Singlet oxygen quenching by thione analogues of canthaxanthin, echinenone and rhodoxanthin

Thione analogues of three naturally occurring carotenones (canthaxanthin, echinenone, and rhodoxanthin) were synthesized just over ten years ago, and it was reported that substitution of the oxygen atom by sulphur brings about a large red shift and some broadening in the optical absorption spectrum of the compound. Since the three carotenothiones are scarce, determination of their molar absorption coefficients presents a challenge. A method for relating the molar absorption coefficient of a carotenothione (Car-S) to that of its ketone analogue (Car-O) has been developed, which has revealed that the peak molar absorption coefficient of a Car-S is only about 60% of the corresponding value for Car-O. Using methylene blue as the sensitizer and acetonitrile as the solvent, we have also investigated the quenching (under photostationary conditions) of the 1270nm phosphorescence emission of singlet oxygen by each of the six carotenoids. The data conform to the Stern-Volmer relation, and show that substitution of a carbonyl oxygen atom by sulphur does not lead to an appreciable change in the value of the quenching constant, which is close to 1.5 x 10(10)M(-1)s(-1) for all six quenchers.     

Quantitative spectrophotometry using integrating cavities

Absorption spectrophotometry, a standard tool for quantitative analysis, suffers from two major drawbacks: lack of sensitivity and vulnerability to scattering. It has been pointed out earlier that the solution to these problems lies in using a reflecting cavity as a sample holder. Due to multiple reflections at the cavity wall, the effective pathlength becomes considerably larger than the diameter of the cavity, and scattering losses are eliminated because scattered light is prevented from escaping the detector. Though much effort has been spent in analysing and improving the performance of such a device, often called an integrating cavity absorption meter (ICAM), a simple strategy for deducing the absorbance of the sample is still lacking. It is shown here that the absorbance A' measured by using an ICAM exhibits a sublinear increase with the solute concentration C. The physical reason for this departure from linearity is explained, and a straightforward procedure for converting A' to the true absorbance A (proportional to C) is established. The reliability of the procedure is demonstrated by comparing the ICAM absorption spectrum of dilute dye solutions with the spectra of more concentrated solutions recorded in a conventional spectrophotometer. The ability of the device to cope with scattering was tested by filling the ICAM with a suspension of chloroplasts, and the spectrum was found, as expected, to be free from scattering artefacts.     

Diffusion-controlled reactions in two-dimensional fluids: discussion of measurements of lateral diffusion of lipids in biological membranes

Differences between the reaction kinetics of diffusion-controlled reactions in two and three dimensions are examined, and expressions for the rate of a diffusion-controlled reaction in a two-dimensional fluid are derived. A method of analysing the results of some recent investigations of lateral diffusion of lipids in biological membranes is presented.     

Planar chromatographic separation of petroleum residues and coal-derived liquids

Vacuum distillation residues from two petroleum crudes, a coal liquefaction extract and a coal tar pitch have been fractionated by planar chromatography (PC) using two solvent sequences: pyridine–acetonitrile and tetrahydrofuran (THF)–toluene. Fractions recovered from PC were examined by UV-fluorescence spectroscopy (UV-F), size-exclusion chromatography (SEC). UV-F and SEC of the whole samples showed differences in aromatic cluster size and molecular mass (MM) ranges which could be related to the different origins of the samples. The MM ranges indicated by SEC were greater for the vacuum residues than for coal-derived materials. However, the UV-F spectra of the fractions indicated that the petroleum residue fractions contained similar aromatic types, whereas the fractions from coal liquids contained significantly different aromatic types. SEC profiles of the fractions indicated a separation of coal-derived samples by increasing molecular size with increasing immobility in PC, whereas for petroleum fractions, the same trend was not apparent. MALDI-mass spectra of the set of original samples showed broadly similar ranges of MM distributions but additional work is necessary to identify appropriate matrices and procedures in order to improve the MALDI spectra.     

