Cytotoxic Alkaloids Derived from Marine Sponges: A Comprehensive Review.

Marine sponges (porifera) have proved to be a prolific source of unique bioactive secondary metabolites, among which the alkaloids occupy a special place in terms of unprecedented structures and outstanding biological activities. Identification of active cytotoxic alkaloids extracted from marine animals, particularly sponges, is an important strive, due to lack of knowledge on traditional experiential and ethnopharmacology investigations. In this report, a comprehensive survey of demospongian bioactive alkaloids in the range 1987-2020 had been performed with a special emphasis on the potent cytotoxic activity. Different resources and databases had been investigated, including Scifinder (database for the chemical literature) CAS (Chemical Abstract Service) search, web of science, Marin Lit (marine natural products research) database. More than 230 representatives of different classes of alkaloids had been reviewed and classified, different genera belonging to the phylum porifera had been shown to be a prolific source of alkaloidal molecules, including Agelas sp., Suberea sp., Mycale sp., Haliclona sp., Epipolasis sp., Monanchora sp., Crambe sp., Reniera sp., and Xestospongia sp., among others. The sufficient production of alkaloids derived from sponges is a prosperous approach that requires more attention in future studies to consider the constraints regarding the supply of drugs, attained from marine organisms.

Innovation in academic chemical screening: filling the gaps in chemical biology.

Academic screening centers across the world have endeavored to discover small molecules that can modulate biological systems. To increase the reach of functional-genomic and chemical screening programs, universities, research institutes, and governments have followed their industrial counterparts in adopting high-throughput paradigms. As academic screening efforts have steadily grown in scope and complexity, so have the ideas of what is possible with the union of technology and biology. This review addresses the recent conceptual and technological innovation that has been propelling academic screening into its own unique niche. In particular, high-content and whole-organism screening are changing how academics search for novel bioactive compounds. Importantly, we recognize examples of successful chemical probe development that have punctuated the changing technology landscape.

The Use of JAK-specific inhibitors as chemical biology tools.

The JAK family of protein tyrosine kinases are now recognized as important participants in a wide range of pathologies, from cancer to inflammatory diseases. In the last decade, the drive to develop drugs targeting members of this family has begun to deliver a panel of small molecule inhibitors of JAK family members, with a range of potencies and specificities. A number of these compounds have already found widespread use as biochemical tools in the elucidation of JAK activity in specific signaling and disease processes; however, many of the first generation compounds are poorly characterized with suboptimal potencies and selectivities.Herein, we present the data for those small molecule JAK inhibitors that have been described in the peer-reviewed literature and the benefits and potential issues that may be associated with the use of these tool compounds.

Antinociceptive activity of ethanol extract from Duguetia chrysocarpa Maas (Annonaceae).

The ethanol extract from the fruits of Duguetia chrysocarpa was evaluated for its antinociceptive activity in chemical and thermal models of nociception in mice. The intraperitoneal administration of the ethanol extract (100, 200, and 400 mg/kg body weight) showed a dose-dependent inhibition of acetic-acid-induced abdominal writhes. The extract also produced a significant inhibition of both phases of the formalin test in all doses tested and increased the reaction time in hot-plate test at dose of 200 mg/kg. The data obtained suggest that the antinociceptive effect of the extract may be mediated via both peripheral and central mechanisms. The phytochemical investigation yielded the isolation of the benzenoid derivative 3-methoxy-4-ethoxy benzoic acid which is being reported for the first time in this genus.

Selenium as a structural surrogate of sulfur: template-assisted assembly of five types of tungsten-iron-sulfur/selenium clusters and the structural fate of chalcogenide reactants.

