Desorption of Ammonia Adsorbed on Prussian Blue Analogs by Washing with Saturated Ammonium Hydrogen Carbonate Solution

Prussian blue analogs (PBAs) have been reported as promising ammonia (NH₃) adsorbents with a high capacity compared to activated carbon, zeolite, and ion exchange resins. The adsorbed NH₃ was desorbed by heating and washing with water or acid. Recently, we demonstrated that desorption was also possible by washing with a saturated ammonium hydrogen carbonate solution (sat. NH₄HCO₃ aq) and recovered NH₃ as an NH₄HCO₃ solid by introducing CO₂ into the washing liquid after desorption. However, this has only been proven for copper ferrocyanide and the relationship between the adsorption/desorption behavior and metal ions in PBAs has not been identified. In this study, we investigated the adsorption/desorption behavior of PBAs that are complexes of first row transition metals with hexacyanometalate anions. Six types of PBAs were tested in this study and copper ferricyanide exhibited the highest desorption/adsorption ratio. X-ray diffraction results revealed high structural stability for cobalt hexacyanocobaltate (CoHCC) and nickel ferricyanide (NiHCF). The Fourier transform infrared spectroscopy results showed that the NH₃ adsorbed on the vacancy sites tended to desorb compared to the NH₃ adsorbed on the interstitial sites as ammonium ions. Interestingly, the desorption/adsorption ratio exhibited the Irving-Williams order.     

Preliminary Assessment of the Anti-inflammatory Activity of New Structural Honokiol Analogs with a 4′-O-(2-Fluoroethyl) Moiety and the Potential of Their 18F-Labeled Derivatives for Neuroinflammation Imaging

Neolignans honokiol and 4′-O-methylhonokiol (MH) and their derivatives have pronounced anti-inflammatory activity, as evidenced by numerous pharmacological studies. Literature data suggested that cyclooxygenase type 2 (COX-2) may be a target for these compounds in vitro and in vivo. Recent studies of [¹¹C]MPbP (4′-[¹¹C]methoxy-5-propyl-1,1′-biphenyl-2-ol) biodistribution in LPS (lipopolysaccharide)-treated rats have confirmed the high potential of MH derivatives for imaging neuroinflammation. Here, we report the synthesis of four structural analogs of honokiol, of which 4′-(2-fluoroethoxy)-2-hydroxy-5-propyl-1, 1′-biphenyl (F-IV) was selected for labeling with fluorine-18 (T_1/2 = 109.8 min) due to its high anti-inflammatory activity confirmed by enzyme immunoassays (EIA) and neuromorphological studies. The high inhibitory potency of F-IV to COX-2 and its moderate lipophilicity and chemical stability are favorable factors for the preliminary evaluation of the radioligand [¹⁸F]F-IV in a rodent model of neuroinflammation. [¹⁸F]F-IV was prepared with good radiochemical yield and high molar activity and radiochemical purity by ¹⁸F-fluoroethylation of the precursor with Boc-protecting group (15) with [¹⁸F]2-fluoro-1-bromoethane ([¹⁸F]FEB). Ex vivo biodistribution studies revealed a small to moderate increase in radioligand uptake in the brain and peripheral organs of LPS-induced rats compared to control animals. Pretreatment with celecoxib resulted in significant blocking of radioactivity uptake in the brain (pons and medulla), heart, lungs, and kidneys, indicating that [¹⁸F]F-IV is likely to specifically bind to COX-2 in a rat model of neuroinflammation. However, in comparison with [¹¹C]MPbP, the new radioligand showed decreased brain uptake in LPS rats and high retention in the blood pool, which apparently could be explained by its high plasma protein binding. We believe that the structure of [¹⁸F]F-IV can be optimized by replacing the substituents in the biphenyl core to eliminate these disadvantages and develop new radioligands for imaging activated microglia.     

Synthesis of phosphinic and phosphonic analogs of aromatic amino acids

The reaction of aryl and aralkyl aldoximes with hypophosphorous acid resulted in aminophosphinic acids, which were oxidized into the corresponding aminophosphonic acids. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 137–140, January, 1997.     

Structure-Activity Relationship of Steroidal Insecticides. VIII. Cholestane and Stigmastane Ecdysteroids and Their Structural Analogs

Structural analogs of ecdysteroids were screened for insecticidal activity for larvae of the Colorado beetle Leptinotarsa decemlineata using a contact-feed method. High activity was found for compounds 3, 6b, 7a, and 9a.     

Features of the Reaction of Heterocyclic Analogs of 2'-Alkoxychalcones with Lanthanide Shift Reagents

The reaction of lanthanide shift reagents with the heterocyclic analogs of substituted 2'-alkoxychalcones was studied. It was shown that the coordination of Eu(fod)³ and Yb(fod)³ with them takes place in different ways. The former forms mainly adducts of the chelate type with participation of the oxygen atoms of the carbonyl and alkoxyl groups in coordination, while from the latter only the adduct at the carbonyl group is obtained. For this reason it was concluded that there are some limitations to the use of the reagents for conformational analysis of organic compounds. It was shown that they can only be used to study the conformational movements of the molecules not affecting the complexation process.     

