Deep in blue with green chemistry: influence of solvent and chain length on the behaviour of N- and N,N′- alkyl indigo derivatives

Using green chemistry procedures the synthesis of N-alkyl (NC_nInd) and N,N′-dialkyl (N,N′C_nInd) indigo derivatives, with n = 1–3, 6, 8, 12 and 18, was undertaken, leading to compounds with blueish to greenish colors in solution. The effect of the alkyl chain length on the spectral (including color) and photophysical properties of the compounds was explored. This was done with solvents of different viscosities and polarities (dielectric constants). From time-resolved fluorescence and femtosecond-transient absorption (fs-TA) for the NC_nInd derivatives with n = 1 and 2, the decays are, in methylcyclohexane (MCH) and n-dodecane, single-exponential, while in 2-methyltetrahydrofuran (2MeTHF) they are bi-exponential. The excited state proton transfer (ESPT) is ultrafast (<1 ps) for NC_1,2Ind in MCH and n-dodecane, supported by time-dependent density functional theory (TDDFT) calculations, thus showing that both the chain length and solvent influence the ESPT process. For N,N′C_nInd, from time-resolved experiments, and with the exception of the shortest member of the series, N,N′C₁Ind, two conformers are found to be present in the excited state.

Using green chemistry procedures the synthesis of N- and N,N′-alkyl indigo derivatives was undertaken and the effect of the alkyl chain length on the spectral (including color) and photophysical properties of the compounds explored.     

Halogen atom effect on photophysical and photodynamic characteristics of derivatives of 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin

Brominated and iodinated derivatives of 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin were synthesised directly from the corresponding aldehydes. Photophysical and photochemical properties, singlet oxygen formation quantum yields, photobleaching and log P were measured. Cellular uptake measurements and cytotoxicity assays on WiDr and A375 tumour cell lines were performed. 5,10,15,20-Tetrakis(2-bromo-5-hydroxyphenyl)porphyrin showed the best cytotoxicity with values of IC(50) of 113 nM over WiDr cells and 52nM over A375 cells.     

Fish muscle parvalbumins as marker proteins for native and urea isoelectric focusing

An isoelectric point (pI) calibration kit containing fish muscle parvalbumins was prepared and tested for its suitability for isoelectric focusing (IEF) in the presence of 8 M urea. The pattern obtained by urea CleanGel IEF consisted of nine bands covering the pI range 4.96-5.64. This range is relevant for species identification of heated fish by urea IEF. The kit may also be used for native IEF in the low pH range, as demonstrated by running an extract made from the kit together with water-soluble fish muscle proteins on Servalyt Precotes 3-6.     

Temperature dependence of volumetric behaviour for methyl tert-butylether+1-butanol system

Excess molar volumes and excess isoentropic compressibilities of methyl tert-butylether (MTBE)+1-butanol at 288.15, 293.15, 298.15, 303.15 and 308.15 K and atmospheric pressure have been studied. In order to analyse the temperature dependence of this mixture, isobaric expansibility a, (dV _m ^e dT) _P,xand (dH _m ^e dP ) _T,x, were computed by analytical differentiation of the density and excess molar volume fitting equations. Cubic equation of state (Soave-Redlich-Kwong) has been applied to excess molar volume correlation obtaining binary interaction parameters using different mixing rules. This revised version was published online in July 2006 with corrections to the Cover Date.     

Aggregation-Induced Emission Leading to White Light Emission in Diphenylbenzofulvene Derivatives

The search for a unique molecular system able to efficiently emit in the total visible range of the electromagnetic spectra, i. e., white light emission (WLE), is a topic of intense research. We here show that aggregates formed by diphenylbenzofulvene ( DPBF ) derivatives are from two to four orders of magnitude more emissive than their monomers. From a simple strategy, involving structural modification of a DPBF propelled shape core, a close match with the pure white light emission coordinates is obtained with a combination of two derivatives in films, with featured solid-state emission, without involvement of D−A groups or energy transfer processes.     

Relative permittivities of binary mixtures of 1-butanol + n-alkane AT 298.15 k

A previous study on the physical properties of 1-alkanol + n-alkane has establised a correlation between dielectric permittivity at 1 GHz and excess molar volumes for all binary systems that were studied. In order to determine whether this behaviour is similar at lower frequencies, relative permittivity was measured at 100 kHz. The refractive index was measured to explore the effects at higher frequencies. Mixtures under study are in particular the systems (1-butanol + n-hexane, or n-octane, or n-decane) at the temperature of 298.15 K and atmospheric pressure, over the entire composition range. This revised version was published online in July 2006 with corrections to the Cover Date.     

Correction: Deep in blue with green chemistry: influence of solvent and chain length on the behaviour of N- and N,N′-alkyl indigo derivatives

Correction for ‘Deep in blue with green chemistry: influence of solvent and chain length on the behaviour of N- and N,N′-alkyl indigo derivatives’ by Daniela Pinheiro et al., Chem. Sci., 2020, DOI: 10.1039/d0sc04958a.

The authors regret that incorrect compound names and values are reported in Table 5 of the original article. The corrected Table 5 is shown below.Comparison of the fluorescence decay times, τ_i, obtained from the ultrafast time-resolved TA studies and from the ps-TCSPC technique for N,N′C₁Ind and N,N′C₂Ind in n-dodecane and 2MeTHF at T = 293 K

Modern Methods for the Sustainable Synthesis of Metalloporphyrins

Metalloporphyrins are involved in many and diverse applications that require the preparation of these compounds in an efficient manner, which nowadays, also involves taking into consideration sustainability issues. In this context, we use ball milling mechanochemistry and sonochemistry for the rational development of synthetic strategies for the sustainable preparation of metalloporphyrins. Zinc, copper, cobalt and palladium complexes of hydrophobic porphyrins were obtained in high yields and under mechanical action with a moderate excess of the metal salt, without any solvent or additive. Sonochemistry prove to be a good alternative for the preparation of metal complexes of water-soluble porphyrins in good yields and short reaction times. Both strategies have good sustainability scores, close to the ideal values, which is useful in comparing and helping to choose the more adequate method.     

In Vitro Photodynamic Activity of 5,15-bis(3-Hydroxyphenyl)porphyrin and Its Halogenated Derivatives Against Cancer Cells

5,15-Diarylporphyrins ( 1-5 ) with hydroxyl groups and halogens as substituents were prepared by condensation between unsubstituted dipyrromethane and halogenated m -hydroxybenzaldehydes. Photophysical properties show that the nonhalogenated porphyrin 1 has higher fluorescence yield but lower singlet oxygen formation quantum yield than the halogenated derivatives due to the heavy atom effect. The in vitro activity of these derivatives was tested against WiDr colorectal adenocarcinoma and A375 melanoma cancer cells. All porphyrins present a much higher phototoxicity than Photofrin^® with IC ₅₀ values lower than the 50 n m level for WiDr cells and 25 n m level for A375 cancer cells. The most photoactive compound is the nonhalogenated porphyrin 1 which also presents the highest uptake. Halogenated derivatives present much lower uptakes than 1 . However, their photoactivity is similar to compound 1 showing that their intrinsic photoactivity (ISP) is very high. Iodinated compound 4 presents the highest ISP. The greater ability of these porphyrins to destroy cancer cells could be related to their photophysical and photochemical properties.