Bioinorganic Chemistry

Dye-sensitized solar cells (DSCs) have achieved impressive conversion efficiencies for solar energy of over 11% with an electrolyte that contains triiodide/iodide as a redox couple. Although triiodide/iodide redox couples work efficiently in DSCs, they suffer from two major disadvantages: electrolytes that contain triiodide/iodide corrode electrical contacts made of silver (which reduces the options for the scale up of DSCs to module size) and triiodide partially absorbs visible light. Here, we present a new disulfide/thiolate redox couple that has negligible absorption in the visible spectral range, a very attractive feature for flexible DSCs that use transparent conductors as current collectors. Using this novel, iodide-free redox electrolyte in conjunction with a sensitized heterojunction, we achieved an unprecedented efficiency of 6.4% under standard illumination test conditions. This novel redox couple offers a viable pathway to develop efficient DSCs with attractive properties for scale up and practical applications.

The aim of this study was to investigate the clinical efficacy of vanadium complexes on triglycerides (TG), total cholesterol (Chol), uric acid (UA), urea (U), and antioxidant parameters: nonenzymatic (FRAP—ferric reducing ability of plasma, and reduced glutathione—GSH) and enzymatic (glutathione peroxidase—GPx, catalase—CAT, and GPx/CAT ratio) activity in the plasma of healthy male Wistar rats. Three vanadium complexes: [VO(bpy)2]SO4⋅2H2O, [VO(4,4′Me2bpy)2]SO4⋅2H2O, and Na[VO(O2)2(bpy)]⋅8H2O are administered by gavage during 5 weeks in two different diets such as control (C) and high fatty (F) diets. Changes of biochemical and antioxidants parameters are measured in plasma. All three vanadium complexes statistically decrease the body mass growth in comparison to the control and fatty diet. In plasma GSH was statistically increased in all vanadium complexes-treated rats from control and fatty group in comparison to only control group. Calculated GPX/CAT ratio was the highest in the ...

RESUMEN: se evaluó la acilación biocatalizada del N-(p-toluensulfonil)-2-piperidinmetanol y la alcohólisis de su éster corres- pondiente, como fuente de esterasa se usaron los polvos acetónicos de hígado (PAH) de res, gato, pollo, ratón, puerco, rata y conejo, la reacción se llevó a cabo en medio orgánico. Las mejores condiciones para la acilación fueron en heptano como disolvente, a 50ºC y en presencia de 0.05% v/v de una solución amortiguadora de fosfatos. La alcohólisis se llevó a cabo con pentanol o decanol, en las mismas condiciones de reacción. ABSTRACT: the acylation of N-(p-toluensulfonyl)-2-piperidinemethanol, and the alcoholysis of the corresponding acetate were evaluated using as a source of esterase the liver acetone powders (LAPs) from bovine, cat, chicken, mouse, pig, rat and rabbit in organic media. The best reaction conditions for the acylation were heptane as solvent, at a temperature of 50°C, and in presence of a 0.05% v/v buffer solution, in the same conditions us...

Se describe un metodo de sintesis de amidas por el cual se busca optimizar esta reaccion anadiendo catalizadores a base de mezclas de Cobalto y Fierro HT3SR, HT3CCF y HT3CCF650, los cuales difieren en su composicion quimica y en algunas propiedades fisicas como el tamano de cristales. Estos catalizadores tienen en comun la fuerza acida media, siendo la adecuada para que se lleve a cabo la reaccion. El sistema se sometio a distintos factores circulantes como el cambio de solventes como DCM, THF, DCE y Tolueno, aplicacion de temperatura que puede ser a temperatura ambiente o aplicando 60°C y distintos tiempos de reaccion para verificar el sistema optimo. El sistema a base de DCM/60°C por 24 horas con el catalizador HT3SR, dando un rendimiento alto y planteando una nueva forma de obtencion de amidas, abriendo un tema de investigacion para su posterior realizacion.

2020; AI-Zaidi et al. 2019; Ejidike et al. 2021). The stability of the oxime group in many new synthetic Schiff bases has been verified by various spectroscopic analytical methods such as nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR), ultraviolet visible spectroscopy (UV-Vis) (AL-Zaidi et al. 2018; Manikshete et al. 2013; Barve et al. 2011). Analysis the spectroscopic results of 1 H and 13 C NMR, FT-IR and UV-Vis of the tridentate Schiff-oxime ligand 1-[2-(2,4-dihydroxybenzylidene) aminophenyl] ethanone oxime (H2L) showed that oxime acting as a monobasic tridentate (N,N,O) toward metal complexes (AL-Zaidi et al. 2018). The oxime functional group in another new bidentate Schiff ligand works as monobasic bidentate (N,O) with six metal complexes (AL-Zaidi and AI-Obaidi 2014). Data of UV-Vis and magnetic moment showed that 2-N-(1.,2.-diphenylethanone oxime) benzoic acid provided an octahedral environment around three complexes of metal ions (Manikshete et al. 2013). Analysis of IR, 1 H NMR, mass and HMS spectrum are confirmed the synthesis of ten oximes (IVa-j) from 4methylpyrano-(2,3-β)-phenothiazine-2(11 H)-one (Barve et

