Dinuclear zinc bis(thiosemicarbazone) complexes: Synthesis, in vitro anticancer activity, cellular uptake and DNA interaction study

Four dinucleating bis(thiosemicarbazone) ligands and their zinc complexes have been synthesized and characterized by multinuclear NMR (H-1 and C-13), IR, UV-Vis, ESI-MS and fluorescence spectroscopic techniques. Their purity was assessed by elemental analysis. Cytotoxicity was tested against five human cancer cell lines using the sulphorhodamine B (SRB) assay, where one of the complexes, 1,3-bis{biacetyl-2'-(4 `'-N-pyrrolidinylthiosemicarbazone)-3'-(4 `'-N-pyrrolidinylthiosemicarbazone) zinc(II)} propane (6), was found to be quite cytotoxic against MCF-7 (breast cancer) and HepG2 (hepatoma cancer) cell lines, with a potency similar to that of the well known anticancer drug adriamycin. It is evident from the cellular uptake studies that the uptake is same for the active complex 6 and the inactive complex 8 (1,6-bis{biacetyl- 2'-(4 `'-N-pyrrolidinylthiosemicarbazone)-3'-(4 `'-N-pyrrolidinylthiosemicarbazone) zinc(II)} hexane) in MCF-7 and HepG2 cell lines. In vitro DNA binding and cleavage studies revealed that all complexes bind with DNA through electrostatic interaction, and cause no significant cleavage of DNA. (C) 2'13 Elsevier B. V. All rights reserved.

Imaging Intracellular Zinc by Using a Glyoxal Bis(4-methyl-4-phenyl-3-thiosemicarbazone) Ligand

The ligand glyoxal bis(4-methyl-4-phenyl-3-thiosemicarbazone) (GTSCH2) is shown to be a selective fluorescence turn-on sensor for zinc ions (Zn2+). This sensor is easy to synthesize, exhibits excellent sensitivity and selectivity towards Zn2+ over other physiologically relevant cations, and has sub-nanomolar binding affinity. It displays maximum fluorescence response to Zn2+ when the metal/ligand ratio is 1:1 and displays stable fluorescence over a broad pH range. The potential of GTSCH2 to image Zn2+ inside the cell was demonstrated in MCF-7 cells (human breast cancer cell line) by using flow cytometry and confocal fluorescence microscopy. Cell viability studies reveal that the probe is biocompatible and suitable for cellular applications.

Linear and nonlinear optical studies on 3,6-bis (2 pyridyl) pyridazine

3,6-Bis (2 pyridyl) pyridazine has been synthesized and characterized by NMR, XRD and elemental analyses. The vibrational studies were carried out by using FTIR and Raman spectroscopy and the modes of vibrations were analysed and compared with the theoretically calculated values. The nonlinear optical property of the title compound was examined by Kurtz-Perry method and Hyper Raleigh scattering with the fundamental wavelength of 1064nm. This compound possesses less SHG efficiency but large first hyperpolarizability. (C) 2013 Elsevier GmbH. All rights reserved.

Novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters: synthesis and a new insight into their antioxidant and antimicrobial potential

A simple and efficient protocol for the synthesis of novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters 4(a-q) is described. Initially, p-anisaldehyde 1 was condensed (Mannich reaction) with acetone and ammonium acetate trihydrate afforded 2,6-bis(4-methoxyphenyl)piperidin-4-one 2. Then, methylation followed by oximation with hydroxylamine hydrochloride (NH(2)OHa (TM) HCl) furnished a key scaffold 4. Further, to explore the enhanced biological properties of the piperidin-4-one core i.e. the key scaffold 4 was conjugated with substituted benzoyl chlorides in the presence of anhydrous K2CO3 as base to obtain novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters 4(a-q) in excellent yields. The newly synthesized compounds were characterized by elemental analysis, IR, H-1 NMR, C-13 NMR and mass spectroscopic techniques, and screened for their in vitro antioxidant and antimicrobial activities. Most of the compounds exerted positive efficacy towards the biological assays performed. Among the synthesized analogues, compounds 4l and 4m exhibited promising antioxidant activity and on the other hand compounds 4b and 4d manifested persuasive antibacterial activity, whereas compound 4b displayed stupendous antifungal activity against A. flavus strain.

