Synthesis of a Novel Glycopeptide by Polymeranalogous Reaction of Gelatin with Mono‐6‐para‐toluenesulfonyl‐β‐cyclodextrin and its Supramolecular Properties

A synthetic model glycoprotein was successfully synthesized using gelatin and mono‐6‐para‐toluenesulfonyl‐β‐cyclodextrin which were reacted under microwave conditions in basic media. The resulting glycoprotein is observed to form intermolecular inclusion complexes through complexation of the aromatic moieties along the polymer chain by the attached cyclodextrins. This phenomenon was analyzed and proven by 2D NMR spectroscopy (ROESY) and dynamic light scattering (DLS). Above the denaturation temperature, a strong increase of the hydrodynamic diameter was found due to enhanced supramolecular agglomeration. Such a novel glycoprotein with supramolecular self‐recognition would be promising in biomedical applications serving as a drug‐delivery basis polymer.

     

Atomistic molecular dynamics simulations on the interaction of TEMPO-oxidized cellulose nanofibrils in water

Atomistic molecular dynamics simulations were carried out to obtain information on the rheological, aggregation and disintegration properties of carboxylated (TEMPO-oxidized) cellulose nanofibrils with different functionalization levels. The magnitude of the inter-fibril interaction was quantified for parallel nanofibrils using the umbrella sampling method. The obtained potential of mean force was found highly sensitive to the charge configuration for intermediate functionalization levels. This feature was further studied with an electrostatic model for similar charge configurations and system periodicity as in the case of the molecular dynamics simulations. The electrostatic contribution of the charged surfaces varied from repulsive to attractive depending on the distribution of the carboxylate groups and nearby counter-ions, as well as the distance between the fibrils. The simulated deviations from average behavior for single fibrils in both models suggest heterogeneity in their aggregation and disintegration behavior. This was seen in disintegration experiments, where the differences in disintegration energy and in the structural variation qualitatively agreed with the model predictions. As to aggregation behavior, the studied case with parallel fibrils reflects the upper boundary of the repulsive interaction.     

Hydrophobic modification of polycarbonate for reproducible and stable formation of biocompatible microparticles

We propose a simple and effective scheme for the modification of the walls of microfluidic channels fabricated in polycarbonate (PC) after the device has been bonded. The method prevents both static and dynamic wetting of PC by aqueous solutions including viscous, non-Newtonian solutions of polymers as e.g. alginate. The procedure uses dodecylamine, which readily reacts with the carbonate groups of PC to produce a hydrophobic surface. We characterize the dependence of the contact angles and homogeneity of the modified surfaces on the time, temperature, and concentration-all important parameters-of the reaction and provide optimal conditions for the process.     

A new implementation of electrochemical impedance spectroscopy (EIS) and other methods to monitor the progress of hydration of strontium monoaluminate (SrAl2O4) cement

Journal of Thermal Analysis and Calorimetry - Electrochemical impedance spectroscopy has been employed to monitor hydration of strontium monoaluminate (SrAl2O4) cement. Other supported techniques...     

Application of Polyamines and Amino Acid Derivatives Based on 2-Azabicycloalkane Backbone in Enantioselective Aldol Reaction

Carbon–carbon bond forming reactions, such as aldol reaction and condensation, belong to extremely desired transformations as manifested by >25,000 entries in SciFinder. Their stereoselective variant requires the use of an appropriate catalyst with a strictly defined structure. Hence, chiral 2-azabicycloalkane-based catalysts were designed, synthesized and tested in a stereoselective aldol reaction between cyclic/acyclic ketone and p-nitrobenzaldehyde both in organic and aqueous media. Among catalysts containing a chiral bicyclic backbone, amide based on 2-azabicyclo[3.2.1]octane and pyrrolidine units showed the best catalytic activity and afforded aldol product in excellent chemical yields (up to 95%) and good diastereo- and enantioselectivity (dr 22:78, ee up to 63%).     

