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UV–Vis absorption spectrum of copper(III)-periodate complex. Blue: copper(III)-periodate complex alone, red: after completion of the redox reaction. (Color figure online)
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In the present study the copper(III)-periodate (DPC) has been synthesized in an alkaline medium. The stability of this complex is significantly dependent on the pH of the medium; studies reported its stability in alkaline media. The stability of DPC was investigated in different surfactant media for the first time. The + 3 oxidation state of copper...
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... Their UVvis absorbance spectra show intensive bands in the 300-400 nm region (see the Supporting Information). Because the genuine square-planar d 8 Cu(III) complex with oxygen donor ligands [Cu(HIO 6 ) 2 ] 5À has a maximum absorbance at 416 nm, [13] these bands most likely correspond to the d-d transition of Cu(III). The hypsochromic shift of this band can be explained by ligand effect possessing strong CuÀ C bonding of a partially covalent character. ...
High‐valent Cu(III) trifluoromethyl complexes with 1,3‐diketonates as bidentate oxygen donor ligands LCu(III)(CF3)2 were prepared for the first time and fully characterized, including by X‐ray crystallography. These complexes are bench stable and soluble in most organic solvents. Promising reactivity of Cu(III) trifluoromethyl diketonates in radical and radical‐polar crossover trifluoromethylation reactions was demonstrated. Direct C−H trifluoromethylation of electron‐rich arenes and indoles using Cu(III) trifluoromethyl diketonates under blue light irradiation is described. Azolo‐ and oxy‐trifluoromethylation of terminal alkynes and S‐trifluoromethylation of aromatic thiol can be achieved using LCu(III)(CF3)2 in mild conditions.
... The Cu (III): Cu (II) couple plays a significant role in many reactions since both Cobalt (III) and Cu (III) are active intermediate species in multi-electron transfer reactions [16]. DPC (III) synthesis, stability, analytical uses, structural analysis, and analytical applications have all been covered in several research, which were initially created more than 50 years ago [17,18]. Carbenicillin, a 4 th generation antibiotic, is a semi-synthetic analogue of benzyl-penicillin with carboxyl and benzyl groups. ...
Diperiodatocuprate [DPC (III)] was selected to predict the kinetic studies for carbenicillin (CRBC) oxidation in the basic media. The investigation was completed in the presence of CoCl 3 as catalyst by using a UV/Visible spectrophotometer at 298K temperature and 0.01 mol-dm-3 ionic strength which confirmed a 1:4 stoichiometry between CRBC and DPC (III). Both spectral and elemental analysis was used to identify the final products. Monoperiodatocuperate [MPC (III)] was found to be the primary active species of DPC (III). Pseudo-first order reaction was declared for DPC (III), while fractional order reactions were noticed in case of CRBC (substrate), Co (III) catalyst as well as KOH (alkali). However, for periodate, the reaction was determined to be in negative fractional order. Spectral evidence, determination of various rate constants, and both activation as well as thermodynamic parameters were used to predict plausible mechanism.
... iii) Transdermal gradient The chief reason for absorption in the skin is the "transdermal gradient" triggered by the variance in water content amongst the dehydrated skin surface (approx 20% water) and the epidermis (close to 100%) [32]. iv) Hydrophilicity of the head group of the surfactants For polar molecules surfactants with greater extent in hydrophilicity of the head is more effective than those with lesser hydrophilicity [29,30]. v) Steric forces: Steric hideous forces are instigated by the absorbed molecules with decreased conformational freedom and changes due to molecule/solvent interactions in the two different surfaces [33] (See Table 1). ...
Our world is under serious threat of environmental degradation, climate change and in association with this the out breaks of diseases as pandemics. The devastating impact of the very recent COVID-19, The sharp increase in cases of Cancer, Pulmonary failure, Heart health has triggered questions for the sustainable development of pharmaceutical and medical sciences. In the search of inclusive and effective strategies to meet today's demand, improvised methodologies and alternative green chemical, bio-based precursors are being introduced by scientists around the globe. In this extensive review we have presented the potentiality and Realtime applications of both synthetic and bio-based surfactants in bio-medical and pharmaceutical fields. For their excellent unique amphoteric nature and ability to solubilise in both organic and inorganic drugs, surfactants are one of the most potential candidates for bio-medicinal fields such as dermatology, drug delivery, anticancer treatment, surfactant therapy, vaccine formulation, personal hygiene care and many more. The self-assembly property of sur-factants is a very powerful function for drug delivery systems that increases the bio-availability of the poorly aqueous soluble pharmaceutical products by influencing their solubility. Over the decades many researchers have reported the antimicrobial, anti-adhesive, antibiofilm, anti-inflammatory, antioxidant activities of surfactants regarding its utility in medicinal purposes. In some reports surfactants are found to have spermicidal and laxative activity too. This comprehensive report is targeted to enlighten the versatile applications of Surfactants in drug delivery, vaccine formulation, Cancer Treatment, Therapeutic and cosmetic Pharmaceutical Sciences and prevention of pulmonary failure due to COVID-19.
