Recombinant Δ4,5‐Steroid 5 β‐Reductases as Biocatalysts for the Reduction of Activated CC‐Double Bonds in Monocyclic and Acyclic Molecules

It was found that Δ^4,5‐steroid 5β‐reductases are capable of reducing also small molecules bearing an activated CC double bond such as monocyclic enones and acyclic enoate esters. As preferred Δ^4,5‐steroid 5β‐reductase (5β‐StR) for this purpose, 5β‐StR from Arabidopsis thaliana was used. In part, enzyme activities are even higher than that for progesterone. Successful preliminary biotransformations with enzymatic in situ cofactor recycling were also carried out. When using the prochiral compound isophorone as a substrate, a high enantioselective reaction course (>99% ee) was observed.     

A study of in situ plated tin-film electrodes for the determination of trace metals by means of square-wave anodic stripping voltammetry

This work is a study of tin-film electrodes (SnFEs) for the determination of trace metals by means of square-wave anodic stripping voltammetry (SWASV). SnFEs represent a new promising type of environment-friendly electrodes but their analytical performance has not been explored in detail so far. Initially, the operational parameters for the simultaneous determination of Cd(II) and Zn(II) on in situ plated SnFEs on different substrates were thoroughly investigated. Using the selected conditions, at a preconcentration time of 120 s the limits of detection were 0.7 μg l⁻¹ for Cd and 0.9 μg l⁻¹ for Zn and the percent relative standard deviations were 4.2% for Zn(II) and 3.6% for Cd(II) at the 20 μg l⁻¹ level (n = 8). Subsequently, a study was conducted to investigate the utility of SnFEs as sensors for the determination of other metals, including those with oxidation potentials close to, or more positive than, the oxidation potential of Sn (Tl(I), Pb(II), Cu(II)). Finally, the SnFEs were successfully applied for the determination of Pb(II) and Zn(II) in tap water.     

Novel Hydrogen Sulfide (H2S)-Releasing BW-HS-101 and Its Non-H2S Releasing Derivative in Modulation of Microscopic and Molecular Parameters of Gastric Mucosal Barrier

Hydrogen sulfide (H₂S) is an endogenously produced molecule with anti-inflammatory and cytoprotective properties. We aimed to investigate for the first time if a novel, esterase-sensitive H₂S-prodrug, BW-HS-101 with the ability to release H₂S in a controllable manner, prevents gastric mucosa against acetylsalicylic acid-induced gastropathy on microscopic and molecular levels. Wistar rats were pretreated intragastrically with vehicle, BW-HS-101 (0.5–50 μmol/kg) or its analogue without the ability to release H₂S, BW-iHS-101 prior to ASA administration (125 mg/kg, intragastrically). BW-HS-101 was administered alone or in combination with nitroarginine (L-NNA, 20 mg/kg, intraperitoneally) or zinc protoporphyrin IX (10 mg/kg, intraperitoneally). Gastroprotective effects of BW-HS-101 were additionally evaluated against necrotic damage induced by intragastrical administration of 75% ethanol. Gastric mucosal damage was assessed microscopically, and gastric blood flow was determined by laser flowmetry. Gastric mucosal DNA oxidation and PGE₂ concentration were assessed by ELISA. Serum and/or gastric protein concentrations of IL-1α, IL-1β, IL-2, IL-4, IL-6, IL-10, IL-13, VEGF, GM-CSF, IFN-γ, TNF-α, and EGF were determined by a microbeads/fluorescent-based multiplex assay. Changes in gastric mucosal iNOS, HMOX-1, SOCS3, IL1-R1, IL1-R2, TNF-R2, COX-1, and COX-2 mRNA were assessed by real-time PCR. BW-HS-101 or BW-iHS-101 applied at a dose of 50 μmol/kg protected gastric mucosa against ASA-induced gastric damage and prevented a decrease in the gastric blood flow level. H₂S prodrug decreased DNA oxidation, systemic and gastric mucosal inflammation with accompanied upregulation of SOCS3, and EGF and HMOX-1 expression. Pharmacological inhibition of nitric oxide (NO) synthase but not carbon monoxide (CO)/heme oxygenase (HMOX) activity by L-NNA or ZnPP, respectively, reversed the gastroprotective effect of BW-HS-101. BW-HS-101 also protected against ethanol-induced gastric injury formation. We conclude that BW-HS-101, due to its ability to release H₂S in a controllable manner, prevents gastric mucosa against drugs-induced gastropathy, inflammation and DNA oxidation, and upregulate gastric microcirculation. Gastroprotective effects of this H₂S prodrug involves endogenous NO but not CO activity and could be mediated by cytoprotective and anti-inflammatory SOCS3 and EGF pathways.     

Silver nanoparticles deposited on polysiloxane networks as active catalysts in dye degradation

The article proposes a new method of obtaining silver nanoparticles on polysiloxane networks using the reducing properties of Si–H groups. Three types of networks with different architecture and distribution of Si–H groups were studied as reducing agents for silver ions and as matrices for the obtained silver nanoparticles. As established by FTIR spectroscopic studies, the redox reaction between Ag⁺ ions from the silver heptafluorobutyrate solution in toluene and Si–H groups of the networks occurred, which resulted in the appearance of silver nanoparticles in the systems. The amount of metal introduced into individual polysiloxane networks is closely related to the consumption of Si–H groups in them. The type of polysiloxane networks used affects the size of Ag NPs obtained and their distribution on the carrier. Polysiloxane-Ag systems are observed to be an effective catalyst on reduction of hazardous dye like methyl red, which is confirmed by a decrease in absorbance maximum values.     

