Merging gold plasmonic nanoparticles and L-proline inside a MOF for plasmon-induced visible light chiral organocatalysis at low temperature.

Light-driven asymmetric photocatalysis represents a straightforward approach in modern organic chemistry. In comparison to the homogeneous one, heterogeneous asymmetric photocatalysis has the advantages of easy catalyst separation, recovery, and reuse, thus being cost- and time-effective. Here, we demonstrate how plasmon-active centers (gold nanoparticles - AuNPs) allow visible light triggering of chiral catalyst (proline) in model aldol reaction between acetone and benzaldehyde. The metal-organic framework UiO-66-NH2 was used as an advanced host platform for the loading of proline and AuNPs and their stabilization in spatial proximity. Aldol reactions were carried out at a low temperature (-20 °C) under light illumination which resulted in 91% ee with a closed-to-quantitative yield, 4.5 times higher than that without light (i.e. in the absence of plasmon triggering). A set of control experiments and quantum chemical modeling revealed that the plasmon assistance proceeds through hot electron excitation followed by an interaction with an enamine with the formation of anion radical species. We also demonstrated the high stability of the proposed system in multiple catalytic cycles without leaching metal ions, which makes our approach especially promising for heterogeneous asymmetric photocatalysis.

[Determination of cobalt in plasma blood samples by the ICP-MS method after oral intake of dietary supplements containing low doses of cobalt].

Salts of inorganic cobalt (Со) prevent the degradation of the alpha subunit of the hypoxia-inducible factor (HIF), imitating the state of hypoxia in the body and increasing the production of the endogenous hormone erythropoietin (EPO), and are used as doping substances that increase blood oxygen capacity and endurance, which give competitive advantages in sports. Currently, a large number of dietary supplements, including Co-containing ones, are offered on free sale. Their uncontrolled intake can affect not only the professional career of athletes, but also their health, due to the fact that this trace element and its salts are the strongest inorganic poisons and carcinogens. Despite this, their availability on the pharmaceutical market, a noticeable effect of erythropoiesis stimulation and a convenient oral form of administration lead to the need for their detection in modern doping control. The purpose of this research was to develop an approach to differentiate cobalt from vitamin B12, present in the body in its natural state, from the intake of cobalt salts by quantifying and comparing blood levels of vitamin B12 and total cobalt. Methods. The study involved 9 healthy volunteers (women and men) aged 25 to 45 years, leading an active lifestyle. Three of them took 2500 µg/day of cobalamin for 20 days (comparison group), three - dietary supplement containing cobalt asparaginate (100 µg/day in terms of pure cobalt), and the rest - dietary supplements with cobalt sulfate heptahydrate (100 µg/day in terms of pure cobalt) (administration groups) at the same time after meals. Blood samples were taken at baseline and on days 5, 9, 14 and 20. The concentrations of total cobalt in blood plasma samples of volunteers were measured by inductively coupled plasma mass-spectrometry (ICP-MS), the levels of cobalamin were determined on a Cobas 6000 immunochemical analyzer using the Elecsys Vitamin B12 II Assay ELISA kits. Results. It was found that oral intake of of cobalamin at a therapeutic dose significantly exceeding the recommended daily intake (3 µg), there was a regular slight increase in the blood concentration of total cobalt (1.1 times). At the same time intake of dietary supplements containing cobalt in the form of sulfate or asparaginate (about 100 µg per day in terms of pure cobalt) was accompanied by 4-6.7 fold increase in the concentration of total cobalt while unchanged vitamin B12 plasma concentration was observed. The detection of such changes can reliably indicate the use of prohibited salts and, of course, will be in demand for anti-doping control. Conclusion. Long-term monitoring of vitamin B12 and total cobalt levels, similar to hematological module of the Athlete Biological Passport program, will unambiguously detect possible abuse of cobalt salts and can be an additional evidence of the presence of these doping substances to other analytical methods, such as a combination of liquid chromatography and ICP-MS (LC-ICP-MS).

Plasmon-active optical fiber functionalized by metal organic framework for pesticide detection.

Functional plasmonic fiber for detection and on-line monitoring of organophosphorus pesticides in water or model soil samples is described. The appearance of the plasmon absorption band was realized through the deposition of a thin gold layer on the naked core of multimode optical fiber. The metalorganic frameworks (MOF-5) layer was deposited on the gold surface for the introduction of a high affinity towards the target pesticides. The MOF-5 layer affords the extraction of pesticides and their concentration primarily in the "plasmon evanescent wave" space, allowing the detection by the shift of plasmon absorption band. The growth of MOF-5 layer was confirmed using the Raman, XPS and XRD measurements. The entrapping of pesticides was checked using the Raman spectroscopy and ellipsometry, which also indicate the corresponding changes of MOF-5 refractive index. The series of further experiments demonstrate the applicability of proposed fiber sensor for detection of pesticides in soil without the false signals from surrounding media. The main advantages of proposed sensor can be attributed to simplicity, high sensitivity, low cost and the absence of organic solvents for the probe treatment.

