacting brominated poly(phenylene oxide) (BPPO) with diamines having different alkyl chain lengths, namely N,N,N′,N′-tetramethyl-1,6-hexanediamine (TMHDA), N,N,N′,N′-tetramethyl-1,3-propanediamine (TMPDA), and N,N,N′,N′-tetramethylethylenediamine (TMEDA). When TMHDA, which has the longest alkyl chain, is introduced into PPO, the resulting membrane exhibits high conductivity but low proton-blocking performance. In contrast, when TMEDA, which has the shortest alkyl chain, is introduced, the membrane shows low conductivity and high proton-blocking performance. Therefore, the balance between membrane conductivity and proton-blocking performance can be optimized by adjusting the molar ratio of the two diamines. The composite AEM prepared with the optimal composition simultaneously demonstrates superior conductivity and proton-blocking performance compared to the commercial proton-blocking membrane (ACM, Astom Corp., Tokyo, Japan). Furthermore, the application of this membrane has been shown to effectively improve both the energy efficiency and current efficiency of the BPED process for lithium hydroxide recovery. Full article

Development of new biologically active materials based on natural products has, over the years, attracted considerable attention due to their effectiveness in human health and disease. Polyphenolic compounds, particularly flavonoids, provide a wide range of health benefits, including antioxidant, anti-inflammatory, anticancer, and antibacterial properties. A series of novel Schiff base derivatives of flavonoids with amino-containing linkers was successfully designed and synthesized through condensation reactions. Naringin and naringenin derivatives with diamines, including ethylenediamine (EDA), 1,3-diamino-2-propanol (DA-2-PrOH), tetramethylenediamine (TMEDA), pentamethylenediamine (PMEDA), as well as polyamines spermidine (SPD) and spermine (SPM), were synthesized and well-characterized through FT-IR, UV–Visible, ESI–MS, ¹H and ¹³C NMR spectroscopy, and elemental analysis. The so confirmed and well-characterized derivatives were subjected to photoluminescence studies, exhibiting enhanced activity, especially for naringin-based derivatives, and quenching in some others, thus verifying the significance of chemically modifying the conjugated systems of these molecules. Their biological activity was examined in the case of their antimicrobial efficacy against two Gram (+) (Staphylococcus aureus and Bacillus cereus) and two Gram (−) (Escherichia coli and Xanthomonas campestris) bacterial strains. Antibacterial screening projected selectivity of modified flavonoids against E. coli, proposing new “dense” flavonoid-(poly)amine materials as multifunctional antimicrobial agents and fluorescent probes. Full article

Experimental research was conducted to characterize the ignition delay time and combustion performance of non-toxic reactants as a possible replacement for highly toxic fuels, such as hydrazine. The liquid fuel and oxidizer were N,N,N′,N′-tetramethylethylenediamine (TMEDA) and white fuming nitric acid (WFNA), respectively. The hypergolic ignition delay of the reactants was determined using 100% TMEDA with either >90% or >99.5% WFNA that was distilled, titrated, and droplet-tested in a laboratory setting while controlling the parameters that affect the quality of the yielded product. It was observed that >90% WFNA had three times longer average ignition delay than >99.5% WFNA with both mixtures producing ignition delay times less than 20 ms. Based upon the demonstrated hypergolic droplet test results, a fluid delivery feed system and hypergolic heavyweight bipropellant rocket engine were designed and fabricated to characterize the combustion efficiency of these non-toxic reactants. The rocket injector and characteristic length differed while operating under similar flow conditions to evaluate combustion efficiency. Results demonstrated similar engine performance between both cases of WFNA with improvements of over 30% in combustion efficiency with increased characteristic length. Tests using 100% TMEDA/>90% WFNA achieved a combustion efficiency of 88%. Full article

A highly reactive dicuprate/CuCl aggregate, Nap(Cu₄Cl₂)(TMEDA)₂ (2, Nap = naphthalene-1,8-diyl, TMEDA = tetramethylethylenediamine), was synthesized by the reaction of 1,8-dilithionaphthalene(TMEDA)₂ with four equivalents of CuCl. The X-ray crystal structure of this complex shows that the four copper atoms form a bent parallelogram-shaped core, with terminally bonded chlorine atoms. The naphthalene ring is bonded through carbons in the 1 and 8 positions (peri-positions), each bridging two copper atoms. Full article