A novel heterobinuclear mixed valence complex [Fe III Cu II (BPBPMP)(OAc) 2 ]ClO 4 , 1, with the unsymmetrical N 5 O 2 donor ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2hydroxybenzyl)(2-pyridylmethyl)}aminomethyl]-4-methylphenol (H 2 BPBPMP) has been synthesized and characterized. A combination of data from mass spectrometry, potentiometric titrations, X-ray absorption and electron paramagnetic resonance spectroscopy, as well as kinetics measurements indicates that in ethanol/water solutions an [Fe III -(µ)OH-Cu II OH 2 ]+ species is generated which is the likely catalyst for 2,4-bis(dinitrophenyl)phosphate and DNA hydrolysis. Insofar as the data are consistent with the presence of an Fe III -bound hydroxide acting as a nucleophile during catalysis, 1 presents a suitable mimic for the hydrolytic enzyme purple acid phosphatase. Notably, 1 is significantly more reactive than its isostructural homologues with different metal composition (Fe III M II , where M II is Zn II , Mn II , Ni II , or Fe II ). Of particular interest is the observation that cleavage of double-stranded plasmid DNA occurs even at very low concentrations of 1 (2.5 µM), under physiological conditions (optimum pH of 7.0), with a rate enhancement of 2.7×10 7 over the uncatalyzed reaction. Thus, 1 is one of the most effective model complexes to date, mimicking the function of nucleases.

Magnetic resonance imaging (MRI) enables high-resolution non-invasive observation of the anatomy and function of intact organisms. However, previous MRI reporters of key biological processes tied to gene expression have been limited by the inherently low molecular sensitivity of conventional 1 H MRI. This limitation could be overcome through the use of hyperpolarized nuclei, such as in the noble gas xenon, but previous reporters acting on such nuclei have been synthetic. Here, we introduce the first genetically encoded reporters for hyperpolarized 129 Xe MRI. These expressible reporters are based on gas vesicles (GVs), gas-binding protein nanostructures expressed by certain buoyant microorganisms. We show that GVs are capable of chemical exchange saturation transfer interactions with xenon, which enables chemically amplified GV detection at picomolar concentrations (a 100-to 10,000-fold improvement over comparable constructs for 1 H MRI). We demonstrate the use of GVs as heterologously expressed indicators of gene expression and chemically targeted exogenous labels in MRI experiments performed on living cells.

An original cooperative photoredox catalytic system, [Ru II (trpy)(bpy)(H 2 O)][3,3′-Co(1,2-C 2 B 9 H 11 ) 2 ] 2 (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3′-Co(1,2-C 2 B 9 H 11 ) 2 ] -([1] -) and the oxidation catalyst [Ru II (trpy)-(bpy)(H 2 O)] 2+ (C2′) are linked by noncovalent interactions and not through covalent bonds. The noncovalent interactions to a large degree persist even after water dissolution. This represents a step ahead in cooperativity avoiding costly covalent bonding. Recrystallization of C4 in acetonitrile leads to the substitution of water by the acetonitrile ligand and the formation of complex [Ru II (trpy)(bpy ), structurally characterized. A significant electronic coupling between C2′ and [1] -was first sensed in electrochemical studies in water. The Co IV/III redox couple in water differed by 170 mV when [1] -had Na + as a cation versus when the ruthenium complex was the cation. This cooperative system leads to an efficient catalyst for the photooxidation of alcohols in water, through a proton-coupled electrontransfer process. We have highlighted the capacity of C4 to perform as an excellent cooperative photoredox catalyst in the photooxidation of alcohols in water at room temperature under UV irradiation, using 0.005 mol % catalyst. A high turnover number (TON = 20000) has been observed. The hybrid system C4 displays a better catalytic performance than the separated mixtures of C2′ and Na[1], with the same concentrations and ratios of Ru/Co, proving the history relevance of the photocatalyst. Cooperative systems with this type of interaction have not been described and represent a step forward in getting cooperativity avoiding costly covalent bonding. A possible mechanism has been proposed.

The Directed Assembly Network, an EPSRC Grand Challenge Network, set out in 2010 to build a wide-reaching community of scientists, engineers and industrial members that includes: chemists, biologists, physicists, chemical engineers, mathematicians, and computer scientists, to name but a few. This Roadmap has been constructed by the Network community over years of consultations and continuous engagement through: themed meetings, sandpits, Network awards (proof of concept projects) and strategic meetings. In 2010, the Network was tasked to look 20-40 years into the future, and to capture, short, medium and long term goals. Over the 6 years since its inception the Network has grown to over 1,000 members and hosts several highly acclaimed meetings each year. Early career researchers are at the heart of the Network and benefit greatly from access to, and networking with our world-leading members, senior management team and Network Champions. The Network is now embedded into the culture of the UK landscape and continues to work at the leading edge. The vision of the Network is to be able to control the assembly of matter with sufficient certainty and precision to allow the preparation of materials and molecular assemblies, with far more sophisticated and tuneable properties and functions, than are accessible in materials synthesised using current methods. The UK position and World challenges are set out in this Roadmap to highlight the importance that new materials provide when it comes to solving the Grand Challenges of this century. Challenges include: the development of medicine and implants tailored to each individual; the creation of green alternatives to scarce resources; discovering new energy sources; capturing pollutants; enhancing both crop production & the provision of clean water and developing exciting innovations, such as smart materials, new catalysts, organic computing and high-temperature superconductors that will transform society.