... Copper, gold and platinum are the most promising candidate for electron transfer redox reactions and owing to their mimicking behaviour with the biological systems Cu (III)/Cu (II) redox couple can be used for the oxidation of glucose in BFCs [16]. As an alternative to noble metals, cobalt (Co) can also be considered as promising candidate for electrocatalysis. ...
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... In MEUF different surfactants are used depending on the basis of mutual interaction between dye and surfactant particles. For the qualitative and quantitative description of such dye-surfactant interactions, various techniques were established such as potentiometry, [13,14] conductrometry, [15,16] photo degradation [16] or ion selective electrodes [17,18]. The spectrophotometric measurement is the most common method among them [19 -24]. ...
... In MEUF different surfactants are used depending on the basis of mutual interaction between dye and surfactant particles. For the qualitative and quantitative description of such dye-surfactant interactions, various techniques were established such as potentiometry, [13,14] conductrometry, [15,16] photo degradation [16] or ion selective electrodes [17,18]. The spectrophotometric measurement is the most common method among them [19 -24]. ...
... For CPC, the DG 0 value was -33.269 kJ/mol while the values for saponin and rhamnolipids were - 16 Table 2 The absorbance of CR in absence (A 0 ) and presence (A) of the three distinct micellar systems and calculated number of CR molecules solubilised (n) Aniruddha Pal et al.: A comparative spectral study on the interaction of organic dye congo-red ...
The present study is an investigation of the solubilising ability of natural and conventional surfactants saponin (sapindus saponin or reetha saponin), Rhamnolipids (RLs) and N-cetylpyridinium chloride (CPC) respectively via dye-surfactant interaction. The ionic dye Congo Red was examined by absorption spectroscopy method for the study. The dye interacted strongly with oppositely charged surfactant N-cetylpyridinium chloride in the pre-micellar concentration range and formed a stable dye-surfactant complex. The thermodynamic parameter, free energy change for all the systems was calculated at a constant temperature of 25°C. The ΔG ⁰ value for N-cetylpyridinium chloride is found to be −33.269 kJ/mol while for saponin and rhamnolipids the values were −16.084 kJ/mol and −26.006 kJ/mol respectively. The values clearly indicate the efficiency of N-cetylpyridinium chloride surfactant compared to the other two surfactants. The present study aims to understand the dye solubilization in surfactant media in order to develop environmentally friendly, green and cost effective techniques.
... Similarly, KOH (BDH) and the other required solutions were prepared and stored safely. A study on the synthesis of alkaline copper (III) periodate (DPC) complex with an overview of its redox behavior in aqueous micellar media including stability and redox nature of Cu (III) periodate complex in a microheterogeneous environment has been reported in the recent literature [45]. ...
Kinetics and mechanism of oxidation of carbenicillin by diperiodatocuprate [DPC-III] in aqueous alkaline medium were studied spectrophotometrically at 298 K and an ionic strength of 0.10 mol·dm−3. The reaction between DPC (III) and carbenicillin in the alkaline medium showed (CRBC : DPC-III) 1 : 4 stoichiometry. The reaction products were identified by the CHNS test, FT-IR, and LC-MS spectral reports. The reaction was of pseudo-first order with respect to DPC (III) and fractional order with respect to carbenicillin as well as alkali but retarding effect with respect to periodate. Monoperiodatocuprate (MPC-III) was found to be the main active species in the alkaline medium in the form of [Cu (H2IO6) (H2O)2]. Activation and thermodynamic parameters with respect to uncatalyzed rate constants (ku) and slow step rate constant (k) as well as equilibrium constants were determined. The plausible mechanism consistent with experimental results was proposed and discussed in detail.