Syntheses of five types of tungsten-iron-sulfur/selenium clusters, namely, incomplete cubanes, single cubanes, edge-bridged double cubanes (EBDCs), P(N)-type clusters, and double-cuboidal clusters, have been devised using the concept of template-assisted assembly. The template reactant is six-coordinate [(Tp*)W(VI)S(3)](1-) [Tp* = tris(3,5-dimethylpyrazolyl)hydroborate(1-)], which in the assembly systems organizes Fe(2+/3+) and sulfide/selenide into cuboidal [(Tp*)WFe(2)S(3)] or cubane [(Tp*)WFe(3)S(3)Q] (Q = S, Se) units. With appropriate terminal iron ligation, these units are capable of independent existence or may be transformed into higher-nuclearity species. Selenide is used as a surrogate for sulfide in cluster assembly in order to determine by X-ray structures the position occupied by an external chalcogenide nucleophile or an internal chalcogenide atom in the product clusters. Specific incorporation of selenide is demonstrated by the formation of [WFe(3)S(3)Se](2+/3+) cubane cores. Reductive dimerization of the cubane leads to the EBDC core [W(2)Fe(6)S(6)Se(2)](2+) containing µ(4)-Se sites. Reaction of these species with HSe(-) affords the P(N)-type cores [W(2)Fe(6)S(6)Se(3)](1+), in which selenide occupies µ(6)-Se and µ(2)-Se sites. The reaction of [(Tp*)WS(3)](1-), FeCl(2), and Na(2)Se yields the double-cuboidal [W(2)Fe(4)S(6)Se(3)](2+/0) core with µ(2)-Se and µ(4)-Se bridges. It is highly probable that in analogous sulfide-only assembly systems, external and internal sulfide reactants occupy corresponding positions in the cluster products. The results further demonstrate the viability of template-assisted cluster synthesis inasmuch as the reduced (Tp*)WS(3) unit is present in all of the clusters. Structures, zero-field Mössbauer data, and redox potentials are presented for each cluster type.

Synthesis of fatty acid methyl ester from palm oil (Elaeis guineensis) with Ky(MgCa)2xO3 as heterogeneous catalyst.

Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production.

Wet-chemical synthesis of palladium nanosprings.

We report a methodology for synthesis of palladium (Pd) nanospring structures using an anodic aluminum oxide (AAO) membrane template and facile electrochemical deposition. The hydroxyl-terminated surfaces of alumina nanochannels and localized hydrogen evolution contribute to the growth of Pd atoms at peripheral positions of the alumina nanochannels in the presence of an effectual electric potential and a plating solution consisting of PdCl(2), CuCl(2), and HCl. Structural characterization including EDS line analysis and element mapping revealed Pd nanodomains curling up on the Cu nanorods. A clear Pd nanospring shape was observed after selectively removing Cu. The lengths of the nanosprings were dictated by the charges transported through electrodeposition, and the diameters of the nanosprings were tunable by altering the diameter of the alumina nanochannels. Screw dislocation is the most probable crystallographic defect responsible for the formation of coiled Pd nanostructures. Pd nanosprings have potential applications in nanomachines, nanosensors, nanoinductors, and metamaterials. We anticipate that our synthesis method will motivate and inform the synthesis of more advanced nanomaterials.

A promising phosphorescent iridium complex with fluorine substituents: synthesis, crystal structure, photo- and electro-luminescence performance.

In this paper, we report a phosphorescent Ir(III) emitter of Ir(acac-F6)(F-BT)(2), where acac-F6 = 1,1,1,5,5,5-hexafluoropentane-2,4-dione and F-BT = 2-(2-fluorophenyl)benzo[d]thiazole, including its crystal structure, electronic nature, photophysical characteristics, thermal and electrochemical properties. Data suggest that Ir(acac-F6)(F-BT)(2) is a promising emitter with high quantum yield of 0.19 and good thermal stability, along with its proper energy levels for charge carrier transportation. Electroluminescence (EL) devices using Ir(acac-F6)(F-BT)(2) as emitter are also fabricated, and their electroluminescence performances are investigated in detail. The optimal EL device shows a maximum luminance of 27,000 cd/cm(2) and a peak current efficiency of 8.7 cd/A.

Effect of humic acid on sorption of technetium by alumina.

