Response surface methodology toward the optimization of high-energy carotenoid extraction from Aristeus antennatus shrimp

High-energy assisted extraction techniques, like ultrasound assisted extraction (UAE) and microwave assisted extraction (MAE), are widely applied over the last years for the recovery of bioactive compounds such as carotenoids, antioxidants and phenols from foods, animals and herbal natural sources. Especially for the case of xanthophylls, the main carotenoid group of crustaceans, they can be extracted in a rapid and quantitative way with the use of UAE and MAE.     

Reducing structural changes in van Emde Boas' data structure to the lower bound for the dynamic predecessor problem

We consider the problem of maintaining a dynamic ordered set of n integers in a universe U under the operations of insertion, deletion and predecessor queries. The computation model used is a unit-cost RAM, with a word length of w bits, and the universe size is |U|=2^w. We present a data structure that uses O(|U|/log|U|+n) space, performs all the operations in O(loglog|U|) time and needs O(loglog|U|/logloglog|U|) structural changes per update operation. The data structure is a simplified version of the van Emde Boas' tree introducing, in its construction and functioning, new concepts, which help to keep the important information for searching along the path of the tree, in a more compact and organized way.     

Mössbauer study of the three-coordinate planar Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)): model for the trigonal iron sites of the MoFe(7)S(9):homocitrate cofactor of nitrogenase

The cofactor (M-center) of the MoFe protein of nitrogenase, a MoFe(7)S(9):homocitrate cluster, contains six Fe sites with a (distorted) trigonal sulfido coordination. These sites exhibit unusually small quadrupole splittings, Delta E(Q) approximately 0.7 mm/s, and isomer shifts, delta approximately 0.41 mm/s. M?ssbauer and ENDOR studies have provided the magnetic hyperfine tensors of all iron sites in the S = 3/2 state M(N). To assess the intrinsic zero-field splittings and hyperfine parameters of the cofactor sites, we have studied with M?ssbauer spectroscopy two salts of the three-coordinated Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)). One of the salts, [Ph(4)P][Fe(SR)(3)] x 2MeCN x C(7)H(8), 1, has a planar geometry with idealized C(3h) symmetry. This S = 2 complex has an axial zero-field splitting with D = +10.2 cm(-1). The magnetic hyperfine tensor components A(x) = A(y) = -7.5 MHz and A(z) = -29.5 MHz reflect an orbital ground state with d(z(2)) symmetry. A(iso) = (A(x) +A(y) +A(z))/3 = -14.9 MHz, which includes the contact interaction (kappa P = -21.9 MHz) and an orbital contribution (+7 MHz), which is substantially smaller than A(iso) approximately -22 MHz of the tetrahedral Fe(II)(S-R)(4) sites of both rubredoxin and [PPh(4)](2)[Fe(II)(SPh)(4)]. The largest component of the electric field gradient (EFG) tensor is negative, as expected for a d(z(2)) orbital. However, Delta E(Q) = -0.83 mm/s, which is smaller than expected for a high-spin ferrous site. This reduction can be attributed to a ligand contribution, which in planar complexes provides a large positive EFG component perpendicular to the ligand plane. The isomer shift of 1, delta = 0.56 mm/s, approaches the delta-values reported for the six trigonal cofactor sites. The parameters of 1 and their importance for the cofactor cluster of nitrogenase are discussed.     

Monomeric oxovanadium(IV) compounds of the general formula cis-[V(IV)(=O)(X)(L(NN))(2)](+/0) [X = OH(-), Cl(-), SO(4)(2)(-) and L(NN) = 2,2'-bipyridine (bipy) or 4,4'-disubstituted bipy

Reaction of [V(IV)OCl(2)(THF)(2)] in aqueous solution with 2 equiv of AgBF(4) or AgSbF(6) and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[V(IV)O(OH)(L(NN))(2)]Y [where L(NN) = bipy, Y = BF(4)(-) (1), L(NN) = 4,4'-dtbipy, Y = BF(4)(-) (2.1.2H(2)O), L(NN) = 4,4'-dmbipy, Y = BF(4)(-) (3.2H(2)O), and L(NN) = 4,4'-dtbipy, Y = SbF(6)(-) (4)]. Sequential addition of 1 equiv of Ba(ClO(4))(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of V(IV)OSO(4).5H(2)O yields cis-[V(IV)O(OH)(bipy)(2)]ClO(4) (5). The monomeric compounds 1-5 contain the cis-[V(IV)O(OH)](+) structural unit. Reaction of 1 equiv of V(IV)OSO(4).5H(2)O in water and of 1 equiv of [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4) (9), cis-[V(IV)O(BF(4))(4,4'-dmbipy)(2)]BF(4) (10), and cis-[V(IV)O(SbF(6))(4,4'-dtbipy)(2)]SbF(6) (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF(4) or AgSbF(6) to a dichloromethane solution containing 1 equiv of [V(IV)OCl(2)(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH(3)OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) A, b = 13.33(1) A, c = 27.25(2) A, V = 7851(2) A(3), Z = 8. Compound 6.CH(3)OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) A, b = 14.204(5) A, c = 14.613(6) A, beta = 114.88(1) degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) A, b = 24.176(2) A, c = 13.676(1) A, V = 7628(2) A(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [V(IV)O(bipy)(2)](2+) and [V(IV)OX(bipy)(2)](+/0) species (X = OH(-), SO(4)(2)(-), Cl(-)).     

Theory of coupled optical PT-symmetric structures

Starting from Lagrangian principles we develop a formalism suitable for describing coupled optical parity-time symmetric systems.     

Determination of anabolic androgenic steroids as imidazole carbamate derivatives in human urine using liquid chromatography–tandem mass spectrometry

Anabolic androgenic steroids are widely abused substances in sports doping. Their detection present limitations regarding the use of soft ion sources such as electrospray or atmospheric pressure chemical ionization by liquid chromatography–tandem mass spectrometry. In the current study, a novel derivatization method was developed for the ionization enhancement of selected anabolic androgenic steroids. The proposed method aims at the introduction of an easily ionizable moiety into the steroid molecule by converting the hydroxyl groups into imidazole carbamates using 1,1′‐carbonyldiimidazole as derivatization reagent. The proposed method was applied to water and urine samples spiked with exogenous anabolic androgenic steroids in various concentration levels. Steroid imidazole carbamate derivatives have shown intensive [M+H]⁺ signals under electrospray ionization and common fragmentation patterns in tandem mass spectrometry mode with [M‐CO₂+H]⁺ and [M‐ΙmCO₂+H]⁺ as major ions with low collision energy. The obtained results showed that the majority of steroids were detectable at concentrations equal or lower to their minimum required performance level according to the World Anti‐Doping Agency technical document. The proposed method is sensitive with a preparation procedure that could be easily applied to the analysis of doping control samples.     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.