scholarly journals Radiochemical Studies of Hydrogen Exchange in Organic Compounds

2021 ◽  
Author(s):  
◽  
Colin Truscott Johnson
Keyword(s):  
Organic Compound ◽  
Grignard Reagent ◽  
Hydrogen Exchange ◽  
Molecular Size ◽  
Water Soluble ◽  
Side Reactions ◽  
Hydrogen Atoms ◽  
Incomplete Reaction ◽  
The One ◽  
Extreme Care

<p>A property of a new or unknown organic compound which must be determined once the empirical formula and molecular weight are known, is the number of active or replaceable hydrogen atoms which the compound contains. These include hydrogen atoms present in amine, hydroxyl, carboxyl and other groups, where the hydrogen is not bound to a carbon atom but to an oxygen, nitrogen or sulphur atom or is in a position where it can ionize. The most general method by which this may be done quantitatively, is the one originally due to Zerewitinoff Zerewitinoff - Berichte 40 2023 (1907) 41 2233 (1908) 42 4802 (1909) 43 3590 (1910) 47 1659 (1914) 47 2417 (1914) and since developed on a micro scale by Roth A. Soltys Mikrochemie 20 107 (1936), Flaschentrager A. Roth Mikrochemie 11 140 (1932), whose method incorporates work by Tschugaeff - Flaschentrager z. Physiol Chem. 146 219 (1923) and the other two authors, and Soltys L. Tschugaeff Berichte 35 3912 (1902), and incorporates many of the latest improvements. This involves the quantatatively evolution of methane from reaction of the Grignard reagent MeMgI on groups such as -SH, -OH, -NH2, -COOH etc., i.e. those groups containing active or replaceable hydrogen atoms. Analysis by this method requires extreme care in technique and exact attention to experimental details. High results are obtained if the solvent or any part of the apparatus contains moisture and the whole determination must be carried out in an atmosphere of nitrogen to avoid reaction of the Grignard reagent with any oxygen present. Low results are obtained if the test solution does not dissolve completely in the chosen solvent and it is essential to carry out a blank prior to each analysis. The proceedure is labourious and painstaking and gives an accuracy of not greater than 5% using 3-5 mgm of organic compound. It also has the disadvantage that the Grignard Reagent will also react with other groups, such as carbonyl, aldehyde, nitrile etc., which may be present. This method cannot be applied to highly water soluble compounds which do not dissolve in ethers or other organic solvents and as the molecular size or complexity of the sample increases, the accuracy of the gasometric reactions becomes less, due to side reactions and incomplete reaction.</p>

scholarly journals Radiochemical Studies of Hydrogen Exchange in Organic Compounds

2021 ◽  
Author(s):  
◽  
Colin Truscott Johnson
Keyword(s):  
Organic Compound ◽  
Grignard Reagent ◽  
Hydrogen Exchange ◽  
Molecular Size ◽  
Water Soluble ◽  
Side Reactions ◽  
Hydrogen Atoms ◽  
Incomplete Reaction ◽  
The One ◽  
Extreme Care

<p>A property of a new or unknown organic compound which must be determined once the empirical formula and molecular weight are known, is the number of active or replaceable hydrogen atoms which the compound contains. These include hydrogen atoms present in amine, hydroxyl, carboxyl and other groups, where the hydrogen is not bound to a carbon atom but to an oxygen, nitrogen or sulphur atom or is in a position where it can ionize. The most general method by which this may be done quantitatively, is the one originally due to Zerewitinoff Zerewitinoff - Berichte 40 2023 (1907) 41 2233 (1908) 42 4802 (1909) 43 3590 (1910) 47 1659 (1914) 47 2417 (1914) and since developed on a micro scale by Roth A. Soltys Mikrochemie 20 107 (1936), Flaschentrager A. Roth Mikrochemie 11 140 (1932), whose method incorporates work by Tschugaeff - Flaschentrager z. Physiol Chem. 146 219 (1923) and the other two authors, and Soltys L. Tschugaeff Berichte 35 3912 (1902), and incorporates many of the latest improvements. This involves the quantatatively evolution of methane from reaction of the Grignard reagent MeMgI on groups such as -SH, -OH, -NH2, -COOH etc., i.e. those groups containing active or replaceable hydrogen atoms. Analysis by this method requires extreme care in technique and exact attention to experimental details. High results are obtained if the solvent or any part of the apparatus contains moisture and the whole determination must be carried out in an atmosphere of nitrogen to avoid reaction of the Grignard reagent with any oxygen present. Low results are obtained if the test solution does not dissolve completely in the chosen solvent and it is essential to carry out a blank prior to each analysis. The proceedure is labourious and painstaking and gives an accuracy of not greater than 5% using 3-5 mgm of organic compound. It also has the disadvantage that the Grignard Reagent will also react with other groups, such as carbonyl, aldehyde, nitrile etc., which may be present. This method cannot be applied to highly water soluble compounds which do not dissolve in ethers or other organic solvents and as the molecular size or complexity of the sample increases, the accuracy of the gasometric reactions becomes less, due to side reactions and incomplete reaction.</p>

