用动力学方法研究8,9-苯并-2-亚甲基-1,4,6-三氧螺[4,4]壬烷的聚合反应机理

根据在自由基引发剂存在下,8,9-苯并-2-亚甲基-1,4,6-三氧螺(4,4)壬烷(Ⅰ)可能存在的竞争反应,推导了动力学方程式。用红外光谱法测定了单体的消失速率和苯酞的生成速率。实验结果与推导动力学方程式相符。进一步证明了单体(Ⅰ)的增长反应由加成聚合和开环—异构化—加成这两个反应组成。这两个反应对总速率的相对贡献与单体浓度有关。得到了共聚物的结构。     

Trends in the CNDO/2 molecular orbital study of electronic structure in some neurotransmitter drugs

An investigation of electronic structure in some neurotransmitter drugs has been made using the CNDO/2 semi-empirical molecular orbital method.The electronic structure has been conveniently characterized by the electronic parameters nett atomic population (NAP) and bond index (BI). A variation of these electronic parameters with respect to conformation has been studied and has been found unlikely to exceed 0.1 e in most. cases. Further, the useful extent to which the electronic parameters of some commonly occurring functional groups may be regarded as conformationally invariant has been demonstrated. Also presented are (i) a discussion on the intramolecular close-approach of functional groups — the interaction between terminal —COO^? and ?NH₃⁺ groups of α-ω anaino acids is explicitly considered; (ii) an enquiry into the extension of ‘standard’ (idealized) geometry models in the elucidation of electronic structure.The implication of the results and observations presented here are briefly discussed with reference to classical and quantum structure-activity studies of drug molecules.     

Transformed steroids

A preparative method for 9a-hydroxylation of ⁵-3-hydroxysteroids using the fungi ofCircinella sp. 10Kh-1220 not capable of modifying theA ring has been developed. It is established that the yields of the main and the side products greatly depend on the transformation conditions, mycelium age, and the structure of the steroid substrate. Under the optimal transformation conditions novel 9-hydroxysubstituted derivatives of androstenolone, pregnenolone, 16-dehydro-16,17-epoxy-, and-16-methoxypregnenolone have been obtained in 36–80 % yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 737–743, April, 1994.     

Structure and magnetic properties of Ca14MnP11

The compound Ca₁₄MnP₁₁ crystallizes in the Ca₁₄AlSb₁₁ structure type with the tetragonal space group I4₁/acd (Z=8) and lattice parameters of , c=20.7565(9) at 90 K. The structure consists of MnP₄⁹⁻ tetrahedron, P₃⁷⁻ trimer, 4 P³⁻ isolated anions and 14 Ca²⁺ cations. Similar to other compounds of this structure type containing phosphorous, the P₃⁷⁻ trimer has a central P atom that is best modeled in the structure as being equally split between two sites. In addition, there is no additional distortion of the manganese-containing tetrahedron compared with the main group analog, Ca₁₄GaP₁₁, suggesting that the Mn oxidation state is Mn²⁺. Temperature-dependent magnetic susceptibility shows that the compound is paramagnetic over the entire temperature range measured (2-300 K). The data can be fit with a modified Curie-Weiss law and provide an effective magnetic moment of 5.80 (2) B.M. with a Weiss constant of −2.13(2) K and . This moment is significantly higher than those measured for any of the Mn-containing analogs and is consistent with Mn²⁺. This result will be discussed in light of the electron counting scheme for Mn compounds of the Ca₁₄AlSb₁₁ structure-type.     

Conditional solubility versus pO2− of cerium(III) oxide in molten equimolar NaCl+KCl at 727°C

Reactions between cerium trichloride and oxide ions were studied in NaCl+KCl (1/1) at 1000°K, by potentiometry with a calcia-stabilized zirconia membrane electrode. Titration curves clearly demonstrated the existence of soluble cerium oxychloride (CeO⁺) and precipitated cerium oxide (Ce₂O₃), with respective dissociation constants 10^?11 and 10^?30 (molality scale). The corresponding conditional solubility diagram {log S (Ce^III)=f(pO^2?)} is presented and discussed.     