A novel catalytic system for homocoupling terminal acetylenes was elaborated based on CuCl as a catalyst (10 mol%), TMEDA as a base and CCl₄ as an oxidant. The influence of the solvent, base, amount of catalyst and CCl₄ on the reaction was investigated. Methanol was found to be the solvent of choice. The broad synthetic scope of the reaction was demonstrated. Diynes with various substituents were prepared in up to 92% yields. The possible reaction mechanism is discussed. Full article

Interaction of [VO(OiPr)₃] with 6-bis(o-hydroxyaryl)pyridine, 2,6-{HOC(Ph)₂CH₂}₂(NC₅H₃), LH₂, afforded [VO(OiPr)L] (1) in good yield. The reaction of LNa₂, generated in-situ from LH₂ and NaH, with [VCl₃(THF)₃] led to the isolation of [VL₂] (2) in which the pyridyl nitrogen atoms are cis; a regioisomer 3∙2THF, in which the pyridyl nitrogen atoms are trans, was isolated when using [VCl₂(TMEDA)₂]. The reaction of the 2,6-bis(o-hydroxyalkyl)pyridine {HOC(iPr)₂CH₂}₂(NC₅H₃), L¹H₂, with [VO(OR)₃] (R = nPr, iPr) led, following work-up, to [VO(OR)L¹] (R = nPr (4), iPr (5)). Use of the bis(methylpyridine)-substituted alcohol (tBu)C(OH)[CH₂(C₅H₃Me-5)]₂, L²H, with [VO(OR)₃] (R = Et, iPr) led to the isolation of [VO(μ-O)(L²)]₂ (6). Complexes 1 to 6 have been screened for their ability to act as pre-catalysts for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL), and rac-lactide (r-LA) and compared against the known catalyst [Ti(OiPr)₂L] (I). Complexes 1, 4–6 were also screened as catalysts for the polymerization of ethylene (in the presence of dimethylaluminium chloride/ethyltrichloroacetate). For the ROP of ε-CL, in toluene solution, conversions were low to moderate, affording low molecular weight products, whilst as melts, the systems were more active and afforded higher molecular weight polymers. For δ-VL, the systems run as melts afforded good conversions, but in the case of r-LA, all systems as melts exhibited low conversions (<10%) except for 6 (<54%) and I (<39%). In the case of ethylene polymerization, the highest activity (8600 Kg·mol·V⁻¹bar⁻¹h⁻¹) was exhibited by 1 in dichloromethane, affording high molecular weight, linear polyethylene at 70 °C. In the case of 4 and 5, which contain the propyl-bearing chelates, the activities were somewhat lower (≤1500 Kg·mol·V⁻¹bar⁻¹h⁻¹), whilst 6 was found to be inactive. Full article

Three molecular sulfido complexes containing a Cd-S-Sn structure motive, [{(tmeda)Cd}₃(SnPh)₂S₆] (1), [{(tmeda)Cd}₂(SnPh₂)₂S₄] (2) and [{(ⁱPr₃P)Cd}₃Cd₄(SnPh₂)₆S₁₃] (3), have been synthesized and characterized by single-crystal X-ray diffraction. So far, 2 is the first cadmium tin sulfido complex soluble in common organic solvents. Analysis by ¹¹³Cd and ¹¹⁹Sn NMR spectroscopy shows a slow rearrangement in solution, while spin coupling between the nuclei can be used to identify the species in solution. Thermolysis of 2 results in CdS and SnS as solid thermolysis products. Full article