... Diperiodatocuprate (III) was first synthesized by Malatesta 16 more than a half-century ago and thence followed by G. P. Panigrahi and A. C. Pathy 17 .Many research works have been reported on the determination of the nature of this complex 18 . Synthesis, Stability and redox nature of Cu (III) periodate complex in a micro heterogeneous environment like the surfactantmicelle medium has been reported in recent literature 19 .Diperiodatocuprate (III) has a flexible one electron-donating nature and biochemistry, stability as well as sensitivity of trivalent copper are already described in literatures 20 . It acts as an analytical reagent and hence used in many biological and analytical electron transfer reactions 21 . ...
The kinetics and mechanism of oxidation of Amoxicillin by diperiodatocuprate [DPC (III)] in aqueous alkaline medium was studied spectrophotometrically at 298 K and ionic strength of 0.10 mol dm-3. The reaction between DPC and Amoxicillin in alkaline medium showed (AMX: DPC-III) 1:2 stoichiometry. The reaction products were identified by spot test, FT-IR and LC-MS spectral studies. The reaction was of pseudo first order with respect to DPC (III) and fractional order with respect to amoxicillin as well as alkali. The addition of periodate showed retarding effect on the rate of oxidation. Monoperiodatocuprate (MPC-III) was found to be the main active species in the alkaline medium in the form of [Cu (H2IO6)(H2O)2]. Activation parameters with respect to rate constants were computed. The plausible mechanism consistent with experimental results was proposed and discussed in detail.
The study investigates the kinetics associated with the oxidation of D-Mannitol (D-Mann) by diperiodatocuprate(III) (DPC) in an aqueous alkaline medium using spectrophotometric method. Reaction medium’s ionic strength was maintained constant at 0.60 mol dm-3. First-order kinetics in [DPC] and less than unit order for [D-Mann] and [alkali] were observed in the reaction. It was of the negative fractional order in [periodate]. It was determined that the reaction of substrate D-Mann with DPC in an alkaline medium shows 1(D-Mann):4(DPC) stoichiometry. Ionic strength of the medium had no effect on the rate of reaction and same was the observation with dielectric constant. The products of reaction were identified by FTIR and confirmed by LC-ESI-MS spectral data. The reaction constants for each step of the mechanism were determined. For the slow step of reaction mechanism, activation parameters were calculated and discussed. Further, thermodynamic quantities for the reactions were also estimated.
Based on the literature survey, DPC was chosen for the current study. DPC was prepared by the reported methods as cited in the manuscript. Stable reaction mixtures were prepared in two different reagent bottles and maintained at a desired temperature using a water bath. The reaction between the oxidant DPC and substrate D-Mannitol was spectrophotometrically analyzed by a UV-Vis spectrophotometer. With the help of data obtained, graphs were plotted to obtain kobs for different variations, and the mechanism was synthesized. A rate law for the reaction under investigation was proposed based on the results and mechanism.
The present research work is concerned with the systematic account of the catalytic behaviour of binary surfactant solutions during the oxidation of 2-butanol by the diperiodatocuprate(III) copper(III)–periodate complex (DPC) in an aqueous solvent. The work primarily deals with the kinetics of the mixed micelle diperiodatocuprate(III) copper(III)–periodate complex (DPC)-catalysed oxidation of 2-butanol by maintaining pseudo-first-order reaction conditions. The cetylpyridinium chloride (CPC)/Triton X-100 (TX-100) mixed micelle serves as a nano-reactor for the oxidation reaction offering a micro-heterogeneous system in an aqueous media. A strong and pronounced catalytic effect has been exhibited by a mixture of CPC and TX-100 surfactants in 1:7 molar ratio compared to any of the single surfactant. The binary surfactant system cooperatively accelerated the oxidation rate of 2-butanol by reducing the reaction completion time up to 40 times. The cetyltrimethylammonium bromide (CTAB) micelle in the reaction system substantially decreased the oxidation rate compared to the reaction in aqueous media only. Proton NMR spectra are conducted to characterize the oxidation product 2-butanone. NMR data precisely correlate the interaction behaviour of CPC and TX-100 in association with the formation of mixed micellar aggregates in the reaction system. The calculated kinetic parameters such as rate constant (kobs), half-life (t1/2) and effective rate constant (keff) values for the oxidation of 2-butanol by DPC in binary surfactant system are correlated with micellar pseudo-phase model and proton NMR analysis of mixed micelles. The blended micellar catalyst has been recovered and recycled for the next reaction as soon as the oxidation of 2-butanol is finished up.