The synthesis, crystal structure and variable‐temperature magnetic measurements of compounds [M2(μ‐Hade)2(μ‐mal)2(H2O)2]·2H2O [M = Ni (1), Co (2)], [Co2(μ‐Hade)2(μ‐mal)2(H2O)2] (3), {(H2ade)2[Cu(μ‐mal)2]·2H2O}n (4) and (H2ade)2[Cu(mmal)2(H2O)] (5; H2ade = adeninium, Hade = adenine, mal = malonato, mmal = methylmalonato) are reported. Compounds 1–3 contain neutral paddle‐wheel [M2(μ‐Hade)2(μ‐mal)2(H2O)2] [M = Ni (1), Co (2 and 3)] units where the 7H‐tautomeric form of the nucleobase and the malonate dianion act as μ‐κN3:κN9 and μ‐κ2O1,O2:κO1 bridging ligands, respectively. The supramolecular crystal structures of 1–3 are essentially maintained by hydrogen‐bonding interactions involving the nucleobases, the carboxylate groups and crystallisation water molecules (in compounds 1 and 2). Compounds 4 and 5 show a hybrid inorganic‐organic lamellar structure containing layers of anionic metal‐malonato complexes and supramolecular aggregates of the 1H,9H‐adeninium cation. Their overall three...

The application of various spectroscopic techniques to investigate the coordination of transition metal ions is reviewed using examples which include the preparation of highly dispersed catalysts, the investigation of the coordination sphere of supported transition metal ions on oxide surfaces, the coordination sphere of catalytically active sites and the migration of transition metal ions into the bulk of oxides during catalyst pretreatment. The features of coordination chemistry for supported transition metal ions appear to be very similar to their solution analogues and the same concepts can thus be applied.

Ceruloplasmin, a multicopper oxidase essential for copper metabolism and oxidative defense, from blood serum of domestic goats (Capra aegagrus hircus) has been purified to homogeneity by using three steps of column chromatography. The purified goat ceruloplasmin (gCP) protein has an estimated molecular weight of approximately 141 kDa as determined by SDS-PAGE. ICP-AES analysis indicates that each molecule of the protein contains 5.6 ± 0.2 atoms of copper. The optimum pH of catalysis for gCP was found to be pH 5.5. Using the Hill equation, the K m and V max values for gCP are estimated to be 0.41 ± 0.01 mM and 0.35 ± 0.01 μmol/min/mg, respectively. The enzyme has an average of 3.3 ± 0.33 substrate binding sites per molecule. Both, circular dichroism (CD) spectroscopy studies and computational analysis using PDBsum reveals that gCP is primarily composed of β-strands distinguishing it from the α-helix-rich human ceruloplasmin. Also, computational analysis of gCP reveals six copper-binding sites, composed of histidine (his), methionine (Met), and cysteine (cys). Cyclic voltammetry studies of gCP immobilized on a glassy carbon electrode indicate the presence of Type 1 and Type 2/3 copper centers within the protein identified by two unique redox potential values of +294 mV and-250 mV versus the normal hydrogen electrode (NHE), respectively. The positive redox potential site that probably acts as the electron-transfer center had a slightly lower redox potential compared to that reported in other ceruloplasmin. The negative redox potential site of the protein possibly corresponds to the catalytic site containing trinuclear copper center proposed earlier. The redox potential of the Type 1 center aligns closely with azurin, suggesting evolutionary homology and suitability for direct electron transfer (DET). The distinct electrochemical properties of gCP may enhance applications in biofuel cells, biosensors, and other bioelectronic devices due to its efficient electron-transfer capabilities. This study provides valuable insights into the functional versatility of ceruloplasmin across species and highlights the biotechnological potential of this unique variant.

Gonadotropin releasing hormone (GnRH) triggers secretion of luteinizing hormone and follicle stimulating hormone from gonadotropic cells in the anterior pituitary gland. GnRH is able to bind copper, and both in vitro and in vivo studies have suggested that the copper-GnRH complex is more potent at triggering gonadotropin release than GnRH alone. However, it remains unclear whether copper-GnRH is the active species in vivo. To explore this we have estimated the GnRH-copper affinity and have examined whether GnRH remains copper-bound in the presence of serum albumin and the neuropeptide neurokinin B, both copper-binding proteins that GnRH will encounter in vivo. We show that GnRH has a copper dissociation constant of ~0.9 Â 10 À9 M, however serum albumin and neurokinin B can extract metal from the copper-GnRH complex. It is therefore unlikely that a copper-GnRH complex will survive transit through the pituitary portal circulation and that any effect of copper must occur outside the bloodstream in the absence of neurokinin B.