Synthesis and fungicidal activity study of novel daphneolone analogs with 2,6-dimethylmorpholine

A series of novel daphneolone analogs was designed and synthesized on the basis of natural product 1,5-diphenyl-2-penten-1-one(I) from Stellera chamaejasme L. as lead compound, whereby 2,6-dimethylmorpholine moiety was introduced to replace 1-phenyl group. Their structures were confirmed by IR,1H NMR, and HRMS(ESI) or elemental analysis,13 C NMR for some representative compounds. The two isomers of target compounds were separated and identified by NOESY technique and chemical method.All of the synthesized compounds have been evaluated for anti-plant pathogenic fungi activities. The results showed that some compounds exhibited moderate to good antifungal activities against tested fungi at the concentration of 50 mg/L. Among them, compound 7d, with a 4-bromine-substituted phenyl group and cis-2,6-dimethylmorpholine moiety, displayed best activity with an EC50 of 23.87 mmol/L against Valsa mali, superior to lead compound I. In addition, preliminary structure–activity relationship analysis indicated that, between two isomers of target compounds, the antifungal activities of the isomer with cis-2,6-dimethylmorpholine were better than the trans-isomer.     

Human Y-chromosome haplotyping by allele-specific polymerase chain reaction

We describe the application of allele-specific PCR (AS-PCR) for screening biallelic markers, including SNPs, within the nonrecombining region of the human Y-chromosome (NRY). The AS-PCR method is based on the concept that the perfectly annealed primer-template complex is more stable, and therefore, more efficiently amplified under the appropriate annealing temperature than the complex with a mismatched 3'-residue. Furthermore, a mismatched nucleotide at the primer's 3'-OH end provides for a poor extension substrate for Taq DNA polymerase, allowing for discrimination between the two alleles. This method has the dual advantage of amplification and detection of alleles in a single expeditious and inexpensive procedure. The amplification conditions of over 50 binary markers, mostly SNPs, that define the major Y-haplogroups as well as their derived lineages were optimized and are provided for the first time. In addition, artificial restriction sites were designed for those markers that are not selectively amplified by AS-PCR. Our results are consistent with allele designations derived from other techniques such as RFLP and direct sequencing of PCR products.     

Synthesis and evaluation of the bioactivity of simplified analogs of the seco-pseudopterosins; progress toward determining a pharmacophore

The pseudopterosins are marine natural products that display significant anti-inflammatory and wound healing properties. We describe the synthesis of six structural analogs of the seco-pseudopterosin-like core that are devoid of all but one of the stereocenters found in the carbocyclic core of the natural products. Our targets were selected in an attempt to identify the minimal pharmacophore for the pseudopterosins and their seco analogs. A deliberate effort was made to utilize a conservative synthetic approach based upon the use of well-established reactions, which enabled us to develop routes that proved to be efficient, practical, and easy to implement. The results of several bioassays, including an assessment of the ability to inhibit phagocytosis and to competitively bind to the adenosine receptor A_2A, demonstrate that greatly simplified structural analogs of the pseudopterosins and their seco forms are capable of maintaining several of the important bioactivities that characterize the natural products, and do so with comparable efficacy. Those systems bearing two rather than one oxygen atom appended directly to the aromatic ring are the more effective binding agents. This observation may provide a significant clue regarding the key structural features of the minimal pharmacophore.     

New conversion of Friendlander reaction of 3-amino-1H-benzo[f]chromene-2-carbonitriles with cyclohexanone

Two different skeletons of heterocyclic compounds, quinoline and quinazolinone analogs could be obtained by a novel one-pot synthesis from substituted 3-amino- 1H-benzo[f]chromene-2-carbonitrile derivatives and cyclohexanone in DMF in the catalyst of anhydrous Zinc chloride under reflux. A plausible mechanism was proposed. 2007 Jia Rong Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Unusual supramolecular donor—acceptor complexes of bis(crown)stilbenes and bis(crown)azobenzene with viologen analogs

The results of the comprehensive study of novel supramolecular donor-acceptor complexes of bis(crown)stilbenes and bis(crown)azobenzene with viologen analogs are generalized. The original methodology for self-assembling of the organic donor-acceptor complexes possessing a very high thermodynamic stability is described. The hydrogen bonds between the peripheral fragments of the donor and acceptor play the key role in the self-assembling. The influence of different structural factors on the thermodynamic stability of the supramolecular donor-acceptor complexes and the efficiency of charge-transfer interactions between the donor and acceptor are discussed. The driving forces of the reaction leading to exotic trimolecular charge-transfer complexes are considered. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 779–787, April, 2008.