The discovery of aniline and the origin of the term “aniline dye”

An historical background is provided for the term, “aniline dye,” which is still widely used as a synonym for “synthetic dye.” The discovery of aniline and the role of Hofmann in clarifying it are described. The subsequent discovery of mauveine (mauve) by a student of Hofmann's, William Perkin, and his difficulties in transforming an academic synthesis into a commercial product also are discussed. The key role of Scottish dyers, the Pullars of Perth and Thomas Keith in London, in this technology transfer is described. The subsequent ascendancy of the German dyestuff industry over British manufacturers is noted.     

The “polarizing inducer” in hydra: A reexamination of its properties and its origin

Summary In order to prove the gradient hypothesis an attempt was made to isolate and accumulate the polarizing inducer present in homogenates of hydra and assumed to be a neurosecretory product. By means of gel chromatography two fractions were obtained which brought about the development of supernumary apical structures (tentacles and hypostomes) thus exhibiting the symptoms attributed to this polarizing agent: a low molecular fraction with only modest effectiveness and a main fraction with strong animalizing ability. Increasing the concentration affected only the quantity but not the qualitative properties of the structures produced, a result inconsistent with the postulate of the gradient hypothesis. By analysing the chemical and biological nature of the main agent and by applying pure isolated toxins compelling evidence is given that the inducer in question is nothing but a component of the nematocyst toxins. This component, being heat-stable and trypsin-sensitive, elicites its animalizing effect in unspecific means by disturbing the normal pattern of morphallactic events. A side effect with interest in respect of graded tissue properties could be recorded: by the influence of the relevant toxin, growing together of regenerating animals occurs whereby predominantly apical primordia fuse with apical primordia, thus forming stable parabioses. This observation may indicate the significance of surface bound, contact establishing components in polar differentiation.

---

Zusammenfassung Zur Prüfung der entwicklungsphysiologischen Gradiententheorie wird der Versuch unternommen, den polarisierenden Induktor zu isolieren und anzureichern, der in Homogenaten von Hydra zugegen ist und als neurosekretorisches Produkt angesehen wird. Die Gelchromatographie wäßriger Extrakte liefert 2 Fraktionen, welche die Entwicklung überzähliger apikaler Strukturen (Tentakel und Mundkegel) hervorrufen: eine niedermolekulare Fraktion mit nur mäßiger Wirksamkeit und eine Hauptfraktion im mittelmolekularen Bereich mit starker animalisierender Kapazität. Entgegen dem Postulat der Gradiententheorie besteht keine Korrelation zwischen der applizierten Konzentration und der Qualität ausgelöster Formbildungen. Nur die Anzahl überzähliger Strukturen ist dosisabhängig. Die Analyse der biologischen und chemischen Eigenschaften der Hauptfraktion bringt den Hinweis, daß das polarisierende Agens eine Hitze-stabile, Trypsin-sensitive Komponenteder Nesselgifte ist, die ihre animalisierende Wirkung in unspezifischer Weise zeitigt. Die Applikation isolierter, reiner Nesselgifte erhärtet diese Vermutung zum klaren Beweis. Ein Nebeneffekt des relevanten Gifts legt graduierte Gewebseigenschaften offen: Unter seinem Einfluß verwachsen die Testpolypen, sowie sie in Kontakt zueinander kommen. Hierbei verbinden sich vorzugsweise apikale Primordien mit apikalen Primordien, um stabile Parabiosen zu bilden. Diese Beobachtung mag die Bedeutung Kontakt-vermittelnder Oberflächenstrukturen für das polare Differenzierungsgeschehen anzeigen.

---

---

Supported by Deutsche Forschungsgemeinschaft.     

On the 48÷80-induced secretion of tissue mast cells and its mitogenic effect on nearby cells in the intact rat

Histamine release from tissue-bound mast cells and cell proliferation in the proper mesentery in the intact rat was quantitated following in intraperitoneal injection of graded doses of compound 48/80. The dose-response curves were sigmoid-like in linear-log plots. ED50 for histamine release was 0.035-0.040 and for increased cell proliferation 0.040-0.048 microgram per g BW. The proliferative response following mast-cell secretion ceased after a period of between 48-72 h, irrespective of whether a high or a low dose of 48/80 was used. Basal on the net rate of histamine synthesis (ca. 0.45 microgram/g mesentery wet weight/h) after an initial injection of 48/80, on the extent of histamine release and the proliferative response after a repeated injection of 48/80, it is concluded that there is a lag period of at least 3 days before proliferation can be re-stimulated by renewed 48/80-induced mast-cell secretion.     

