Insight into the Structure of MOF-Containing Hybrid Polymeric Microspheres

Polymer science exploited metal organic frameworks (MOFs) for various purposes, which is due to the fact that these materials are ideal platforms for identifying design features for advanced functional materials. The mechanism of polymerization using MOFs, is still largely unexplored and the detailed characterization of both materials in essential to understand the important interactions between the components. In this work modern advanced research methods were used to investigate the properties of MOF-containing hybrid polymeric microspheres. Hydrothermal conversion of CFA-derived iron particles was used to obtain MOF nanostructures, which were then introduced to the structure of hybrid polymer microspheres based on ethylene glycol dimethylacrylate (EGDMA) and triethoxyvinylsilane (TEVS). Chemical structures were confirmed by ATR-FTIR method. To provide information about the elemental composition of the tested materials and for the determination of chemical bonds present in the tested samples XPS method was applied. Morphology was studied using SEM microscopy, whereas porosity was investigated using ASAP technique. Swellability coefficients were determined using typical organic solvents and distilled water. Moreover, the ecological aspect concerning the use of fly ashes deserves to be emphasized.     

Chromatographic Capillary Columns of Nonround Cross Sections

Two designs of gas-chromatographic capillary columns of nonround (rectangular) cross section with cross-sectional areas equal to that of a round capillary 0.16 mm in diameter were tested. It was found that capillary columns of nonround cross section with efficiencies of up to 500–600 theoretical plates per meter could easily be prepared.__________Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 7, 2005, pp. 729–733.Original Russian Text Copyright © 2005 by Rudenko, Zuev, Nikiforov, Naida, Shoromov.     

Mass Spectra and Ion Collision Cross Sections of Hemoglobin

Mass spectra of commercially obtained hemoglobin (Hb) show higher levels of monomer and dimer ions, heme-deficient dimer ions, and apo-monomer ions than hemoglobin freshly prepared from blood. This has previously been attributed to oxidation of commercial Hb. Further, it has been reported that that dimer ions from commercial bovine Hb have lower collision cross sections than low charge state monomer ions. To investigate these effects further, we have recorded mass spectra of fresh human Hb, commercial human and bovine Hb, fresh human Hb oxidized with H₂O₂, lyophilized fresh human Hb, fresh human Hb both lyophilized and chemically oxidized, and commercial human Hb oxidized with H₂O₂. Masses of α-monomer ions of all hemoglobins agree with the masses expected from the sequences within 3 Da or better. Mass spectra of the β chains of commercial Hb and oxidized fresh human Hb show a peak or shoulder on the high mass side, consistent with oxidation of the protein. Both commercial proteins and oxidized fresh human Hb produce heme-deficient dimers with masses 32 Da greater than expected and higher levels of monomer and dimer ions than fresh Hb. Lyophilization or oxidation of Hb both produce higher levels of monomer and dimer ions in mass spectra. Fresh human Hb, commercial human Hb, commercial bovine Hb, and oxidized commercial human Hb all give dimer ions with cross sections greater than monomer ions. Thus, neither oxidation of Hb or the difference in sequence between human and bovine Hb make substantial differences to cross sections of ions.     

A Database of Transition-Metal-Coordinated Peptide Cross-Sections: Selective Interaction with Specific Amino Acid Residues

Ion mobility mass spectrometry (IMS-MS) techniques were used to generate a database of 2288 collision cross sections of transition-metal-coordinated tryptic peptide ions. This database consists of cross sections for 1253 [Pep + X]²⁺ and 1035 [Pep + X + H]³⁺, where X²⁺ corresponds to Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. This number of measurements enables the extraction of structural trends for transition-metal-coordinated peptide ions. The range of structures and changes in collision cross sections for X²⁺-coordinated species (compared with protonated species of the same charge state) is similar to Mg²⁺-coordinated species. This suggests that the structures are largely determined by similarities in cation size with differences among the cross section distributions presumably caused by X²⁺ interactions with specific functional groups offered by the residue R-groups or the peptide backbone. Cross section contributions for individual residues upon X²⁺ solvation are assessed with the derivation of intrinsic size parameters (ISPs). The comparison of the [Pep + X]²⁺ ISPs with those previously reported for [Pep + Mg]²⁺ ions displays a lower contribution to the cross section for His, carboxyamidomethylated Cys, and Met, and is consistent with specific metal-residue interactions identified within protein X-ray crystallography databases.