scholarly journals A Water-Soluble Copper-Immobilized Covalent Organic Framework Functioning as an “OFF–ON” Fluorescent Sensor for Amino Acids

2021 ◽  
Author(s):  
Lamiaa Reda Ahmed ◽  
Ahmed F. M. EL-Mahdy ◽  
Cheng-Tang Pan ◽  
Shiao-Wei Kuo
Keyword(s):  
Amino Acids ◽  
Fluorescent Sensor ◽  
Water Soluble ◽  
One Pot ◽  
Covalent Organic Framework ◽  
The One ◽  
Organic Framework

In this paper, we describe the construction of a new fluorescent hydroxyl- and hydrazone-based covalent organic framework (TFPB-DHTH COF) through the one-pot polycondensation of 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 2,5-dihydroxyterephthalohydrazide (DHTH) under...

Recent progress in the freeze-etching technique

1971 ◽  
Vol 261 (837) ◽  
pp. 121-131 ◽  
Keyword(s):  
High Vacuum ◽  
Molecular Size ◽  
Etching Technique ◽  
Structural Distortions ◽  
Shadow Casting ◽  
Structural Details ◽  
Freeze Etching ◽  
The One ◽  
Insight Into ◽  
Made In

The freeze-etching technique must be improved if structures at the molecular size level are to be seen. The limitations of the technique are discussed here together with the progress made in alleviating them. The vitrification of living specimens is limited by the fact that very high freezing rates are needed. The critical freezing rate can be lowered on the one hand by the introduction of antifreeze agents, on the other hand by the application of high hydrostatic pressure. The fracture process may cause structural distortions in the fracture face of the frozen specimen. The ‘double-replica’ method allows one to evaluate such artefacts and provides an insight into the way that membranes split. During etching there exists the danger of contaminating the fracture faces with condensable gases. Because of specimen temperatures below —110 °C, special care has to be taken in eliminating water vapour from the high vacuum. An improvement in coating freeze-etched specimens has resulted from the application of electron guns for evaporation of the highest melting-point metals. If heat transfer from gun to specimen is reduced to a minimum, Pt, Ir, Ta, W and C can be used for shadow casting. Best results are obtained with Pt-C and Ta-W . With the help of decoration effects Pt-C shadow castings give the most information about the fine structural details of the specimen.

scholarly journals Pelargonium graveolens Aqueous Decoction: A New Water-Soluble Polysaccharide and Antioxidant-Rich Extract

2018 ◽  
Vol 2018 ◽  
pp. 1-11 ◽  
Author(s):  
Malek Ennaifer ◽  
Taroub Bouzaiene ◽  
Moncef Chouaibi ◽  
Moktar Hamdi
Keyword(s):  
Antioxidant Activity ◽  
Flow Behavior ◽  
Chemical Properties ◽  
Extraction Yield ◽  
Water Soluble ◽  
Pelargonium Graveolens ◽  
Parameters Extraction ◽  
Soluble Polysaccharide ◽  
Dpph Scavenging ◽  
The One

Background. The decoction of Pelargonium graveolens yields an antioxidant-rich extract and a water-soluble polysaccharide. This study aims (1) to investigate the effect of process parameters (extraction time and temperature) on the antioxidant activity of the decoction and the extraction yield of CPGP by response methodology and (2) to study the chemical properties of the optimized decoction and rheological properties of the corresponding extracted polysaccharide. Results. The antioxidant-rich decoction contained about 19.76 ± 0.41 mg RE/g DM of flavonoids and 5.31 ± 0.56 mg CE/gDM of condensed tannins. The crude Pelargonium graveolens polysaccharide (CPGP) contained 87.27 % of sugar. Furthermore, the CPGP solutions (0.5%, 1%, and 2%) exhibited shear-thinning or pseudoplastic flow behavior. A central composite design (CDD) was applied to assess the effects of temperature and time on the antioxidant activity of the decoction, on the one hand, and on water-soluble polysaccharide yield, on the other. The decoction optimization of Pelargonium graveolens aimed to use less energy (93°C for 11 minutes) leading to the highest values of decoction phenolic content (33.01 ±0.49 mg GAE/gDM) and DPPH scavenging activity (136.10 ± 0.62 mg TXE/gDM) and the highest values of CPGP yield (6.97%). Conclusion. The obtained results suggest that the CPGP rheological characteristics are suitable for applications in many industries, especially food. The values of optimal conditions showed that Pelargonium graveolens decoction operation could have multiple uses, especially for consuming less energy.