Sorption of technetium by alumina has been studied in absence as well as in presence of humic acid using (95)Tc(m) as a tracer. Measurements were carried out at fixed ionic strength (0.1M NaClO(4)) under varying pH (3-10) as well as redox (aerobic and reducing anaerobic) conditions. Under aerobic conditions, negligible sorption of technetium was observed onto alumina both in absence and in presence of humic acid. However, under reducing conditions (simulated with [Sn(II)] = 10(-6)M), presence of humic acid enhanced the sorption of technetium in the low pH region significantly and decreased at higher pH with respect to that in absence of humic acid. Linear additive as well as surface complexation modeling of Tc(IV) sorption in presence of humic acid indicated the predominant role of sorbed humic acid in deciding technetium sorption onto alumina.

Chemical interferences when using high gradient magnetic separation for phosphate removal: consequences for lake restoration.

A promising method for lake restoration is the treatment of lake inlets through the specific adsorption of phosphate (P) on strongly magnetizable particles (Fe) and their subsequent removal using in-flow high gradient magnetic separation (HGMS) techniques. In this work, we report an extensive investigation on the chemical interferences affecting P removal efficiencies in natural waters from 20 Mediterranean ponds and reservoirs. A set of three treatments were considered based on different Fe particles/P concentration ratios. High P removal efficiencies (>80%) were found in freshwater lakes (conductivities<600 µ S cm(-1)). However, a significant reduction in P removal was observed for extremely high mineralized waters. Correlation analysis showed that major cations (Mg(2+), Na(+) and K(+)) and anions (SO(4)(2-) and Cl(-)) played an essential role in P removal efficiency. Comparison between different treatments have shown that when increasing P and Fe concentrations at the same rate or when increasing Fe concentrations for a fixed P concentration, there exist systematic reductions in the slope of the regression lines relating P removal efficiency and the concentration of different chemical variables. These results evidence a general reduction in the chemical competition between P and other ions for adsorption sites on Fe particles. Additional analyses also revealed a reduction in water color, dissolved organic carbon (DOC) and reactive silicate (Si) concentrations with the addition of Fe microparticles.

Combining bio- and chemo-catalysis: from enzymes to cells, from petroleum to biomass.

In the future, biomass will continue to emerge as a viable source of chemicals. The development of new industries that utilize bio-renewables provides opportunities for innovation. For example, bio- and chemo-catalysts can be combined in 'one pot' to prepare chemicals of commercial value. This has been demonstrated using isolated enzymes and whole cells for a variety of chemical transformations. The one-pot approach has been successfully adopted to convert chemicals derived from biomass, and, in our opinion, it has an important role to play in the design of a more sustainable chemical industry. To implement new one-pot bio- and chemo-catalytic processes, issues of incompatibility must be overcome; the strategies for which are discussed in this opinion article.

Free-standing membranes via covalent cross-linking of polyelectrolyte multilayers with complementary reactivity.

Polyelectrolyte multilayers were prepared by the layer-by-layer (LbL) technique from polyanions bearing aldehyde and polycations with 4-methylpyridinium moieties. The aldol reaction of these complementary reactive groups can be followed by the formation of fluorescent merocyanine dyes, resulting in cross-linked, ultrathin polymer films. The efficient stabilization of the polymer films allows for their intact removal from high surface energy supports, such as glass or surface oxidized silicon wafers, by simple treatment with salt solutions, yielding free-standing membranes. Increasing separation of the reactive polycation and polyanion layers with layers of inert polycation and polyanion analogues only gradually prevents the coupling reaction. From this dependence, polyions assembled in consecutive adsorption layers seem to be able to penetrate into as far as three neighboring layers.

Direct measurement of acid-base interaction energy at solid interfaces.