6-Benzylaminopurine Alleviates the Impact of Cu2+ Toxicity on Photosynthetic Performance of Ricinus communis L. Seedlings

Copper (Cu) is an essential element involved in various metabolic processes in plants, but at concentrations above the threshold level, it becomes a potential stress factor. The effects of two different cytokinins, kinetin (KIN) and 6-benzylaminopurine (BAP), on chlorophyll a fluorescence parameters, stomatal responses and antioxidation mechanisms in castor (Ricinus communis L.) under Cu²⁺ toxicity was investigated. Ricinus communis plants were exposed to 80 and 160 μM CuSO₄ added to the growth medium. Foliar spraying of 15 μM KIN and BAP was carried out on these seedlings. The application of these cytokinins enhanced the tissue water status, chlorophyll contents, stomatal opening and photosynthetic efficiency in the castor plants subjected to Cu²⁺ stress. The fluorescence parameters, such as Fm, Fv/Fo, Sm, photochemical and non-photochemical quantum yields, energy absorbed, energy trapped and electron transport per cross-sections, were more efficiently modulated by BAP application than KIN under Cu²⁺ toxicity. There was also effective alleviation of reactive oxygen species by enzymatic and non-enzymatic antioxidation systems, reducing the membrane lipid peroxidation, which brought about a relative enhancement in the membrane stability index. Of the various treatments, 80 µM CuSO₄ + BAP recorded the highest increase in photosynthetic efficiency compared to other cytokinin treatments. Therefore, it can be concluded that BAP could effectively alleviate the detrimental effects of Cu²⁺toxicity in cotyledonary leaves of R. communis by effectively modulating stomatal responses and antioxidation mechanisms, thereby enhancing the photosynthetic apparatus’ functioning.     

Human Papillomaviruses as Infectious Agents in Gynecological Cancers. Oncogenic Properties of Viral Proteins

Human papillomaviruses (HPVs), which belong to the Papillomaviridae family, constitute a group of small nonenveloped double-stranded DNA viruses. HPV has a small genome that only encodes a few proteins, and it is also responsible for 5% of all human cancers, including cervical, vaginal, vulvar, penile, anal, and oropharyngeal cancers. HPV types may be classified as high- and low-risk genotypes (HR-HPVs and LR-HPVs, respectively) according to their oncogenic potential. HR-HPV 16 and 18 are the most common types worldwide and are the primary types that are responsible for most HPV-related cancers. The activity of the viral E6 and E7 oncoproteins, which interfere with critical cell cycle points such as suppressive tumor protein p53 (p53) and retinoblastoma protein (pRB), is the major contributor to HPV-induced neoplastic initiation and progression of carcinogenesis. In addition, the E5 protein might also play a significant role in tumorigenesis. The role of HPV in the pathogenesis of gynecological cancers is still not fully understood, which indicates a wide spectrum of potential research areas. This review focuses on HPV biology, the distribution of HPVs in gynecological cancers, the properties of viral oncoproteins, and the molecular mechanisms of carcinogenesis.     

Part II: surface-enhanced Raman spectroscopy investigation of methionine containing heterodipeptides adsorbed on colloidal silver

Surface-enhanced Raman scattering (SERS) spectra of methionine (Met) containing dipeptides: Met-X and X-Met, where X is: L-glycine (Gly), L-leucine (Leu), L-proline (Pro), and L-phenylalanine (Phe) are reported. Using pre-aggregated Ag colloid we obtained high-quality SERS spectra of these compounds spontaneously adsorbed on colloidal silver. Additionally, we measured Raman spectra (RS) of these heterodipeptides in a solid state as well as in acidic and basic solutions. The RS and SERS spectra of Met-X and X-Met presented in this work appear to be different. One of the most prominent and common features in the SERS spectra of all these dipeptides is a band in the 660-690 cm(-1) range that is due to the C-S stretching, v(CS), vibration of Met. This suggests that all the abovementioned compounds adsorb on the silver surface through a thioether atom. On the other hand, the SERS spectra of X-Met show clearly that not only the S atom but also the carboxylate group interact with the colloid surface as manifested by the enhancement of bands in the 920-930 and 1380-1396 cm(-1) regions. These bands are ascribed to the v(C-COO(-)) and v(sym)(COO(-)) vibrations, respectively. Additionally, a SERS spectrum of Phe-Met indicates that the interaction of the thioether atom, amine group, and aromatic side chain with the silver surface is favorable and may dictate the orientation and conformation of adsorbed peptide.     

Polyaniline–rhodium composites: Preparation,physicochemical characterization,and catalytic properties

In this work, polyaniline (PANI)–rhodium composites have been obtained for the first time. Their preparation procedure has involved reduction of Rh³⁺ ions in RhCl₃ aqueous solutions with NaBH₄ in the presence of PANI. Using UV–vis spectroscopy, it has been found that the reduction process is fast. X‐ray diffraction and Rh3d XPS studies have confirmed that metallic rhodium is incorporated into PANI matrix. SEM and TEM investigations allowed to establish that the sizes of Rh crystallites formed depend on the amount of metal in the composite as well as on the preparation conditions. It has been demonstrated that the composites containing Rh nanoparticles whose size is predominantly below 10 nm can be obtained. IR spectroscopy has proved that PANI chain is protonated in the Rh³⁺ reduction process. Catalytic properties of PANI–Rh composites have been investigated using isopropyl alcohol conversion as the test reaction. It has been found that the composites containing Rh nanoparticles show high redox activity. Catalytic activity of the composites in which larger, agglomerated metal particles have been present is about three times lower. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008