Gonadotropin releasing hormone (GnRH) triggers secretion of luteinizing hormone and follicle stimulating hormone from gonadotropic cells in the anterior pituitary gland. GnRH is able to bind copper, and both in vitro and in vivo studies have suggested that the copper-GnRH complex is more potent at triggering gonadotropin release than GnRH alone. However, it remains unclear whether copper-GnRH is the active species in vivo. To explore this we have estimated the GnRH-copper affinity and have examined whether GnRH remains copper-bound in the presence of serum albumin and the neuropeptide neurokinin B, both copper-binding proteins that GnRH will encounter in vivo. We show that GnRH has a copper dissociation constant of ∼0.9 × 10 M, however serum albumin and neurokinin B can extract metal from the copper-GnRH complex. It is therefore unlikely that a copper-GnRH complex will survive transit through the pituitary portal circulation and that any effect of copper must occur outside the blood...

A Cu(II) complex was obtained from the reaction of 4-(diethylamino)-3-quinolin-3-yliminomethyl-2-phenol with [CuCl2(PPh3)2]. The ligand coordinated to the metal ion in a monobasic bidentate fashion. The molecular structure of the complex has been confirmed by single crystal X-ray diffraction. Both the ligand and complex were characterized by various spectroscopic techniques. Using the UV-visible and fluorescence spectroscopic studies, the binding interactions of the compounds with CT-DNA and bovine serum albumin protein were evaluated. The results indicated that the compounds are efficient DNA/protein binders. The cytotoxicity of the ligand and complex against A549 (lung cancer) and MCF7 (breast cancer) cell lines was also investigated in vitro conditions using the MTT assay method which showed significant anticancer activity.

Et 4 N[L′′Fe III ]‚3DCM (1) is directly synthesized by adding ferric chloride into a solution of a lithium salt of tetrakis(cyclohexyl)porphyrinogen (L′′). [L′′] 4-is a good chelating ligand for both Fe-(III) and Fe(II) ions. It is an avid proton scavenger but not a reducing agent. 1 showed a magnetic moment (µ eff ) of 4.3 µ B in the solid, which changed to 6.0 µ B in solution. This change in spin state is common for all iron porphrinogens. 1 showed polymorphism, and with pyridine in the lattice, it changed to Et 4 N-[L′′Fe III ]‚DCM 0.5 Py 1.5 (2), possessing two different conformers. Calculation of these conformers at the density functional theory level showed the relative energies of all d orbital changes in three conformers, highlighting the influence of the disposition of a peripheral ligand. Iodine oxidation of 1 yielded [L′′ ∆∆ Fe II I][I 3 ‚I 2 + ‚I 3 -] (3) with the introduction of two C R -C R bonds with concomitant reduction of Fe(III) to Fe(II). Its µ eff (5.4 µ B ) in the solid changed to 4.8 µ B in solution, suggesting a high spin state (S ) 2) for Fe(II).

We report results, based on density functional theorygeneralized gradient approximation calculations, that shed light on how NO, CO, and O 2 interact with Fe 2 S 2 , Fe 3 S 4 , and Fe 4 S 4 clusters and how they modify their structural and electronic properties. The interest in these small iron sulfide clusters comes from the fact that they are at the protein cores and that elucidating fundamental aspects of their interaction with those light molecules which are known to modify their functionality may help in understanding complex behaviors in biological systems. CO and NO are found to bind molecularly, leading to moderate relaxations in the clusters, but nevertheless to changes in the spin-polarized electronic structure and related properties. In contrast, dissociative chemisorption of O 2 is much more stable than molecular adsorption, giving rise to significant structural distortions, particularly in Fe 4 S 4 that splits into two Fe 2 S 2 subclusters. As a consequence, oxygen tends to strongly reduce the spin polarization in Fe and to weaken the Fe-Fe interaction inducing antiparallel couplings that, in the case of Fe 4 S 4 , clearly arise from indirect Fe-Fe exchange coupling mediated by O. The three molecules (particularly CO) enhance the stability of the iron-sulfur clusters. This increase is noticeably more pronounced for Fe 2 S 2 than for the other iron-sulfur clusters of different compositions, a result that correlates with the fact that in recent experiments of CO reaction with Fe m S m (m = 1-4), the Fe 2 S 2 CO product results as a prominent one.

Microorganisms, such as bacteria, viruses, fungi, and parasites, have the capacity to cause harm to the organisms they infect. The severity of this injury can vary greatly, ranging from moderate and selflimiting to severe and potentially lethal. Microbial infections are commonly treated with antimicrobial medicines, which might include antibiotics, antivirals, antifungals, or antiparasitic medications, depending on the specific microorganism causing the sickness. Dithiocarbamate complexes have remarkable biological efficacy, and their adaptable coordination chemistry has positioned them as promising antibacterial agents. This chapter provides a summary of the latest advancements in the synthesis and utilization of dithiocarbamate complexes as potent antibacterial agents. It emphasizes their wide-ranging efficacy in fighting against many hazardous pathogens, such as viruses, fungi, and bacteria. The abstract concludes by emphasizing the need for more research to enhance the design and synthesis of dithiocarbamate complexes.