Polymers based on renewable monomers are projected to have a significant role in the sustainable economy, even in the near future. Undoubtedly, the cationically polymerizable β-pinene, available in considerable quantities, is one of the most promising bio-based monomers for such purposes. In the course of our systematic investigations related to the catalytic activity of TiCl₄ on the cationic polymerization of this natural olefin, it was found that the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl₄/N,N,N′,N′-tetramethylethylenediamine (TMEDA) initiating system induced efficient polymerization in dichloromethane (DCM)/hexane (Hx) mixture at both −78 °C and room temperature. At −78 °C, 100% monomer conversion was observed within 40 min, resulting in poly(β-pinene) with relatively high M_n (5500 g/mol). The molecular weight distributions (MWD) were uniformly shifted towards higher molecular weights (MW) in these polymerizations as long as monomer was present in the reaction mixture. However, chain–chain coupling took place after reaching 100% conversion, i.e., under monomer-starved conditions, resulting in considerable molecular weight increase and MWD broadening at −78 °C. At room temperature, the polymerization rate was lower, but chain coupling did not occur. The addition of a second feed of monomer in the polymerization system led to increasing conversion and polymers with higher MWs at both temperatures. ¹H NMR spectra of the formed polymers indicated high in-chain double-bond contents. To overcome the polarity decrease by raising the temperature, polymerizations were also carried out in pure DCM at room temperature and at −20 °C. In both cases, rapid polymerization occurred with nearly quantitative yields, leading to poly(β-pinene)s with M_ns in the range of 2000 g/mol. Strikingly, polymerization by TiCl₄ alone, i.e., without any additive, also occurred with near complete conversion at room temperature within a few minutes, attributed to initiation by adventitious protic impurities. These results convincingly prove that highly efficient carbocationic polymerization of the renewable β-pinene can be accomplished with TiCl₄ as catalyst under both cryogenic conditions, applied widely for carbocationic polymerizations, and the environmentally benign, energy-saving room temperature, i.e., without any additive and cooling or heating. These findings enable TiCl₄-catalyzed eco-friendly manufacturing of poly(β-pinene)s, which can be utilized in various applications, and in addition, subsequent derivatizations could result in a range of high-added-value products. Full article

The present research analyzes chemical solvents based on the use of diamines (Ethylenediamine-EDA, 1,2-Dimethylethylenediamine-DMEDA and Tetramethylethylenediamine-TMEDA) for carbon dioxide absorption, taking into account the type of amino centers in the molecules. The presence and type of radicals can affect amine solubility in water, reaction mechanism, reaction kinetics, etc. Diamines have been considered interesting candidates for carbon dioxide chemical absorption, observing a high influence of the molecule structure. The present work analyzes a series of solvents based on diamines with the same chain length between amino centers, but different types of radicals. This study shows an important variability in the behavior of these solvents. EDA-based solvents have shown high absorption rates and stability, but carbamate hydrolysis is relatively low, avoiding an increase in carbon dioxide loading. Full article

In this paper, we describe the lithiation of N-benzylpyrene-1-carboxamide with RLi-TMEDA. We found that the reaction outcome strongly depends on the electrophile used in the quenching step. The electrophile can be introduced at either the benzylic position or at the C-2 position in the pyrene nucleus. Furthermore, when H⁺ was used as the quencher, the product of the intramolecular carbolithiation of the pyrene K-region was formed. Dehydrogenation of the obtained compound with DDQ allowed the synthesis of a novel nitrogen polycyclic compound with an aza-benzo[c,d]pyrene (azaolympicene) skeleton. Attempts to extend the reaction scope to the amides substituted in the phenyl ring 8a and 8b gave an unexpected result. The reaction of both compounds with BuLi gave 1-valerylpyrene (9) in good yield. Photophysical properties, including absorption spectra, emission spectra and quantum yields of the emission of selected products, were studied and discussed. Full article

The interest in the NLO response of organic compounds is growing rapidly, due to the ease of synthesis, availability, and low loss. Here, in this study, Cu(II)-catalyzed selective N-arylation of 2-aminobenzimidazoles derivatives were achieved in the presence of different bases Et₃N/TMEDA, solvents DCM/MeOH/H₂O, and various aryl boronic acids under open atmospheric conditions. Two different copper-catalyzed pathways were selected for N-arylation in the presence of active nucleophilic sites, providing a unique tool for the preparation of NLO materials, C-NH (aryl) derivatives of 2-aminobenzimidazoles with protection and without protection of NH₂ group. In addition to NMR analysis, all synthesized derivatives (1a–1f and 2a–2f) of 5-bromo-2-aminobenzimidazole (1) were computed for their non-linear optical (NLO) properties and reactivity descriptor parameters. Frontier molecular orbital (FMO) analysis was performed to get information about the electronic properties and reactivity of synthesized compounds. Full article