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Chemical and Biological Aspects of Peptide Catecholamine Conjugates

Polymeric derivatives of D-isoproterenol have been prepared by diazotization to water-soluble, random copolypeptides of hydroxypropylglutamine and p-aminophenylalanine, molecular weight 1500, 3000, and 9600. The polymeric isoproterenol derivatives were purified by gel chromatography which reduced contamination by the parent catecholamine to undetectable levels (i. e., less than 0.01 wt %) and by 6-aminoisoproterenol (a possible decomposition product) to less than 0.4%. The derivatives were found to elicit positive chronotropic responses in isolated perfused guinea pig hearts, with mean effective doses (ED₅₀) which were between 1.3 and 2.0 orders of magnitude (for the 1500 and 9600 molecular weight derivatives, respectively) less than the ED50 for D-isoproterenol. Inotropic response decay times in isolated cat papillary muscles following washouts suggest that the polymer-bound drug does not diffuse into muscle tissues. In vivo biological studies (in conscious dogs) indicate that the polymeric drugs have significantly prolonged durations of action of between 5.5 ± 0.4 min for the derivative of highest (9600) molecular weight and 27.4 ± 4.9 min for the derivative of lowest (1500) molecular weight compared with 4.5 ± 0.14 min for a comparable dose of free isoproterenol. Possible explanations for the inverse relationship between the molecular weights of the derivatives and their in vivo durations of action are suggested. Our findings demonstrate that under controlled conditions isoproterenol can retain biological activity while covalently bound to a soluble polymeric support. The in vivo biological data suggest that the tethering of drugs to polymers may provide a means of maximizing the therapeutic utility of drugs with short half-lives.     

具有大的双光子吸收截面的A-A-A型双苯乙烯基苯类化合物的合成

合成了A-A-A型双苯乙烯基苯类化合物FR[2,5-二氰基-1,4-二(4'-氟苯乙烯基)苯],并采用核磁共振、红外光谱和元素分析等手段对其进行了表征.用飞秒脉冲诱导荧光光谱法分别研究了2个A-A-A型双苯乙烯基苯类化合物FR与CY[2,5-二氰基-1,4-二(4'-氰基苯乙烯基)苯]以及2个D-A-D型双苯乙烯基苯类化合物MO[2,5-二氰基-1,4-二(4'-甲氧基苯乙烯基)苯]和MA[2,5-二氰基-1,4-二(4'-二甲胺基苯乙烯基)苯]的单、双光子吸收与发射特性.实验结果表明,最大单光子吸收与发射波长随末端取代基供电子能力的增强而增大,末端强吸电子基化合物FR和CY具有相当高的荧光量子产率(分别为0.92与0.89)、较长的荧光寿命(分别为5.8与6.1 ns)及较大的双光子吸收系数(分别为19.1与20.5).末端带强吸电子基的化合物FR与CY的双光子吸收截面(δ,分别为6350 GM和6870 GM)比末端带供电子基的化合物MO和MA的δ(分别为270 GM与1790 GM)要大得多,表明A-A-A型双苯乙烯基苯类化合物具有异常大的δ.     

Measurement of Photoionization Cross Sections of the Excited States of Titanium

Resonance-enhanced multiphoton ionization of the titanium atoms has been investigated in the 293 321 nm wavelength. We couple a laser-ablated metal target into a molecular beam to produce free atoms. Ions produced from photoionization of the neutral atoms are monitored by a home-built time-of-flight mass spectrometer. Photoionization cross sections of the excited states of Ti I were deduced from the dependence of the ion signal intensity on the laser intensity for photon energies close to the ionization threshold. The values obtained range from 0.2 Mb to 6.0 Mb. No significant isotope-dependence was found from measurements of the photoionization cross sections of ^46Ti, ^47Ti, and ^48Ti.     

一种可用于评估肽质量指纹谱数据的方法——反转错位数据库

反转数据库常被用于估算大规模蛋白质组研究中串联质谱搜索数据库结果的可靠性。然而,对于经典的且现在依然在产出的肽质量指纹谱的数据,这种方法并不适用。为解决该问题,构建了另外一种随机数据库,称为反转错位数据库。这种数据库是在反转数据库的基础上,将序列中的K和R及其后的氨基酸交换位置(对于胰蛋白酶切割的结果)获得。这种处理避免了某些肽段因前后胰蛋白酶酶切位点氨基酸相同而在序列反转后质量依然不变,导致肽质量指纹谱法无法区分的问题。通过串联质谱和肽质量指纹谱测试数据的搜索结果,证明了这种方法同时适用于串联质谱和肽质量指纹谱的数据。这种方法扩大了经典反转数据库的适用范围,将对评估和整合串联质谱和肽质量指纹谱的数据具有重要意义。     

A General Synthetic Approach for Designing Epitope Targeted Macrocyclic Peptide Ligands

We describe a general synthetic strategy for developing high‐affinity peptide binders against specific epitopes of challenging protein biomarkers. The epitope of interest is synthesized as a polypeptide, with a detection biotin tag and a strategically placed azide (or alkyne) presenting amino acid. This synthetic epitope (SynEp) is incubated with a library of complementary alkyne or azide presenting peptides. Library elements that bind the SynEp in the correct orientation undergo the Huisgen cycloaddition, and are covalently linked to the SynEp. Hit peptides are tested against the full‐length protein to identify the best binder. We describe development of epitope‐targeted linear or macrocycle peptide ligands against 12 different diagnostic or therapeutic analytes. The general epitope targeting capability for these low molecular weight synthetic ligands enables a range of therapeutic and diagnostic applications, similar to those of monoclonal antibodies.     