[Authentication study of the preparation 'Avastin' by means of chemical-toxicological analysis]. / Issledovanie podlinnosti preparata 'Avastin' metodami khimiko-toksikologicheskogo analiza.

Falsification and use of low-quality drugs of biological origin creates a threat to public health. To a greater extent, costly drugs, including bevacizumab, are exposed to similar abuses. Timely determination of cases of forgery or the improper clinical use of monoclonal antibody preparations is one of the necessary measures that can be taken to limit the risks and preserve the health of patients. This paper presents the results of the investigation of the bevacizumab preparation 'Avastin', which was withdrawn from ophthalmic clinical practice in the course of the investigation. We compared the qualitative and quantitative composition of the drug samples, which were determined using commonly available methods of chemical and toxicological analysis.

Label-free surface-enhanced Raman spectroscopy with artificial neural network technique for recognition photoinduced DNA damage.

Taking advantage of surface-enhanced Raman scattering (SERS) methodology with its unique ability to collect abundant intrinsic fingerprint information and noninvasive data acquisition we set up a SERS-based approach for recognition of physically induced DNA damage with further incorporation of artificial neural network (ANN). As a proof-of-concept application, we used the DNA molecules, where the one oligonucleotide (OND) was grafted to the plasmonic surface while complimentary OND was exposed to UV illumination with various exposure doses and further hybridized with the grafted counterpart. All SERS spectra of entrapped DNA were collected by several operators using the portable spectrometer, without any optimization of measurements procedure (e.g., optimization of acquisition time, laser intensity, finding of optimal place on substrate, manual baseline correction, etc.) which usually takes a significant amount of operator's time. The SERS spectra were employed as input data for ANN training, and the performance of the system was verified by predicting the class labels for SERS validation data, using a spectra dataset, which has not been involved in the training process. During that phase, accuracy higher than 98% was achieved with a level of confidence exceeding 95%. It should be noted that utilization of the proposed functional-SERS/ANN approach allows identifying even the minor DNA damage, almost invisible by control measurements, performed with common analytical procedures. Moreover, we introduce the advanced ANN design, which allows not only classifying the samples but also providing the ANN analysis feedback, which associates the spectral changes and chemical transformations of DNA structure.

Metal-organic framework (MOF-5) coated SERS active gold gratings: A platform for the selective detection of organic contaminants in soil.

In this work, we proposed the functionalization of a surface plasmon-polariton (SPP)-supported gold grating surface with the metal-organic framework (MOF-5) for sensitive, selective and reproducible surface-enhanced Raman scattering (SERS) detection of organophosphorus pesticides. Homogeneous distribution of plasmon intensity along the Au grating surface ensures the high reproducibility of SERS results (deviation of Raman peak intensity does not exceed the 4% along the sample). The surface-assisted growth of thin MOF-5 film was accomplished in two steps procedure: (i) covalent grafting by 4-carboxyphenyl groups and (ii) the immersion of samples in the mother liquid of MOF-5. Proposed SERS chip proved itself to be a perfect analytical probe for the detection of organophosphorus pesticides with high reliability and low detection limit up to 10-12 M. Moreover, selective detection and recognition of several relevant organic contaminants (azo-dye, mycotoxin, and pesticide) from the simulated soil was successfully demonstrated. All SERS measurements were performed using portable Raman spectrometer and can easily be expanded to environmental conditions. Our work combines the high affinity of organic contaminants to the MOF-5 with excellent plasmonic excitation on the surface plasmon-polariton supported structure and shows the way to the realization of closed-to-ideal analytical SERS chip.

Vapor Annealing and Colloid Lithography: An Effective Tool To Control Spatial Resolution of Surface Modification.

Colloid lithography represents a simple and efficient method for creation of a large-scale template for subsequent surface patterning, deposition of regular metal nanostructures, or periodical surface structures. However, this method is significantly restricted by its ability to create only a limited number of structures with confined geometry and symmetry features. To overcome this limitation, different techniques, such as plasma treatment or tilting angle metal deposition, have been proposed. In this paper, an alternative method based on the vapor annealing of ordered single polystyrene (PS) microspheres layer, followed by the surface grafting with arenediazonium tosylates is proposed. Application of vapor treatment before surface grafting allows effective control of the area screened by PS microspheres. Pristine and vapor-annealed microsphere arrays on the gold substrate were electrochemically modified using ADTs. Subsequent removal of the PS microsphere mask enabled to prepare well-defined nanostructures with controllable surface features. In particular, prepared periodic arrangements were achieved by the grafting of OFGs to the empty interspaces between nanopore arrays. The process of sample preparation was controlled, and the properties of prepared structures were characterized by various techniques, including atomic force microscopy (AFM), conductive AFM, scanning electron microscopy energy-dispersive X-ray spectrometry, Raman spectroscopy, and voltammetry.