Designing Ternary Co-crystals with Stacking Interactions and Weak Hydrogen Bonds. 4,4 `-Bis-hydroxyazobenzene

Three ternary co-crystals of the title compound are reported. The design strategy hinges on the identification of a robust synthon with O-H center dot center dot center dot N hydrogen bonds in a binary co-crystal. Construction of this module allows the tuning of pi center dot center dot center dot pi stacking interactions and weak hydrogen bonds to incorporate the third component into the crystal structure. Screening of various co-formers showed that a delicate balance of electrostatics is required for stacking to favor the formation of ternaries. A C-H center dot center dot center dot N hydrogen-bonded motif was also found to occur repetitively in the ternary co-crystals. The directional nature of weak hydrogen bonds allows them to be used effectively in this study.

Construction of Bis-pyrazole Based Co(II) Metal-Organic Frameworks and Exploration of Their Chirality and Magnetic Properties

In continuation of our interest in pyrazole based multifunctional metal-organic frameworks (MOFs), we report herein the construction of a series of Co(II) MOFs using a bis-pyrazole ligand and various benzene polycarboxylic acids. Employment of different acids has resulted in different architectures ranging from a two-dimensional grid network, porous nanochannels with interesting double helical features such as supramolecular chicken wire, to three-dimensional diamondoid networks. One of the distinguishing features of the network is their larger dimensions which can be directly linked to a relatively larger size of the ligand molecule. Conformational flexibility of the ligand also plays a decisive role in determining both the dimensionality and topology of the final structure. Furthermore, chirality associated with helical networks and magnetic properties of two MOFs have also been investigated.

Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2-bis(4-pyridyl)ethylene and Phloroglucinol:Phenazine

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol-dipyridylethylene (PGL:DPE) and phloroglucinol-phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single-component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape.

Synthesis, antioxidant, and cytotoxic activities of bis(oxazolyl/thiazolyl/imidazolyl)amidomethanesulfonyl Acetamides

A new class of bis(oxazolyl/thiazolyl/imidazolyl)amidomethanesulfonyl acetamides was prepared from the respective (oxazolyl/thiazolyl/imidazolyl)carbamoyl-methylthio acetic acid and studied their antioxidant activity and cytotoxic activitity against A549 lung adenocarcinoma cells. The methyl-substituted sulfonyl bisoxazoles exhibited excellent radical scavenging activity. On the other hand, the chloro-substituted sulfonyl bisthiazoles (IC50 = 49 A mu M) and sulfonyl bisimidazoles (IC50 = 24 A mu M) showed noticeable cytotoxic activity on A549 cells.

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

The crystal structure landscape of the 2:1 benzoic acid:dipyridylethylene cocrystal (BA:DPE-I) is explored experimentally with fluoro-substituted benzoic acids and extended with studies employing the Cambridge Structural Database (CSD). The interpretation of the cocrystal landscape is facilitated by considering the kinetically favored and robust acidpyridine heterosynthon as a modular unit. Information based on high-throughput crystallography shows that polymorphs and pseudopolymorphs may belong to the same landscape but arise from different crystallization pathways because of complex and different kinetic features, and secondary synthon preferences. Using the CSD as a guide, the coformer was changed from 1,2-bis(4-pyridyl)ethylene (DPE-I) to 1,2-bis(4-pyridyl)ethane (DPE-II) and this provides an extended interpretation of the BA:DPE-I cocrystal landscape, also highlighting the complexity of the kineticthermodynamic dichotomy during the molecule-to-crystal progression.

Raumordnung in der AWZ: Mittlere Anlandungen der deutschen und internationalen Fischereiflotten aus deutschen Nordseegewässern im Zeitraum von 2000 bis 2004

The pressure of users other than shipping and fishery on the national EEZs for territorial claims has increased in recent years. So it becomes necessary to carry out a spatial planning for which all users have to indicate their recent and planned future activities. For the German waters in the North Sea a first attempt was made to calculate the mean international landings for the commercially important fish and crustacean species on the spatial scale of ICES-rectangles. The relationships between the German and international landings per species are listed in a table and the distribution of the landings for each species within the area are shown in 13 figures.