We have studied acid-base interactions at solid-liquid and solid-solid interfaces using interface-sensitive sum frequency generation (SFG) spectroscopy. The shift of the sapphire hydroxyl peak in contact with several polar and nonpolar liquids and polymers was used to determine the interaction energy. The trend in the interaction energies cannot be explained by measuring only water contact angles. Molecular rearrangements at the sapphire interface, to maximize the interaction of the acid-base groups, play a dominant role, and these effects are not accounted for in the current theoretical models. These results provide important insights into understanding adhesion, friction, and wetting on solid interfaces.

Oxidation of inorganic compounds by Ferrate(VI) and Ferrate(V): one-electron and two-electron transfer steps.

Ferrate(VI) (Fe(VI)O(4)(-), Fe(VI)) and ferrate(V) (Fe(V)O(4)(3-), Fe(V)) have a high oxidizing power and upon decomposition form a nontoxic byproduct, Fe(III), which makes them environmentally friendly oxidants in water and wastewater treatment. The kinetics of the reaction between Fe(VI) and I(-) was determined using a stopped-flow technique. The second-order rate constants (k, M(-1) s(-1)) for the oxidation of I(-) and other inorganic compounds by protonated ferrate(VI) (HFe(VI)O(4)(-)) and ferrate(V) (Fe(V)O(4)(3-)) ions were correlated with thermodynamic reduction potentials to understand the reaction mechanisms. A linear relationship was found between log k and 1-e(-) reduction potentials for iodide, cyanides, and superoxide while oxy-compounds of nitrogen, sulfur, selenium, and arsenic demonstrated a linear relationship for 2-e(-) reduction potentials. The estimated limits for the reduction potentials of the couple are E(o)(Fe(VI)/Fe(V)) >or= 0.76 V and E(o)(Fe(VI)/Fe(IV)) >or= -0.18 V. Conclusions drawn from the correlations are consistent with the mechanisms postulated from stoichiometries, intermediates, and products of the reactions. Implication of the kinetic results in treatment using ferrate(VI) is briefly discussed.

Global biogeochemical changes at both ends of the proterozoic: insights from phosphorites.

The distribution of major phosphate deposits in the Precambrian sedimentary rock record is restricted to periods that witnessed global biogeochemical changes, but the cause of this distribution is unclear. The oldest known phosphogenic event occurred around 2.0 Ga and was followed, after more than 1.3 billion years, by an even larger phosphogenic event in the Neoproterozoic. Phosphorites (phosphate-rich sedimentary rocks that contain more than 15% P(2)O(5)) preserve a unique record of seawater chemistry, biological activity, and oceanographic changes. In an attempt to emphasize the potentially crucial significance of phosphorites in the evolution of Proterozoic biogeochemical cycles, this contribution provides a review of some important Paleoproterozoic phosphate deposits and of models proposed for their origin. A new model is then presented for the spatial and temporal modes of occurrence of phosphorites along with possible connections to global changes at both ends of the Proterozoic. Central to the new model is that periods of atmospheric oxygenation may have been caused by globally elevated rates of primary productivity stimulated by high fluxes of phosphorus delivery to seawater as a result of increased chemical weathering of continental crust over geological timescales. The striking similarities in biogeochemical evolution between the Paleo- and Neoproterozoic are discussed in light of the two oldest major phosphogenic events and their possible relation to the stepwise rise of atmospheric oxygen that ultimately resulted in significant leaps in biological evolution.

Sonochemical synthesis of liquid-encapsulated lysozyme microspheres.

Liquid-encapsulated lysozyme microspheres were successfully synthesized using a sonochemical method. The encapsulation of four different liquids, namely, sunflower oil, tetradecane, dodecane and perfluorohexane on the formation, stability and morphology of the lysozyme microspheres was studied. Among the four different liquids used for encapsulation, perfluorohexane-filled microspheres were found to be most stable in the dried state with a narrow size distribution. In order to explore the possibility of encapsulating biofunctional molecules (e.g., drugs) within these microspheres, liquids containing a fluorescent dye (Nile red) were encapsulated and the ultrasound-induced release of these dye-loaded liquids was studied. The fluorescence data for the liquid-filled lysozyme microspheres demonstrated the potential use of the sonochemical technique for synthesizing these "vehicles" for the encapsulation and the controlled delivery of dyes, flavours, fragrances or drugs.