Foaming and Structural Studies on the Acidic Subunit of Amaranth 11S Globulin Modified with Antihypertensive Peptides as a Function of pH and Ionic Strength

Some studies aimed at revealing the relationship between protein structure and their functional properties. However, the majority of these reports have been carried out using protein isolates. There are limited reports on the possible relationship between the functional properties and the structure of a purified protein. In this work the amaranth 11S globulin acidic subunit (AAC) and five mutations of the same protein that were modified in their variable regions with antihypertensive peptides (VYVYVYVY and RIPP), were analyzed at two ionic strength (2.9 and 17.6 g/L NaCl) and pH (3.0–7.0). Results revealed better solubility for the proteins mutated at the terminal ends (AACM.1 and AACM.4) and lower solubility for the protein inserted with RIPP peptide. Spectroscopy studies revealed an increase of β-sheet structure at high salt concentration for all proteins. It was also observed that salt concentration acted as a modulator, which allowed a better foam features for all modified proteins limiting movement of side chains and reducing red-shifted displacement of λmax. All proteins showed foam capacity ranging from 76 to 93% although foam stability was twofold better for modified proteins than for AAC at high salt concentration. This study allowed better understanding about the structural changes that influence the foaming properties of engineered proteins.     

Electrochemical Immunoassay for Tumor Marker CA19-9 Detection Based on Self-Assembled Monolayer

A CA19-9 electrochemical immunosensor was constructed using a hybrid self-assembled membrane modified with a gold electrode and applied to detect real samples. Hybrid self-assembled membranes were selected for electrode modification and used to detect antigens. First, the pretreated working electrodes were placed in a 3-mercaptopropionic acid (MPA)/β-mercaptoethanol (ME) mixture for 24 h for self-assembly. The electrodes were then placed in an EDC/NHS mixture for 1 h. Layer modification was performed by stepwise dropwise addition of CA19-9 antibody, BSA, and antigen. Differential pulse voltammetry was used to characterize this immunosensor preparation process. The assembled electrochemical immunosensor enables linear detection in the concentration range of 0.05–500 U/mL of CA19-9, and the detection limit was calculated as 0.01 U/mL. The results of the specificity measurement test showed that the signal change of the interfering substance was much lower than the response value of the detected antigen, indicating that the sensor has good specificity and strong anti-interference ability. The repeatability test results showed that the relative standard deviations were less than 5%, showing good accuracy and precision. The CA19-9 electrochemical immunosensor was used for the actual sample detection, and the experimental results of the standard serum addition method showed that the RSD values of the test concentrations were all less than 10%. The recoveries were 102.4–115.0%, indicating that the assay has high precision, good accuracy, and high potential application value.     

In Silico Drug Repurposing of FDA-Approved Drugs Highlighting Promacta as a Potential Inhibitor of H7N9 Influenza Virus

Influenza virus infections continue to be a significant and recurrent public health problem. Although vaccine efficacy varies, regular immunisation is the most effective method for suppressing the influenza virus. Antiviral drugs are available for influenza, although two of the four FDA-approved antiviral treatments have resulted in significant drug resistance. Therefore, new treatments are being sought to reduce the burden of flu-related illness. The time-consuming development of treatments for new and re-emerging diseases such as influenza and the high failure rate are increasing concerns. In this context, we used an in silico-based drug repurposing method to repurpose FDA-approved drugs as potential therapies against the H7N9 virus. To find potential inhibitors, a total of 2568 drugs were screened. Promacta, tucatinib, and lurasidone were identified as promising hits in the DrugBank database. According to the calculations of MM-GBSA, tucatinib (−54.11 kcal/mol) and Promacta (−56.20 kcal/mol) occupied the active site of neuraminidase with a higher binding affinity than the standard drug peramivir (−49.09 kcal/mol). Molecular dynamics (MD) simulation studies showed that the C-α atom backbones of the complexes of tucatinib and Promacta neuraminidase were stable throughout the simulation period. According to ADME analysis, the hit compounds have a high gastrointestinal absorption (GI) and do not exhibit properties that allow them to cross the blood–brain barrier (BBB). According to the in silico toxicity prediction, Promacta is not cardiotoxic, while lurasidone and tucatinib show only weak inhibition. Therefore, we propose to test these compounds experimentally against the influenza H7N9 virus. The investigation and validation of these potential H7N9 inhibitors would be beneficial in order to bring these compounds into clinical settings.     

9-Bromomethylacridine a Novel Fluorescent Labeling Reagent of Carboxylic Group for HPLC

Abstract

9-Bromomethylacridine (9-Br · Ma) gave blue fluorescent 9-acridinylmethyl (9-AM) esters by the reaction with carboxylic acids. The reactions were performed simply by mixing the 9-Br · Ma, tetraethylammonium carbonate (TEA C) and carboxylic acids in N,N-dimethylformamide at room temperature. The 9-AM derivatives of fifteen kinds of fatty acids were separated and detected with high performance liquid chromatography. By this method, fatty acids could be determined at levels down to either pmol order by fluorometry or 10 pmol order by UV method. After saponification, those in triacylglycerols were also determined. When four kinds of fatty acids were added to a butter, their recoveries were 92–101%. The coefficient of variation of myristate as a representative was 2.5% (42.8 pmol, n=6).