scholarly journals Improvement of Imiquimod Solubilization and Skin Retention via TPGS Micelles: Exploiting the Co-Solubilizing Effect of Oleic Acid

Pharmaceutics ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1476
Author(s):  
Martina Ghezzi ◽  
Silvia Pescina ◽  
Andrea Delledonne ◽  
Ilaria Ferraboschi ◽  
Cristina Sissa ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Water Solubility ◽  
Skin Penetration ◽  
Water Soluble ◽  
Drug Solubility ◽  
Two Photon Microscopy ◽  
Skin Delivery ◽  
Polyethylene Glycol 1000 ◽  
The One ◽  
Skin Retention

Imiquimod (IMQ) is an immunostimulant drug approved for the topical treatment of actinic keratosis, external genital-perianal warts as well as superficial basal cell carcinoma that is used off-label for the treatment of different forms of skin cancers, including some malignant melanocytic proliferations such as lentigo maligna, atypical nevi and other in situ melanoma-related diseases. Imiquimod skin delivery has proven to be a real challenge due to its very low water-solubility and reduced skin penetration capacity. The aim of the work was to improve the drug solubility and skin retention using micelles of d-α-tocopheryl polyethylene glycol 1000 succinate (TPGS), a water-soluble derivative of vitamin E, co-encapsulating various lipophilic compounds with the potential ability to improve imiquimod affinity for the micellar core, and thus its loading into the nanocarrier. The formulations were characterized in terms of particle size, zeta potential and stability over time and micelles performance on the skin was evaluated through the quantification of imiquimod retention in the skin layers and the visualization of a micelle-loaded fluorescent dye by two-photon microscopy. The results showed that imiquimod solubility strictly depends on the nature and concentration of the co-encapsulated compounds. The micellar formulation based on TPGS and oleic acid was identified as the most interesting in terms of both drug solubility (which was increased from few µg/mL to 1154.01 ± 112.78 µg/mL) and micellar stability (which was evaluated up to 6 months from micelles preparation). The delivery efficiency after the application of this formulation alone or incorporated in hydrogels showed to be 42- and 25-folds higher than the one of the commercial creams.

Silver nanoparticles modified by water-soluble leaning tower[6]arenes for sensing and catalysis

2021 ◽  
Author(s):  
Yi-Nan Zhang ◽  
Zheng Li ◽  
Suriguga Meng ◽  
Alideertu Dong ◽  
Ying-Wei Yang
Keyword(s):  
Silver Nanoparticles ◽  
Hybrid Material ◽  
Water Soluble ◽  
One Pot ◽  
Sodium Salts ◽  
Good Dispersion ◽  
One Pot Synthesis ◽  
The One ◽  
Excellent Stability

Carboxylated leaning tower[6]arene sodium salts are used as an efficient stabiliser for the one-pot synthesis of silver nanoparticles. The resulting hybrid material with good dispersion, excellent stability and narrow size...

scholarly journals Nanostructured Polyelectrolyte Complexes Based on Water-Soluble Thiacalix[4]Arene and Pillar[5]Arene: Self-Assembly in Micelleplexes and Polyplexes at Packaging DNA

Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 777 ◽  
Author(s):  
Luidmila S. Yakimova ◽  
Aigul R. Nugmanova ◽  
Olga A. Mostovaya ◽  
Alena A. Vavilova ◽  
Dmitriy N. Shurpik ◽  
...  
Keyword(s):  
Self Assembly ◽  
Water Soluble ◽  
Macrocyclic Compounds ◽  
Polyelectrolyte Complexes ◽  
Calf Thymus ◽  
Polyfunctional Compounds ◽  
Mixed Nanoparticles ◽  
The One ◽  
New Generation ◽  
Straightforward Approach