Multiarm cyclam-grafted mesoporous silica: a strategy to improve the chemical stability of silica materials functionalized with amine ligands.

We have explored in this work the stability and the reactivity of multiarm cyclam-grafted mesoporous silica samples in aqueous solution. A series of hybrid materials have been prepared by grafting silylated cyclam molecules bearing one, two, or four silyl groups onto both amorphous silica gel (K60) and ordered mesoporous silica (SBA15). Under these conditions, cyclam moieties are attached to the silica walls via one, two, or four arms. Various physicochemical techniques have been applied to characterize the functionalized solids (elemental analysis, 1H-29Si and 1H-13C CPMAS NMR, and N2 adsorption-desorption isotherms). The interest in two and four arms for improving the chemical stability in solution, by comparison with the system displaying only one arm, has been demonstrated by using a set of complementary experiments involving pH measurements and silicon determination with ICP-AES. Then, the investigation of their protonation and binding properties toward copper(II) has revealed a significant decrease in the reactivity of these hybrids as a consequence of multiarm tethering. A comparison of amorphous and ordered materials has permitted us to point out the influence of mesostructuration on the reactivity of these functionalized solids, especially from a kinetic point of view.

Deacidification of high free fatty acid-containing rice bran oil by non-conventional reesterification process.

Rice bran (Oryza sativa) oil is known for containing higher amount of free fatty acid (FFA) generated by hydrolytic enzyme. This FFA causes heavy neutral oil losses due to saponification and emulsification since it produces large amount of soap in the conventional alkali refining process. In the present study the FFA of degummed rice bran oil (RBO) was significantly reduced by reesterifying it with glycerol. The reesterification process was carried out by varying the temperature and amount of excess glycerol using 0.2% catalyst (SnCl(2)). The maximum efficiency of the process could be attained at 200 degrees C using 70% excess glycerol and the maximum reduction in acid value (from 24.3 to 3.0) of RBO was observed within 4 h. The reesterified RBO was used to prepare stand oil and varnish and their performance characteristics were compared with those of the products obtained from dehydrated castor oil (DCO).

Bleaching of mustard oil with some alternative bleaching agents and acid activated clay.

An attempt was made to study the bleaching ability of some alternative adsorbents like rice husk ash (HC), acid activated rice husk ash (AC), rice husk silica (S), and Al(OH)(3) gel to replace commercial Acid Activated Clay (AAC, like Tonsil Earth: TE) for bleaching of mustard oil. Quantities of AAC used were varied from 0.5 to 2.0 % (w/w). It was used as such and along with commercial activated carbon (0.25-0.75 %, w/w), and laboratory prepared Al(OH)(3) gel, rice husk ash and silica isolated from husk. The results show that quantity of AAC to be used can be reduced to 1.00 to 1.25% (w/w) by using a combination of AAC along with rice husk ash; Al(OH)(3) gel; rice husk silica either by wet bleaching or by conventional bleaching method.

Preparation and characterization of n-alkane/water emulsion stabilized by cyclodextrin.

Emulsions consisting of n-alkane/water using alpha, beta, and gamma-cyclodextrin (alpha, beta, and gamma-CD) as an emulsifier were prepared and characterized by means of several physicochemical techniques. A phase diagram of the n-alkane/CD/water system showed that an oil in water (O/W) emulsion can be prepared from a mixture of the appropriate composition. The dissolved n-alkane/CD complexes formed at low CD concentrations showed surface-activity, but emulsions could not be prepared from these complexes. On the other hand, the precipitated complexes formed at high CD concentrations when adsorbed to the oil/water interface, and served as an emulsifier for formation of emulsions. These results showed that the emulsions formed were of the Pickering emulsion. In addition emulsion formation was governed by the wettability and the surface free energy of the precipitated complexes.