The effect of temperature on the electrochemical properties of copper—DNA membranes

The influence of temperature, electrode plate metals and protamine on the membrane potential of an electrochemically prepared copper—DNA (Cu-DNA) membrane (size, 2.5×6cm; thickness, 80μm; Cu/P molar ratio, 0.4) was investigated. The results obtained showed that the membrane potential increased with temperature as well as with increasing order of ionization tendency of the divalent metals used, and decreased with an increase of protamine bound to the membrane. These results indicated that electrons accumulated on the anode side, and positive holes formed on the cathode side, of a Cu-DNA membrane prepared by electrolysis.     

The many “faces” of copper in medicine and treatment

Copper (Cu) is an essential microelement found in all living organisms with the unique ability to adopt two different redox states—in the oxidized (Cu²⁺) and reduced (Cu⁺). It is required for survival and serves as an important catalytic cofactor in redox chemistry for proteins that carry out fundamental biological functions, important in growth and development. The deficit of copper can result in impaired energy production, abnormal glucose and cholesterol metabolism, increased oxidative damage, increased tissue iron (Fe) accrual, altered structure and function of circulating blood and immune cells, abnormal neuropeptides synthesis and processing, aberrant cardiac electrophysiology, impaired myocardial contractility, and persistent effects on the neurobehavioral and the immune system. Increased copper level has been found in several disorders like e.g.: Wilson’s disease or Menke’s disease. New findings with the great potential for impact in medicine include the use of copper-lowering therapy for antiangiogenesis, antifibrotic and anti-inflammatory purposes. The role of copper in formation of amyloid plaques in Alzheimer’s disease, and successful treatment of this disorder in rodent model by copper chelating are also of interest. In this work we will try to describe essential aspects of copper in chosen diseases. We will represent the evidence available on adverse effect derived from copper deficiency and copper excess. We will try to review also the copper biomarkers (chosen enzymes) that help reflect the level of copper in the body.     

The coordination of copper(II) with β-casomorphin and its fragments

The synthesis of β-casomorphin-5 (Tyr-Pro-Phe-Pro-Gly, H₂L) and a number of its peptide fragments is described. Complexes formed between these peptides and Cu(II) have been investigated spectrophotometrically, using CD and EPR spectroscopy, and potentiometrically. Results show that, with tyrosine as the N-terminal residue, the major complex formed at physiological pH is the dimeric species, [Cu₂L₂], bonded through the phenolic O^? of the Tyr residue of one ligand and the N-terminal amine nitrogen of the second ligand molecule. There is no evidence for coordination through the peptide nitrogens unless the terminal Tyr group is removed.     

The mango—its botany,cultivation, uses and future improvement,especially as observed in india

This delicious tropical fruit has been under cultivation tor about 4,000 years and today it is grown on about two million acres in India, its original home. Nearly 1,000 cultivated varieties are known throughout the tropics oi the world. The fruits are rich in vitamins A and C, and have better food value than apple.     

Quantum-chemical investigation of the structure and the antioxidant properties of α-lipoic acid and its metabolites

Quantum-chemical computations were used to investigate the structure-antioxidant parameter relationships of α-lipoic acid and its natural metabolites bisnorlipoic acid and tetranorlipoic acid in their oxidized and reduced forms. The enantiomers of lipoic and dihydrolipoic acid were optimized using the B3LYP/6-311+G(3df,2p), B3LYP/aug-cc-pVDZ and MP2(full)/6-31+G(d,p) levels of theory as isolated molecules and in the presence of water. The geometries of the metabolites and the values of their antioxidant parameters (proton affinity, bond dissociation enthalpy, adiabatic ionization potential, spin density, and the highest occupied molecular orbital energy) were calculated at the B3LYP/6-311+G(3df,2p) level of theory. The results obtained reveal similarities between these structures: a pentatomic, nonaromatic ring is present in the oxidized forms, while an unbranched aliphatic chain (as found in saturated fatty acids) is present in both the oxidized and the reduced forms. Analysis of the spin density and the highest occupied molecular orbital energy revealed that the SH groups exhibited the greatest electron-donating activities. The values obtained for the proton affinity, bond dissociation enthalpy and adiabatic ionization potential indicate that the preferred antioxidant mechanisms for α-lipoic acid and its metabolites are sequential proton loss electron transfer in polar media and hydrogen atom transfer in vacuum.     