Nanomaterial-based biosensors for detection of prostate specific antigen

Screening serum for the presence of prostate specific antigen (PSA) belongs to the most common approach for the detection of prostate cancer. This review (with 156 refs.) addresses recent developments in PSA detection based on the use of various kinds of nanomaterials. It starts with an introduction into the field, the significance of testing for PSA, and on current limitations. A first main section treats electrochemical biosensors for PSA, with subsections on methods based on the use of gold electrodes, graphene or graphene-oxide, carbon nanotubes, hybrid nanoparticles, and other types of nanoparticles. It also covers electrochemical methods based on the enzyme-like activity of PSA, on DNA-, aptamer- and biofuel cell-based methods, and on the detection of PSA via its glycan part. The next main section covers optical biosensors, with subsections on methods making use of surface plasmon resonance (SPR), localized SPR and plasmonic ELISA-like schemes. This is followed by subsections on methods based on the use of fiber optics, fluorescence, chemiluminescence, Raman scattering and SERS, electrochemiluminescence and cantilever-based methods. The most sensitive biosensors are the electrochemical ones, with lowest limits of detection (down to attomolar concentrations), followed by mass cantilever sensing and electrochemilumenescent strategies. Optical biosensors show lower performance, but are still more sensitive compared to standard ELISA. The most commonly applied nanomaterials are metal and carbon-based ones and their hybrid composites used for different amplification strategies. The most attractive sensing schemes are summarized in a Table. The review ends with a section on conclusions and perspectives.

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Graphical abstract Schematic representation of nanostructure-based biosensors for detection of prostate specific antigen using various detection schemes and biorecognition elements such as antibodies (Abs), aptamers (APT), lectins (LEC), and molecularly imprinted polymers (MIP).

     

Aldimines of 5-aminouracil as reagents in 1,3-dipolar cycloaddition reaction

Abstract  

The condensation of 5-aminouracil with aromatic aldehydes gave the appropriate C-arylimines, which were used in [2+3] cycloaddition with nitrile oxides derived from 4-substituted benzaldoximes. As a result of the dipolar cycloaddition reaction several hitherto unknown 5-(3,5-diphenyl-1,2,4-oxadiazol-4(5H)-yl)pyrimidine-2,4(1H,3H)-diones have been obtained in satisfactory yields.     

Assessment of the sorption capacity and regeneration of carbon dioxide sorbents using thermogravimetric methods

Adsorption methods using solid sorbents are an alternative to the absorption technology in the processes of purification gases from carbon dioxide. There is a need to rapidly assess the suitability of sorbents for use it in PSA, TSA, or VPSA installations. Important parameters which determine the quality of the sorbent are the sorption capacity of sorbent, selectivity to CO₂ and the possibility of regeneration. This paper presents the results of sorption/desorption of CO₂ study on the impregnated porous materials using thermogravimetric methods. Thermogravimetry allows for rapid assessment of sorption capacity and regeneration of the sorbents. Specially selected temperature program allowed to determine the sorption capacity of sorbents depending on the concentration of CO₂ in the gas mixture and temperature. Degree of sorbent purification was determined in desorption process.     

A convenient synthesis of 5-(1,2,4-oxadiazol-5-yl)pyrimidine-2,4(1H,3H)-diones

The synthesis of 5-heteroaryl-substituted uracil derivatives is presented. The 1,3-dipolar cycloaddition reaction was applied for the construction of a heterocyclic ring. The nitrile oxides were obtained from the appropriate 4-substituted benzaldoximes using N-chlorosuccinimide (NCS) under basic conditions. [2+3] Cycloaddition of nitrile oxides with 5-cyanouracil as a dipolarophile gave the corresponding 5-(3-substituited-1,2,4-oxadiazol-5-yl)uracils in satisfactory yields under mild conditions. 5-Substituted uracils having an additional heterocyclic ring were obtained as a result of the [2+3] cycloaddition of 5-cyanouracil to nitrile oxides generated from thiophene-2-carbaldehyde and 5-formyluracil derivatives.