Recent trends in ring opening of epoxides by amines as nucleophiles

β-Amino alcohols are versatile intermediates in the synthesis of various biologically potent compounds, which can also be achieved by ring opening of epoxides by amines. In the present review, focus has been placed on the ring opening of epoxides with amines under a variety of reaction parameters reported during 2011–2015. All the factors that resulted in excellent yields and high regioselectivity, are environmentally benign, and use mild conditions have been discussed in detail. In addition, the applications of these methods in the synthesis of biologically active compounds such as β-blockers have also been described.     

Raman scattering studies of sodalite for crystal structure and coloration mechanism

Summary Group-theoretical study of the vibrational modes of chlorosodalite [Na₄Al₃(SiO₄)₃]₂ has been carried out for theT _d ¹ space group. The Raman-active modes are evaluated and comparison is made with the experimental results on sodalite. It is shown that the experimental Raman spectrum does not support the structure of sodalite to beT _d ¹ but confirms it to beT _d ¹ . Raman scattering studies were performed on X-ray irradiated As-grown single crystal of chloro-sodalite to identify the coloration mechanism. Enhancement of oxygen twisting and stretching mode intensities on X-ray irradiation indicates the formation of neutral sodium colloidal aggregate during the coloration process. The authors of this paper have agreed to not receive the proofs for correction.     

Radiation properties of a uniaxial chiral quadratic inhomogeneous slab under oblique incidence

In this paper, the focussing of the transmitted electromagnetic field through a quadric inhomogeneous slab of lossless uniaxial chiral medium is derived using transmission coefficient under oblique incidence. The inhomogeneity in the uniaxial chiral slab has been incorporated through permittivity parameter. Asymptotic ray theory provides valid field everywhere except at focal point where it gives infinite value. Singularity of the field at focal point is addressed using Maslov's method. The derived analytical field expressions at caustic or focal point of uniaxial quadratic inhomogeneous slab have been solved numerically using MATHEMATICA. The effects of chirality parameter, axial permittivity, transvers permittivity, angle of incidence on the refracted field are discussed and the effects of Brewster angle on the focussed field are also discussed. The results obtained using Maslov's method are compared with Huygens–Kirchhoff's integral which are in good agreement.     

Hydrotropic Behavior of Sodium Salicylate in Presence of Additives

It is well known that, like surfactants aggregating at a certain concentration (called critical micelle concentration, CMC), hydrotropes also have minimum hydrotrope concentration (MHC). However, unlike surfactant CMC, this MHC value is usually very high, thereby reducing their application. In this paper we report the results of conductivity and viscosity measurements with a well known hydrotrope sodium salicylate (NaSal) solutions in presence and absence of additives (propanol, PrOH; butanol, BuOH; pentanol, PeOH and tetrabutylammonium bromide, Bu₄NBr). We have found that MHC value of NaSal decreases in presence of additives. Alcohols increase the hydrophobic interactions and decrease the MHC while Bu₄NBr, in addition to ameliorating the hydrophobic interactions, reduces the charge on head groups and MHC decreases more steeply in its presence. Increased solubility of riboflavin in NaSal containing the above additives corroborates the results.     

Study of the Cloud Point of the Phenothiazine Drug Chlorpromazine Hydrochloride: Effect of Surfactants and Polymers

Surfactants/polymers are used extensively in drug delivery as drug carriers. We herein report the effect of surfactants and polymers on the cloud point (CP) of amphiphilic drug chlorpromazine hydrochloride. At fixed drug concentration (50 mM) and pH (6.7) these additives affect the CP in accordance to their nature and structure: anionic surfactants show an increase followed by a decrease, whereas cationic (conventional as well as gemini) and nonionic surfactants show continous increase. The behavior with polymers is dictated by the number of units present in a particular polymer. Increase in drug concentration and pH, in presence of fixed amounts of CTAB, increases and decreases the CP, respectively. Variation of CP with pH at various fixed gemini concentrations shows that gemini surfactants are better candidates for drug delivery.