Na pitanje 'što je razumijevanje?' neki su filozofi iz pozicije hermeneutike pokušali dati odgovor. Jedan od tih filozofa je Friedrich Daniel Ernst Schleiermacher koji je u postupku tumačenja vidio preduvjet razumijevanja, a za pojam razumijevanja zahtijevao da se promatra u okviru hermeneutike. Wilhelm Dilthey je čak hermeneutiku smatrao preduvjetom duhovnih znanosti. Martin Heidegger u svojim je djelima Bitak i vrijeme, Ontologija i Prolegomena za povijest pojma vremena preuzeo neke elemente navedenih prethodnika, ali je stvorio i svoj vlastiti hermeneutički put. Hermeneutika je u Heideggerovoj misli dostigla razinu one koja omogućava tubitku da sam sebe razumijeva. Taj tubitak briguje, egzistira pod određenim okolnostima, a karakterizira ga bačenost. Fakticitet je jedno takvo življenje, ali koje u sebi sadrži odnos prema sebi i svijetu. Iz toga proizlazi i zadatak hermeneutike koja analizira taj fakticitet čineći tako – hermeneutiku fakticiteta

A gamma x quadratic response surface model was used to predict the growth rate over the 14-week growth period of zucchini squash (Cucurbita pepo L.) cv. Blackjack in sand culture with nitrogen (N) levels of 2, 7, 14, 29 and 43 mmol/L. Growth rate relative to maximum was plotted against tissue N concentration every 2 weeks, to derive diagnostic petiole sap; leaf nitrate-N and leaf total-N in youngest fully opened leaf, youngest fully expanded leaf and oldest green leaf; and total N in bulked leaf samples. Critical concentrations corresponding to 90% maximum growth rate for deficiency and toxicity are presented. Petiole sap and leaf nitrate-N were much more responsive than leaf total N concentrations over the 2-14 mmol N/L range where positive growth responses were recorded. At 2 mmol N/L, plants were severely N-deficient and growth rate was low (1.6 g/plant.week at fruit set). Tissue nitrate concentrations were negligible, while leaf total N concentrations exceeded 2.6%. Salt toxicit...

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destabilized by two gauche 0-0 interactions. Two conformers are consistent with 3Jc3,H1 (0 N 90') and neither can be distinguished by 3JH1,H2. The data, therefore, are insufficient to assign a preferred C 1 4 2 bond conformation in this isomer. Hydrates and dimethyl acetals appear to adopt similar conformations. Orientation of the methyl groups of dimethyl acetals (Cl-01 bond torsions) was not examined. The uncertainties that arise in the conformational analysis of furanosyl rings have been discussed in this and other reports. The assignment of conformations of these structures based on only three 3J coupling values is tenuous at best, although, as shown here, additional information is available from 13C-lH couplings. Unequivocal chemical shift assignment is a prerequisite for conformational analysis. Assignment of the individual methylene (C4) protons of the tetrofuranosyl ring is particularly important because their coupling to C1 is a sensitive indicator of the conformation in the region of the anomeric center. Assignment of the resonances to individual C4 protons based on substituent effects, magnitudes of 2JCH and 3JCH, and selective [2H] substitution, all demonstrate that H4S is the more shielded methylene proton in tetrofuranosyl rings. The "syn-upfield" rule for 1,2interactions is upheld in these systems. Three 13C-lH couplings across the ring oxygen reflect the preferred orientation of 01. Conformations with 01 quasi-axial (or near quasi-axial) are preferred for all ring configurations, a manifestation of the anomeric effect which appears to dominate all other factors in determining ring conformation. Ring flexibility appears to increase as 1,2-and 1,3411teractions increase, such that, in the tetroses, the a-threo isomer appears to be most stable and the P-erythro isomer least. We are currently testing this conclusion with the use of ab initio molecular orbital calculations. While this study has shown that a first-order analysis of 'H-lH and 13C-lH coupling constants and 13C relaxation times does not provide a complete understanding of tet-rofuranosyl ring conformation, it has produced an extensive body of data that must be accommodated in future models. The use of 13C-lH coupling data in conformational studies of five-membered rings provides a better basis upon which conformational inferences can be made. Internuclear lH-lH distances, determined in solution by DE-SERTm and/or dynamic NOE methods,51 as well as more recent two-dimensional NMR approaches, may provide complementary information on the conformational properties of these ring systems. 'H NMR spectra of methyl p-D-[1-'3c]-, [2-13C]-, and [4-13C]erythrofuranosides (Figure 5) (3 pages). Ordering information is given on any current masthead page.

Biohydrogen production by microorganisms including Clostridium and Enterobacter are covered. Artificial microbial consortia have no complications as the pure culture. Further avails the effect of environments interaction on each other and yield of hydrogen production. The present review paper discloses the pathway of hydrogen production by Enterobacter and Clostridium, the rate of growth of the microorganism, The potential of carbohydrate substrate metabolism, pH and temperature influence, and the ratio of experimental to theoretical yield under anaerobic conditions. Enterobacter by Pyruvate formate-lyase (PFL) and Clostridium Pyruvate-ferredoxin oxidoreductase (PFOR) yield 2 mol 𝐻 2 / mol glucose and 4 mol 𝐻 2 / mol glucose. On the count of the present comparison 1.36 to 2.205 mol 𝐻 2 /mol glucose produced by Enterobacter and Clostridium, respectively, 38% discrepancy of practical yield is observed. For hydrogen production Clostridium needs strict anaerobic environments and L-cysteine are added, while Enterobacter in consortia uses oxygen and as a result the production cost is reduced. The consortia are potential to metabolize simple and complex carbon sources like glucose, starch wastewater and lignocellulose wastes. Moreover, reasonably high inoculate ratio of Enterobacter, pH, and, temperature ranges of 5-7 and 30-39°C are effective for biohydrogen production.