The effect of ruthenium on the performance of porphyrin dye and porphyrin–fullerene dyad solar cells predicted by DFT and TD-DFT calculations

The effect of ruthenium on the performance of porphyrin dye and porphyrin–fullerene (PF) dyad solar cells is investigated by using density functional theory and time-dependant density functional theory calculations. The results reveal that ruthenium facilitates rapid electron injection from porphyrin to fullerene, narrows the band gaps of porphyrin dye and PF dyad and alters the density of states near the corresponding Fermi levels. The HOMOs are localised on the donor moieties and the LUMOs on the acceptor moieties. The donor and acceptor dyads form good donor–acceptor pairs for photo-to-current conversion under the effect of ruthenium. HOMOs of porphyrin and ruthenium metalloporphyrin dyes fall within the (TiO₂)₆₀ and Ti₃₈O₇₆ gaps, and support the issue of typical interfacial electron transfer reaction. The calculated transition energies of porphyrin are almost insensitive to ethanol solvent effects. The introduction of ruthenium to the porphyrin ring leads to more active nonlinear optical performance, stronger response to the external electric field and induces higher photo-to-current conversion efficiency. Moreover, ruthenium shifts the absorption bands of porphyrin and makes it a potential candidate for harvesting light for photovoltaic applications.     

The effect of the use of copper carbonate and copper nanoparticles in the diet of rats on the level of β-amyloid and acetylcholinesterase in selected organs

BackgroundCopper has an important role in nervous system function, as a cofactor of many enzymes and in the synthesis of neurotransmitters. Both the dose and the chemical form of copper can determine the impact of this element on metabolism, the neurological system and the immune system.AimsThe aim of the study was to determine whether and in what form the addition of copper changes the level of amyloid beta and acetylcholinesterase level in selected rat tissues.MethodsThirty, healthy, male, albino Wistar rats aged 7 weeks were randomly divided into 3 groups. Three experimental treatments were used to evaluate the effects of different levels and sources of Cu (6.5 mg kg of diet) in the diet: Cu₀ – rats fed a diet without Cu supplementation; Cu_salt – rats fed a diet with CuCO₃ (6.5 mg kg of diet) during two months of feeding; Cu_NPs - rats fed a diet with Cu nanoparticles (6.5 mg kg of diet) during two months of feeding. In blood serum and tissue homogenates there rated the indicators proving the potential neurodegenerative effect and epigenetic DNA damage induced by chemical form of copper or lack of additional copper supplementation in diet were determined. There were analysed: level of acetylcholinesterase, β-amyloid, low-density lipoprotein receptor-related protein 1, apyrimidinic endonuclease, thymidine glycosidase, alkylpurine-DNA-N-glycosylase and glycosylated acetylcholinesterase.ResultsIrrespective of the form of copper added, it was found to increase acetylcholinesterase level in the brain, spleen and liver, as well as in the blood plasma of the rats. Copper in the form of CuCO₃ was found to increase acetylcholinesterase level in the kidneys. The addition of both forms of copper caused a marked increase in the plasma concentration of β-amyloid in comparison with the diet with no added Cu. The addition of both forms of copper caused a marked increase in the plasma concentration of β-amyloid in comparison with the diet with no added Cu.ConclusionsA lack of added Cu in the diet of rats reduces the concentration of amyloid-β in the blood, whereas administration of copper, in the form of either CuNPs or CuCO₃, increases the level of this peptide in the blood. The use of copper in the form of CuNPs in the diet of rats does not increase the level of β-amyloid more than the use of the carbonate form of this element. The use of CuNPs or CuCO₃ in the diet of rats increases acetylcholinesterase level in the brain, spleen, liver, and blood. CuNPs in the diet of rats were not found to increase acetylcholinesterase level to a greater extent than Cu⁺² carbonate.     