Reversible switching of PEDOT:PSS conductivity in the dielectric-conductive range through the redistribution of light-governing polymers.

One of the biggest challenges in the field of organic electronics is the creation of flexible, stretchable, and biofavorable materials. Here the simple and repeatable method for reversible writing/erasing of arbitrary conductive pattern in conductive polymer thin film is proposed. The copolymer azo-modified poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) was synthesized to achieve reversible photo-induced local electrical switching in the insulator-semimetal range. The photoisomerization of the polymer was induced by grafting nitrobenzenediazonium tosylate to the PSS main chains. While the as-deposited PEDOT:PSS thin films showed good conductivity, the modification procedure generated polymer redistribution, resulting in an island-like PEDOT distribution and the loss of conductivity. Further local illumination (430 nm) led to the azo-isomerization redistribution of the polymer chains and the creation of a conductive pattern in the insulating polymer film. The created pattern could then be erased by illumination at a second wavelength (470 nm), which was attributed to induction of reverse azo-isomerization. In this way, the reversible writing/erasing of arbitrary conductive patterns in thin polymer films was realized.

[DIURETIC ACTIVITY OF 4-O-CARBOXYPHENYL-D-GLUCOPYRANOSIDE SODIUM SALT ADMINISTERED VIA DIFFERENT ROUTES].

It was compared the diuretic activity of the sodium salt of 4-(O-ß-D-glucopyranosyloxy)benzoic acid for enteral (intragastric) and parenteral ways of administration. The test substance was administered enterally and parenterally (subcutaneously in the region of the withers) in a daily dose of 18 µmol/kg for the first seven days and in a dose of 54 mmol/kg for the next seven days. Diuretic activity of the sodium salt of 4-(O-ß-D-glucopyranosyloxy)benzoic acid was evaluated in terms of urine volume. Urine was analyzed for creatinine and the concentration of sodium, potassium and chloride ions. Experiments showed that the sodium salt of 4-(O-ß-D-glucopyranosyloxy)benzoic acid produced a diuretic effect only for the enteral administration route.

[STUDYING GASTRIC ULCERATION EFFECT OF A NEW DRUG INTENDED FOR TREATMENT OF CHRONIC INFLAMMATORY DISEASES OF KIDNEYS AND URINARY TRACT.]

Gastric ulceration properties (gastrointestinal toxicity) of the sodium salt of 4-(0-ß-D-glucopyranosyloxy) benzoic acid, a new nonsteroidal anti-inflammatory drug (NSAID) intended for the treatment of chronic inflammatory diseases of the kidney and urinary tract, have been tested on laboratory animals. Acute NSAID-induced gastropathy was induced in rats by oral administration of indomethacin, nimesulide, diclofenac, acetylsalicylic acid and the new drug. Test animals were killed by instantaneous decapitation 4 h after treatment and their gastrointestinal tracts were studied by pathomorphological methods on micropreparations and histological sections of gastric mucosa. It was established that the new drug, in contrast to reference NSAIDS, did not exhibit gastropathic action on the gastric mucosa.

ANTI-INFLAMMATORY ACTIVITY OF SODIUM SALT OF 4-(O-ß-D-GLUCOPYRANOSYLOXY)BENZOIC ACID.

We have evaluated the anti-inflammatory activity of the sodium salt of 4-(O-ß-D-glucopyranosyloxy)benzoic acid in comparison to well-known nonsteroidal anti-inflammatory drugs (NSAIDs). Carrageenan suspension (1%, 0.1 mL) was injected into subplantar region of the right hindpaw of rats (n = 12) pretreated (7 days and 60 min before carrageenan injection) intragastrically with methyl ester of 4(ß-D-glucopyranosyloxy)benzoic acid (20 mg/kg), acetylsalicylic acid (20 mg/kg), 4-hydroxybenzoic acid (20 mg/kg), or vehicle (2 mL of purified water). Paw edema volume was measured plethysmographically at 1, 2 and 4 h after carrageenan injection. The results showed that intragastric administration of the sodium salt of 4-(O-ß-D-glucopyranosyloxy)benzoic acid in a dose of 20 mg/kg for 7 days decreased the intensity of experimental inflammation.