Background: The 4T1 cells tumor growth and metastatic pattern in BALB/c mice very closely mimic human breast cancer. These herbal remedies used in traditional folk medicine have been the source of many medically beneficial drugs. The aim of the current study was to evaluate the anti-proliferative activity of the asafoetida, ginseng and fennel ethanolic extracts on mouse breast cancer 4T1 cell-line invitro.Method: in this experimental study, Asafoetida, gensing and fennel were extracted; 4T1 mouse mammary tumor cell line were cultured in 48-well flat bottom plate in density of 50x103 per well in 100 µl RPMI1640 medium then different dilutions of each extract (25 , 50, 100, 200, 500, and 2000 μg/ml) were added to cell culture. Cells then were incubated at 37 oC for 24 hours. After 24 h, cell Proliferation was determined by the BRDU assay . dataset of experiments were collected and analysed with SPSS19 software. Significant level of Data was Examined with one-way ANOVA method and P

We report the first Ru(II) coordination compounds that interact with DNA through a canonical minor groove insertion mode and with selectivity for A/T rich sites. This was made possible by integrating a bis‑benzamidine minor groove DNA-binding agent with a ruthenium(II) complex. Importantly, one of the enantiomers (Δ‑[Ru(bpy)&lt;sub&gt;2&lt;/sub&gt;&lt;b&gt;b4bpy&lt;/b&gt;]&lt;sup&gt;2+&lt;/sup&gt;, &lt;b&gt;Δ‑4Ru&lt;/b&gt;) shows a considerably higher DNA affinity than the parent organic ligand and than the other enantiomer, particularly for the AATT sequence, while the other enantiomer preferentially targets long AAATTT sites with overall lower affinity. Finally, we demonstrate that the photophysical properties of these new binders can be exploited for DNA cleavage using visible light.

Magnesium, calcium, strontium, and barium complexes of uracil were prepared in a 2:1 ligand to metal ratio to investigate the ligational character of the uracil (Ura). The modes of chelation were explained depending on elemental analyses, FT. IR, 1 H-NMR spectra as well as scanning electron microscopy. Uracil has two donation sites either through N(3) and C(2)=O, or through N(3) and C(4)=O with the molecular formulas [M(Ura)2(H2O)2]Cl2 where M = Mg(II), Ca(II), Sr(II) and Ba(II) . The morphological surface and particle size of uracil metal complexes were determined using SEM and TEM. The thermal behaviors of the complexes were studied by the TGA (DTG) technique. The data obtained agreed well the proposed structures and showed that the complexes were finally decomposed to the corresponding metal oxide. The thermodynamic parameters are calculated from the thermal analysis curves using the Coats-Redfern and Horowitz-Metzger methods. The negative values of ∆S * deduced the ordered structures of the prepared complexes compared to their starting reactants. Antibacterial activity of ligands and complexes is evaluated with two types of bacteria Staphylococcus aureus (gram-positive) and Escherichia coli (gram-negative) by the agar-well diffusion technique using DMSO as a solvent.

The oxo-bridged Os dimer [(bpy)2(HzO)Os1'100s'V(OH)(bpy)2]4+ has been isolated and characterized. Electrochemical experiments in aqueous solution have revealed an extensive redox chemistry for the dimer based on the following couples: Os(III)Os(IV)/Os(IlI)Os(IlI), Os(IlI)Os(III)/Os( II)Os(Il). The pH dependences of the potentials for the series of couples are presented and compared to those of the corresponding Ru dimer. The electrochemical results shed considerable light on the role of p H and electronic effects in stabilizing or destabilizing various oxidation states in the thermodynamic sense, in defining decomposition pathways, and in giving insight into the role that the thermodynamic properties of the various oxidation states have in dictating the reactivity properties of the dimers. o s ( v ) o s ( v ) / o s ( I v ) o s ( v ) , os(Iv)os(v)/os(Iv)os(Iv), os(Iv)os(v)/os(III)os(rv), os(rv)os(Iv)/os(lrI)os(IV). When oxidized, the dimer [(~~~),(OH,)RU~~~ORU'~~(H~O)-( b ~y ) ~] ~' provides a basis for t h e catalytic oxidation of H 2 0 t o 0,' and of CIt o CI2., Characterization of t h e active form(s) of t h e dimer a n d of t h e mechanism(s) involved in water or C1oxidation a r e complicated by t h e reactivity of t h e oxidized dimer. by t h e high potentials needed t o access its active form or forms, and by its reactivity toward water which is t h e solvent. In equivalent coordination environments analogous monomeric polypyridine complex of Os(Il) are easier t o oxidize t h a n Ru(l1) by 0.32-0.60 V.3-9 The p a t t e r n also extends t o t h e higher oxidation s t a t e couples involving oxidation states M(VI)/M(V), M(V)/M(IV), and M(IV)/M(III).'o W i t h t h e greater ease of oxidation of Os in mind we have turned t o t h e Os analogue of t h e Ru dimer with two thoughts in mind: (1) The Os dimer could provide a relatively unreactive model for the oxidized, active fornis of t h e Ru dimer. (2) The Ru dimer is a catalyst for the oxidation of w a t e r t o oxygen, a reaction which it carries o u t near t h e thermodynamic potential for the 0 2 / H 2 0 couple. If the reactivity characteristics of t h e Ru dimer are carried over t o t h e Os dimer b u t a t a decreased potential, it is conceivable t h a t t h e Os dimer could function a s a catalyst for t h e microscopic reverse, t h e reduction of O2 t o water near t h e thermodynamic potential for the O2/H2O couple. Materials. House distilled water was purified by distillation from alkaline permanganate. Solutions of trifluoromethanesulfonic acid, HOS02CF3, were prepared from 10-g ampules of the neat acid obtained from Aldrich. Redistilled perchloric acid was obtained from G . F. Smith. Lithium trifluoromethanesulfonate was obtained from Alfa. All other chemicals were reagent grade and were used without further purification. (1) (a