Fischlarven der westlichen Ostsee – Biodiversitätsuntersuchungen von 2000 bis 2005

Fish larvae surveys provide information on the species composition in an area of investigation and leads to a better understanding of the entire fish community. Since 2000 every year in April/May an ichthyoplankton survey in ICES-Subdivision 22 and 24 has been performed to sample the plankton community in the western Baltic Sea. One objective was to acquire indicators of possible changes in the natural structures of the fish community. The time series derived from the Bongo-Net samples is too short to show a trend in larval densities. Up to now samples in the western Baltic Sea yielded only low mean densities. According to the reproductive biology the fish species were divided in three major groups: -Fish species with a long developmental phase in the plankton community -Small short living species with benthic eggs and a reduced planktonic phase -Guests without local spawning populations Species were identified, which were absent in the plankton of the western Baltic Sea in the 1960s and 1970s.

30. Sitzung des Codex Alimentarius Komitees für Fische und Fischerzeugnisse in Agadir, Marokko, vom 28.9. bis 2.10.2009

The Codex Committee on Fish and Fishery Products held its 30th Session in Agadir, Morocco from 28 September to 2 October 2009, at the kind invitation of the Government of Morocco. The Session was chaired by Dr Bjørn Røthe Knudsen, Regional Director of the Norwegian Food Safety Authority. The Session was attended by 218 delegates representing 78 Member States, one Member Organization (EC) and 1 international organization.

Untersuchungen des Zanderbestandes in den deutschen Küstengewässern der Ostsee von 1992 bis 2002

Pike-perch is an important resource for the coastal fishery in the brackish waters of the eastern part of the coast. For the conservation of the stocks regulation measures (minimum landing size, closed season and minimum mesh size) have been introduced since many years. Basic biological material of the last decade sampled from the commercial fishery and for recruitment by a standard trawl survey. For the “Eastern stock” this paper presents the results concerning age distribution, year-class strengths, growth, proportion spawners, natural mortality and yield-per-recruit analyses.

Fischarten der westlichen Ostsee – Untersuchungen von 2000 bis 2002

Ichthyoplankton provides information on the species com-position in an area of investigation and leads to a better understanding of the entire fish community. Every year since 1993 May/June (from 2000 in April/May) an ichthyoplankton survey in ICES Subdivision 22 and 24 has been done to sample the plankton community in the western Baltic Sea. One objective was to acquire indicators of possible changes in the natural structures of the fish com-munity. The time series derived from the Bongo-Net samples is too short to show a trend in larval densities. Up to now samples in the western Baltic Sea yielded only low mean densities. According to the reproductive biology the fish species were divided in three major groups: •Fish species with a long developmental phase in the plankton community •Small short lived species with benthic eggs and a reduced planktonic phase •Guests without local spawning populations. Species were identified, which were absent in the plankton of the western Baltic Sea in the 1960s and 1970s.

Winterfischerei auf Garnelen. Die Anteile der europäischen Garnelenflotten an den Anlandungen von Crangon crangon im Zeitraum Januar bis März der Jahre 1990 bis 1999

„Winter fishery“ on brown shrimp does not imply a special type of fishery. It merely means the continuation of the standard fishing procedure of parts of the fleet during wintertime, when the majority of the mostly smaller vessels stay in harbour due to generally unfavourable weather conditions for their activity. During 1990 to 1999 mean European wide landings in January and February summedup to 854 tonnes making up to only 4 % of the mean annual landings (21 805 t). While German vessels landed0.7 % (68.7 t) of their mean annual landings during that period, the other countries caught about 7 % of their individual, mean annual landings at the same time. The Netherlands and Denmark contributed highest tonnages of 580and 110 tonnes, respectively, to the total European landings, making up 81 % of them. As about 70 % of brown shrimp may carry eggs in January, the winter fishery took a mean total of about 2.15 x 1012brown shrimp eggs out of the stocks in that period annually. As there is no reliable assessment available concerning the brown shrimp stocks, it is despite of these high losses of eggs not possible to trace a negative effect of the winter fishery in scientific terms. However, precautional catch reductions in winter would be in favour of higher survival rates of eggs, which are the carrying source for the recruitment of brown shrimp stocks and catches in forthcoming summer and autumn seasons according to Dutch investigations.