The cysteine-rich domain of synaptosomal-associated protein of 23 kDa (SNAP-23) regulates its membrane association and regulated exocytosis from mast cells

Synaptosomal-associated protein of 23 kDa (SNAP-23) plays an important role during regulated exocytosis of various inflammatory mediators, stored in secretory granules, from mast cells in response to physiological triggers. It is however synthesized as a soluble protein, and the mechanisms by which free SNAP-23 gets peripherally associated with membrane for the regulation of exocytosis, are poorly defined. SNAP-23 contains a hydrophobic domain with five closely spaced cysteines which get palmitoylated, and we show that SNAP-23 cysteine mutants show differential membrane association when transfected in rat basophilic leukemia (RBL) mast cells. SNAP-23 Cys⁻ mutant, devoid of all five cysteines, and SNAP-23 P119A (proline to alanine) mutant, that likely interferes with palmitoylation of SNAP-23 by palmitoyl transferases are completely cytosolic. Mutating specific cysteines (Cys; C) to leucine or phenylalanine (L or F; retains hydrophobicity but lacks palmitoylation) partially decreases the membrane association of SNAP-23 which is further hampered by alanine (A; has lesser hydrophobicity, and lacks palmitoylation) mutation at C79, C80 or C83 position. Cloning a transmembrane domain MDR3_1–145 from multidrug resistance protein into SNAP-23 Cys⁻ mutant is able to partially restore its membrane association. Regulated exocytosis studies using co-transfected human growth hormone (hGH) secretion reporter plasmid revealed that overexpression of SNAP-23 Cys⁻ and P119A mutants significantly inhibits the overall extent of exocytosis from RBL mast cells, whereas expression of SNAP-23 Cys⁻-MDR3_1–145 fusion protein is able to restore exocytosis. These results establish that the cysteine-rich domain of SNAP-23 regulates its membrane association and thereby also regulates exocytosis from mast cells.     

The reaction of zinc sulphide with ionic copper—the biological implications. Part 1. Surface area studies of zinc sulphide and its reaction with copper complexes and copper containing proteins

The role of metal sulphides vis-à-vis the availability of dietary copper in ruminant animals has been investigated using zinc sulphide as a model metal sulphide and a selection of copper complexes and copper containing proteins as models for sources of dietary copper. The extent of reactivity of zinc sulphide towards the copper complexes is dependent upon the type of donor atom co-ordinated to copper:

The order to reactivity is found to be CuO > CuN > CuS complexes and is in keeping with the reported values for the instability constant pK_n of the complexes. In contrast, no reaction is observed between zinc sulphide and the copper containing proteins studied (azurin, superoxide dismutase and cerulophasmin) and is attributed to the protection of the copper centres by the protein backbone. The results facilitate an understanding of copper metabolism in ruminants and a mechanism is proposed for the removal of dietary copper sources in such species.Reactions between copper(II) sulphate solutions and samples of zinc sulphide having a range of specific surface areas (prepared by sintering at differing temperatures) have been studied. The fact that the reactivity is found to be highly dependent upon the specific surface area of the metal sulphide may well be of significance when considering the fate of copper in sulphur-rich biological systems.     

Studies of fluorescent components of the “heparin” drug and its complexing with phenylalanine, tyrosine, and tryptophan

Impurities of free aromatic amino acids (Phe and Tyr) and the elastin protein were found in the heparin commercial drug (Hep) by spectral luminescent and spectrophotometric methods. The fluorescence quenching of the Trp, Tyr, and Phe amino acids by the Hep drug was studied, and the Stern-Folmer constants (K) that reflected stability of the Hep complexes with amino acids were determined. The stability of AA-Hep complexes increased in the following sequence: Trp < Tyr < Phe (K = 19 ± 2 < 39 ± 3 < 710 ± 70 M^?1, respectively). These values probably determined the dominant contribution of the phenylalanine impurity in the heparin drug. The contamination of animal elastin whose structure differed from that of the human elastin is thought to be a reason for allergic reactions and even anaphylactic shock during medical treatment with this drug.     

The myth of “minima” and “maxima”, the species of Physalis in the Indian Subcontinent

The status of the names, Physalis minima L. and P. maxima Mill. (Solanaceae), and their alleged presence on the Indian subcontinent are discussed. The issues of nativity and identity of Linnaean Physalis minima are long-debated while the use of the name P. maxima Mill. and its report from India are recent. The available evidence indicates that the name "P. minima L." is misapplied to two different elements, viz., P. angulata L. and P. lagascae Roem. & Schult. The name Physalis minima L. may be rejected as nomen confusum, for which the paper provides the primary information. As on today, it is submerged under the synonymy of P. angulata L. The correct name for the widely known P. minima is P. lagascae. The name "P. maxima Mill." applied to the escape and naturalized weed in the Indian subcontinent and elsewhere is to be substituted by P. pruinosa L., a name misapplied to P. grisea (Waterf.) M. Martínez.