We present the first case of an early infantile form of galactosialidosis among Brazilians. This very rare and severe lysosomal storage disease has only a dozen patients clearly diagnosed worldwide. Clinical, pathological and biochemical features were consistent with previously published findings. We detected the disorder in a 7-month-old female baby with prenatal diagnosis of ascites. Evolution of the storage disease was monitored through routine thin-layer chromatography (TLC) for urinary oligosaccharides as part of a screening program for inborn errors of metabolism (IEM) in high-risk children, carried out in Rio de Janeiro.

A new series of 12 complexes of cobalt(II) and nickel(II) with N-isonicotinamido-2′,4′-dichlorobenzalaldimine (INH-DCB) with the general composition MX2⋅n(INH-DCB) [M = Co(II) or Ni(II), X = Cl−, Br−,NO3−, NCS−, or CH3COO−, n = 2; X = ClO4−, n = 3] have been synthesized. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, infrared, electronic spectra, magnetic susceptibility, and conductivity measurements. An octahedral geometry has been suggested for all the complexes. The metal complexes were screened for their antifungal and antibacterial activities on different species of pathogenic fungi and bacteria and their biopotency has been discussed.

Ogʻir metallar suv va oqava suv tarkibini ifloslantiruvchi moddalar
orasida eng dolzarb turlaridan biri hisoblanadi. Ularni aniqlashda zamonaviy analitik
usullardan foydalanish sanoat chiqindi suvlari, tuproq, oziq-ovqat maxsulotlari
tarkibidan og’ir metallarning kichik konsentratsiyalarini aniqlash imkonini beradi.
Elektrokimyoviy usullar sezgir va selektiv, shuningdek portativ hisoblanib aniqlash
chegarasi 1·10-9 - 1·10-12 M gacha. Inversion voltamperometriya elektrokimyoviy usul
hisoblanib statsionar simob elektrodidan tashqari o’zgartirilgan elektrodlardan
foydalanish aniqlashning yanada sezgirligini oshiradi.

The photoreactive [Ru(TAP)2(phen)]2+ (TAP = 1,4,5,8‐tetraazaphenanthrene; phen = 1,10‐phenanthroline) complex tethered to the cell‐penetrating peptide (CPP) TAT was studied in vitro and in cellulo. The tethering of the complex does not affect its behavior under blue‐light irradiation in the presence of guanine‐containing oligodeoxyribonucleotides (ODNG). Thus, the luminescence is quenched in the presence of ODNG, and gel electrophoresis experiments showed the appearance of products corresponding to the irreversible attachment of the conjugate to ODNG upon illumination. The cellular uptake of the conjugate was examined by flow cytometry, inductively coupled plasma mass spectrometry (ICP‐MS), and confocal imaging microscopy. These experiments showed that the [Ru(TAP)2(phen‐TAT)] conjugate is readily taken up by HeLa cells and, despite these favorable factors, the cellular survival was 100 %, as measured by a 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. A p...

This study investigates the phytochemical composition and antibacterial activity of aqueous pod extracts from Prosopis juliflora and Prosopis cineraria, two underutilized legumes with significant ethnomedicinal value. Extracts were prepared using the decoction method, and qualitative phytochemical screening revealed the presence of phenolics, flavonoids, tannins, saponins, alkaloids, glycosides, terpenoids, and steroids in both species. Antibacterial activity was evaluated using the turbidity method against E. coli, S. pneumonia, S. aureus, and K. pneumonia.. The results demonstrated dose-dependent antibacterial activity, with P. juliflora showing higher efficacy than P. cineraria, particularly against K. pneumonia. The findings validate the traditional use of Prosopis species in treating bacterial infections and highlight their potential as natural sources of bioactive compounds. Future research should focus on isolating and characterizing active constituents to enhance their pharmacological applications.