Theoretical Aspects of Hydrolysis of Peptide Bonds by Zinc Metalloenzymes

Activation and reaction energies for four model systems capturing the essential physicochemical features of the hydrolysis of the peptide bond have been calculated at various level of theory, including the presumably accurate CCSD(T) calculations. The models studied covered a part of the spectrum encountered in biological systems: the hydrolysis in the absence of metal ions (represented by formamide and Ala–Ala) and the hydrolysis in the presence of one and two zinc(II) ions, mimicking the active sites of mono‐ and dizinc metallopeptidases, respectively (by using thermolysin and glutamate carboxypeptidase II as the model catalytic systems and formamide as the model substrate). The results obtained using CCSD(T)/def2‐TZVP and CCSD(T)/aug‐cc‐pVTZ calculations were used as the benchmark values to which the set of cheaper methods, such as (RI‐)DFT, (RI‐)MP2, and SCS‐MP2, were referenced. It was shown that deviations of 3–5 kcal mol^?1 (translating to 2–3 orders in reaction constants) with respect to the reference CCSD(T) barriers are frequently encountered for many correlated methods and most of studied DFT functionals. It has been concluded that from the set of wave‐function methods, both MP2 and SCS‐MP2 methods can be recommended for smaller models (measured by the mean absolute deviation of the activation barriers over the four systems studied), whereas among the popular DFT functionals, B3LYP and especially M06‐2X are likely to be reasonable choices for calculating the activation barriers of zinc metallopeptidases. Finally, with the model of glutamate carboxypeptidase II, issues related to the convergence of the calculated barriers with the size of the model system used as the representative of the enzyme active site were addressed. The intricacies related to system truncation are demonstrated, and suggest that the correlated wave‐function methods may suffer from problems, such as intramolecular BSSE, which make their usage for the larger system questionable. Altogether, the presented data should contribute to efforts to understand enzymatic catalysis more deeply and to gain control of the accuracy and deficiencies of the available theoretical methods and computational approaches.     

Insight into the Interaction Mechanism of HSA with Aztreonam: A Multispectroscopic and Computational Approach

Aztreonam is a Gram-negative bacteria-targeting synthetic monobactam antibiotic. Human serum albumin (HSA) plays an important role in the transference of pharmaceuticals, hormones, and fatty acids, along with other compounds, determining their biodistribution and physiological fate. Using several biophysical and in silico approaches, we studied the interaction of aztreonam with HSA under physiological environments in this study. Results confirm the formation of HSA-aztreonam complex where aztreonam showed moderate affinity towards HSA. A static mode of quenching was confirmed from the steady state fluorescence data. FRET findings also showed that there was a significant feasibility of energy transfer between HSA and aztreonam. Site marker displacement experimental conclusion suggested the binding site of aztreonam was the sub-domain IB of HSA. Circular dichroic spectroscopic analysis suggested that aztreonam interaction decreases the α-helical content of HSA. Changes in microenvironment were studied through synchronous fluorescence data. According to molecular docking results, the HSA-aztreonam complex is mostly maintained by non-covalent forces, with a binding energy of 7.7 kcal mol⁻¹. The presence of a hydrogen bond, van der Waal interaction, and pi-anion interaction in the binding process, as well as conformational changes in HSA after binding with aztreonam, are all confirmed by molecular dynamic simulation.     

Ruptenes: A Family of Terpene Analogs Give Insight into Cyclisation Mechanisms by Cascade Disruption

The terpenoid substrate analogs (7R)-6,7-dihydrogeranylgeranyl diphosphate (6,7-dihydro-GGPP) and (7R)-6,7-dihydrogeranylfarnesyl diphosphate (6,7-dihydro-GFPP) were synthesised from (S)-citronellol and enzymatically converted with nine diterpene and two sesterterpene synthases, respectively. In two cases the substrate analogs were converted into diterpenes in cyclisation reactions corresponding to those observed for the native substrate GGPP, while the cyclisation cascade was disrupted or redirected in the other nine cases, leading to products that were named ruptenes. Several of the isolated ruptenes represent deprotonation products of cationic intermediates that are analogs of the intermediates proposed along the cyclisation cascades for the native substrates GGPP or GFPP, thus giving insights into the complex reaction mechanisms of terpene synthase mediated biosynthesis.     

Combinatorial Methods and Informatics Provide Insight into Physical Properties and Structure Relationships during IPN Formation

Combinatorial methods and informatics are applied to the study of complex property‐structure‐processing relationships during interpenetrating polymer network formation in an epoxy/acrylate system. Principal component analysis of a dataset that covers different compositions and process sequences successfully identifies the most unique samples as well as relationships between material properties. The relationships between material properties can be exploited in future investigations by allowing high throughput screening and as a guide for engineering materials. The use of combinatorial methods, high throughput screening, and informatics will lead to accelerated material design.

     

Insight into the construction of open-framework aluminophosphates

Over the past twenty five years, a class of open-framework aluminophosphates, denoted AlPOs, has been prepared with neutral zeolitic frameworks and anionic frameworks showing wonderfully complex structural and compositional diversity. An insight into the construction of open-framework AlPOs revealing their general structural features and topological chemistry is provided in this tutorial review, and the role of templating and the designed construction and synthesis of AlPOs are discussed.