N,O-chelating dicarbonylhydrazido-palladium complexes were synthesized by treatment of 1,2-bis(trifluoroacetyl)hydrazine with a mixture of a Pd(0) source, [Pd(dba)₂] (DBA = dibenzylideneacetone), and four-electron donors including 1,3-bis(diphenylphosphino)propane (DPPP), N,N,N’,N’-tetramethylethylenediamine (TMEDA), and two equivalents of triphenylphosphine. The same products from DPPP and TMEDA could be obtained alternatively by using Pd(OAc)₂ through deprotonation of the diacylhydrazine. The five-membered chelate structure was confirmed by NMR spectra and X-ray crystal structure determination. The X-ray structures indicate that the products are formally considered as Pd(II) complexes with a hydrazido(2–) ligand. In the case of the triphenylphosphine-coordinated complex, a fluxional behavior in dichloromethane-d₂ was observed by variable temperature NMR experiments, possibly due to structural changes between the square planar and pseudo-tetrahedral geometries. Full article

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures. Full article

Six new coordination compounds of copper cations and 1,4-dicarboxylic acids have been synthesized and structurally investigated. Aspartic acid (H₂asp), enantiopure, racemic and meso tartaric acid (H₂tart), di-para-toluyltartaric acid (H₂dptta) and dibenzoyltartaric acid (H₂dbta) represent environmentally benign water-soluble proligands which may be deprotonated for oxygen coordination. Chelating ligands such as tetramethylethylenediamine (TMEDA) and 2-aminomethylpyridine (AMPY) efficiently reduce the dimensionality of the target compounds, and additional aqua ligands complete the coordination environments. In this line of argument, the discrete mononuclear complexes [Cu(AMPY)(asp)(H₂O)] and [Cu(Hdbta)₂(H₂O)₄] were obtained; for the latter, only a preliminary structure model can be presented which, however, agrees with the powder diffraction pattern of the bulk. From enantiopure and racemic tartaric acid and TMEDA the closely related chain polymers [Cu^II(H₂tart)(TMEDA)(H₂O)₂)]_n were obtained; the racemic compound consists of individual homochiral strands of opposite chirality. The high steric demand of di-para-toluyltartaric acid leads to one-dimensional [Cu(dptta)(EtOH)(H₂O)₂]_n with coordinated ethanol (EtOH) in the distant Jahn–Teller site of the coordination sphere. Cu(II), meso-tartaric acid and TMEDA aggregate to a trinuclear coordination compound [Cu^II₂Cu^I(H₂tart)(Htart)(TMEDA)₂]. Its peripheral cations show the expected Jahn–Teller geometry of Cu(II), but the unambiguous assignment of the oxidation state +I for central cation required susceptibility measurements: their results prove the presence of only two and only very weakly interacting divalent cations, separated by a diamagnetic center. Full article

N,N,N′,N′-Tetramethylethylenediamine (TMEDA) is one of the candidate substances of hydrazine for hypergolic bipropellant applications. In this study, two experimental analyses were performed to investigate the characteristics of TMEDA and TMEDA mixed with 1,2,4-triazole. First of all, thermogravimetric analysis was performed to analyze thermal decomposition process of the candidate materials. During heating, TMEDA started to evaporate at a temperature below its boiling point and 1,2,4-triazole evaporated subsequently. In addition, evaporation behaviors of TMEDA droplets with two concentrations of 1,2,4-triazole (10% and 20% by weight) were studied at various temperatures. A single droplet experimentation was accomplished in a high-pressure chamber using a heating system under atmospheric nitrogen gas condition. Its droplet behavior was recorded with a high-speed camera and the data were post-processed using Visual Basic software to trace the droplet diameter variation. Bubbling and puffing were observed in the case of the TMEDA containing 1,2,4-triazole above 400 °C. As a result, the rate of evaporation was substantially enhanced by increasing the concentration of 1,2,4-triazole at same temperature. However, the evaporation rates after TMEDA evaporation were the same irrespective of the concentration of 1,2,4-triazole. Full article