1. General Methods All reagents were purchased from commercial suppliers (Aldrich or Fisher) and used without further purification. Cyclobis(paraquat-4,4′-biphenylene) tetrakis(hexafluorophosphate) S1 (1•4PF6), 4,4′(5′)-bis[2-(2-{2-(propargyl)ethoxy}ethoxy)ethoxy]tetrathiafulvalene S2 (7), the TTF/ DNP macrocycle S3 4, and 1,1ʹ′-[4,4ʹ′-biphenylenebis-(methylene)]bis(4,4ʹ′-bipyridinium) bis (hexafluorophosphate) S4 (5•2PF6) were prepared according to literature procedures. Thin layer chromatography (TLC) was performed on silica gel 60 F254 (E. Merck). Column chromatography was performed on silica gel 60F (Merck 9385, 0.040-0.063 nm). Nuclear magnetic resonance (NMR) spectra were recorded at 25 ˚C (unless otherwise noted) on Bruker Avance 500 and 600 spectrometers, with working frequencies of 500 and 600 MHz for 1 H, and 125 and 150 MHz for 13 C nuclei, respectively. Chemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvents S5. All 13 C spectra were recorded with the simultaneous decoupling of proton nuclei. UV-Vis-NIR absorbance spectra

A general approach to various α-phosphorussubstituted oximes (β-oximinoalkyl-substituted phosphonates, phosphine oxides, phosphine−borane complexes, and phosphonium salts) was developed. The strategy exploits hitherto unknown Michael addition of PH-containing compounds (diphenylphosphine oxide, diisopropyl phosphite, phosphine− borane complexes, and triphenylphosphonium bromide) to unstable conjugated nitrosoalkenes, which are generated in situ from corresponding nitrosoacetals. The resulting α-phosphorus-substituted oximes can be considered as useful P-, N-, and O-ligands for catalysis and precursors to valuable βaminophosphonates.

The kinetics of reduction of the mer‐[RuIII(pic)3] complex (pic– = picolinato) by ascorbic acid (AscH2) leading to formation of a red ruthenium(II) species have been studied spectrophotometrically by using both conventional mixing and stopped‐flow methods. The reaction was followed as a function of the reductant concentration over a wide pH range (1.0–7.4). Electron transfer proceeds by an outer‐sphere mechanism involving three protolytic forms of ascorbic acid, AscH2, AscH– and Asc2–, for which specific rate constants have been determined. The Gibbs&#39; energy of activation was found to correlate linearly with the HOMO energies of the protolytic forms of the reductant. The mer‐[RuIII(pic)3] complex is too sparingly soluble in water to inhibit the growth of the Escherichia coli (ATCC 8739) strain. Its cytotoxicity against non‐tumorigenic cells precludes its potential use as an anticancer agent.

Now-a-days textiles are used in different sectors and various purposes beyond imagination. Among this an important and emerging part of the textile industry is medical, hygiene and health sector. Chitosan and its derivatives, trimethyl chitosan chloride (TMCC) and carboxymethyl-trimethyl chitosan chloride (CMTMCC) were prepared. Chitosan, TMCC and CMTMCC were applied on cotton fabric by pad-drycure method. Different properties of chitosan derivatives and modified fabric were characterized. The yield percentage of chitosan, TMCC and CMTMCC was 66.5, 102 and 93% respectively. The profiles of FTIR spectroscopy of the chitosan, TMCC and CMTMCC synthesized from chitosan were almost similar except the different characteristic peak which shows evidence of the conversion of chitosan to TMCC and CMTMCC. CMTMCC modified fabric exhibited best antimicrobial activity. TMCC and CMTMCC treated fabric showed more wicking height (cm) comparatively than chitosan treated fabric. Moisture absorption and moisture liberation, swelling and water vapor permeability of treated fabric were investigated. Thermal stability of treated fabric was also studied. All these characteristics support the TMCC and CMTMCC treated fabric could be the valuable materials for medical textile sector.

The reaction between benzimidazole with N-[4-(2-chloroacetyl)phenyl]acetamide affords N-[4-(2-(1H-benzimidazol-1-yl) acetyl] phenyl acetamide,which upon hydrolysis yield 1-(4aminophenyl)-2-(1H-benzimidazol-1-yl)ethanone. The Diazotion of 1-(4-aminophenyl)-2-(1Hbenzimidazol-1-yl)ethanone couple with salicylic acid,they afford the ligand compound and named as 5-([4-(2-(1H-benzimidazol-1-yl)acetyl)phenyl]diazenyl)-2-hydroxybenzoic acid(SA-BI). The transition metal complexes of Cu 2+ , Co 2+ ,Ni 2+ , Mn 2+ and Zn 2+ of SA-BI have been prepared and characterized by elemental analyses, spectral studies, magnetic moment determination, molar conductivity measurement and microbicidal activity.

A 44-pass fiber optic surface plasmon resonance (SPR) sensor coupled with a field-assist capability for measurement of refractive index change due to positive and negative ions is shown. The field-assist feature forces ions to the SPR surface, causing the SPR signal response to change which reflects a decrease or increase in refractive index depending on whether positive or negative ions are being attracted to the surface. This technique offers the potential for the sensitive detection of cations and anions in a solution.

Author contributions R.M.Y. synthesized materials, performed cell-based experiments and analysed the data. A.U.B. designed and supervised the research, analysed the data and co-wrote the paper. E.M.V.J. synthesized materials, performed experiments and analysed the data. R.M.S.M. designed and supervised the experiments and analysed the data. M.B. came up with the concept, designed the research, analysed the data and co-wrote the paper.