Controlling the self-assembly of polyfunctional compounds in interpolyelectrolyte aggregates is an extremely challenging task. The use of macrocyclic compounds offers new opportunities in design of a new generation of mixed nanoparticles. This approach allows creating aggregates with multivalent molecular recognition, improved binding efficiency and selectivity. In this paper, we reported a straightforward approach to the synthesis of interpolyelectrolytes by co-assembling of the thiacalix[4]arene with four negatively charged functional groups on the one side of macrocycle, and pillar[5]arene with 10 ammonium groups located on both sides. Nanostructured polyelectrolyte complexes show effective packaging of high-molecular DNA from calf thymus. The interaction of co-interpolyelectrolytes with the DNA is completely different from the interaction of the pillar[5]arene with the DNA. Two different complexes with DNA, i.e., micelleplex- and polyplex-type, were formed. The DNA in both cases preserved its secondary structure in native B form without distorting helicity. The presented approach provides important advantage for the design of effective biomolecular gene delivery systems.

scholarly journals Hydrogen exchange reveals Hsp104 architecture, structural dynamics, and energetics in physiological solution

2019 ◽  
Vol 116 (15) ◽  
pp. 7333-7342 ◽  
Author(s):  
Xiang Ye ◽  
Jiabei Lin ◽  
Leland Mayne ◽  
James Shorter ◽  
S. Walter Englander
Keyword(s):  
Hydrogen Exchange ◽  
Atp Hydrolysis ◽  
Physiological Solution ◽  
Mass Spectrometry Analysis ◽  
Structural Element ◽  
Spectrometry Analysis ◽  
Exchange Mass Spectrometry ◽  
Substrate Protein ◽  
Central Pore ◽  
The One

Hsp104 is a large AAA+ molecular machine that can rescue proteins trapped in amorphous aggregates and stable amyloids by drawing substrate protein into its central pore. Recent cryo-EM studies image Hsp104 at high resolution. We used hydrogen exchange mass spectrometry analysis (HX MS) to resolve and characterize all of the functionally active and inactive elements of Hsp104, many not accessible to cryo-EM. At a global level, HX MS confirms the one noncanonical interprotomer interface in the Hsp104 hexamer as a marker for the spiraled conformation revealed by cryo-EM and measures its fast conformational cycling under ATP hydrolysis. Other findings enable reinterpretation of the apparent variability of the regulatory middle domain. With respect to detailed mechanism, HX MS determines the response of each Hsp104 structural element to the different bound adenosine nucleotides (ADP, ATP, AMPPNP, and ATPγS). They are distinguished most sensitively by the two Walker A nucleotide-binding segments. Binding of the ATP analog, ATPγS, tightly restructures the Walker A segments and drives the global open-to-closed/extended transition. The global transition carries part of the ATP/ATPγS-binding energy to the somewhat distant central pore. The pore constricts and the tyrosine and other pore-related loops become more tightly structured, which seems to reflect the energy-requiring directional pull that translocates the substrate protein. ATP hydrolysis to ADP allows Hsp104 to relax back to its lowest energy open state ready to restart the cycle.

scholarly journals 5-Phenyl-10,15,20-Tris(4-sulfonatophenyl)porphyrin: Synthesis, Catalysis, and Structural Studies

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3363 ◽  
Author(s):  
Aitor Arlegui ◽  
Zoubir El-Hachemi ◽  
Joaquim Crusats ◽  
Albert Moyano
Keyword(s):  
Alder Reaction ◽  
Water Soluble ◽  
Experimental Conditions ◽  
One Pot ◽  
Force Microscopy ◽  
Diels Alder Reaction ◽  
Transmission Electron ◽  
Porphyrin Synthesis ◽  
The One ◽  
Water Soluble Porphyrin

A convenient protocol for the preparation of 5-phenyl-10,15,20-tris(4-sulfonatophenyl)porphyrin, a water-soluble porphyrin with unique aggregation properties, is described. The procedure relies on the one-pot reductive deamination of 5-(4-aminophenyl)-10,15,20-tris(4-sulfonatophenyl)porphyrin, that can be in turn easily obtained from 5,10,15,20-tetraphenylporphyrin by a known three-step sequence involving mononitration, nitro to amine reduction and sulfonation of the phenyl groups. This method provides the title porphyrin in gram scale, and compares very favorably with the up to now only described procedure based on the partial sulfonation of TPP, that involves a long and tedious chromatographic enrichment of the final compound. This has allowed us to study for the first time both the use of its zwitterionic aggregate as a supramolecular catalyst of the aqueous Diels–Alder reaction, and the morphology of the aggregates obtained under optimized experimental conditions by atomic force microscopy and also by transmission electron cryomicroscopy.

Sign in / Sign up

Export Citation Format

Share Document