Bio-inspired synthesis of titania with polyamine induced morphology and phase transformation at room-temperature: Insight into the role of the protonated amino group

2013 ◽  
Vol 42 (34) ◽  
pp. 12179 ◽  
Author(s):  
Yong Yan ◽  
Bo Hao ◽  
Xiaobo Wang ◽  
Ge Chen
Author(s):  
Tatsuo Yajima ◽  
Makiko Kimura ◽  
Yoshihiro Hori ◽  
Tadashi Shiraiwa

The crystal structures ofN-acetyl-DL-isoleucine,N-acetyl-DL-alloisoleucine and their ammonium salts show that these four compounds exist as racemic compounds around room temperature. The two ammonium salts are arranged around a 21screw axis, forming a helical column which consists of ammonium ions and single enantiomeric anions similar to the crystals of the ammonium salts of optically activeN-acetyl-L-isoleucine andN-acetyl-D-alloisoleucine. The ammonium ion and the carboxylate ion in the helix are connected by three hydrogen bonds, the fourth hydrogen bond being formed between the ammonium ion and an external acetyl amino group of the neighboring helical column. The fourth hydrogen bond is formed between the ammonium ion and an external acetyl amino group of the neighboring 21column. AmmoniumN-acetyl-DL-alloisoleucinate was revealed to exist as an unstable racemic compound due to conformational similarity between the racemic and optically active compounds in the solid state and was optically resolved by fractional crystallization at 293 K.


2018 ◽  
Vol 74 (9) ◽  
pp. 1058-1067
Author(s):  
Xue-Jie Tan ◽  
Di Wang ◽  
Xu-Gang Lei ◽  
Jun-Peng Chen

A global glide disorder has been discovered during an X-ray investigation of the crystal structure of (Z)-2-[(E)-(4-methoxybenzylidene)hydrazinylidene]-1,2-diphenylethanone (MHDE, C22H18N2O2) at room temperature. In another crystal, however, such disorder disappears (still at room temperature). Even though the disorder may be partly due to the poor quality of the harvested crystal, the structure can shed light on the nature of disorder. With the help of quantum chemical calculations, it is found that the global disorder seems to be connected with the need for stabilization of the somewhat rigid but mobile and unstable molecular structure. The most relevant feature driving the packing of the disordered structure concerns the slight perturbations (such as glide) of two or more disorder components (fractional occupancies) distributed throughout the crystal.


2019 ◽  
Vol 167 (4) ◽  
pp. 357-364
Author(s):  
Yasuhiro Machida ◽  
Takeshi Murakawa ◽  
Akiko Sakai ◽  
Mitsuo Shoji ◽  
Yasuteru Shigeta ◽  
...  

Abstract Threonine synthase catalyses the conversion of O-phospho-l-homoserine and a water molecule to l-threonine and has the most complex catalytic mechanism among the pyridoxal 5′-phosphate-dependent enzymes. In order to study the less-characterized earlier stage of the catalytic reaction, we studied the reaction of threonine synthase with 2-amino-5-phosphonopentanoate, which stops the catalytic reaction at the enamine intermediate. The global kinetic analysis of the triphasic spectral changes showed that, in addition to the theoretically expected pathway, the carbanion is rapidly reprotonated at Cα to form an aldimine distinct from the external aldimine directly formed from the Michaelis complex. The Kd for the binding of inhibitor to the enzyme decreased with increasing pH, showing that the 2-amino-group-unprotonated form of the ligand binds to the enzyme. On the other hand, the rate constants for the proton migration steps within the active site are independent of the solvent pH, indicating that protons are shared by the active dissociative groups and are not exchanged with the solvent during the course of catalysis. This gives an insight into the role of the phosphate group of the substrate, which may increase the basicity of the ε-amino group of the catalytic lysine residue in the active site.


1992 ◽  
Vol 67 (01) ◽  
pp. 111-116 ◽  
Author(s):  
Marcel Levi ◽  
Jan Paul de Boer ◽  
Dorina Roem ◽  
Jan Wouter ten Cate ◽  
C Erik Hack

SummaryInfusion of desamino-d-arginine vasopressin (DDAVP) results in an increase in plasma plasminogen activator activity. Whether this increase results in the generation of plasmin in vivo has never been established.A novel sensitive radioimmunoassay (RIA) for the measurement of the complex between plasmin and its main inhibitor α2 antiplasmin (PAP complex) was developed using monoclonal antibodies preferentially reacting with complexed and inactivated α2-antiplasmin and monoclonal antibodies against plasmin. The assay was validated in healthy volunteers and in patients with an activated fibrinolytic system.Infusion of DDAVP in a randomized placebo controlled crossover study resulted in all volunteers in a 6.6-fold increase in PAP complex, which was maximal between 15 and 30 min after the start of the infusion. Hereafter, plasma levels of PAP complex decreased with an apparent half-life of disappearance of about 120 min. Infusion of DDAVP did not induce generation of thrombin, as measured by plasma levels of prothrombin fragment F1+2 and thrombin-antithrombin III (TAT) complex.We conclude that the increase in plasminogen activator activity upon the infusion of DDAVP results in the in vivo generation of plasmin, in the absence of coagulation activation. Studying the DDAVP induced increase in PAP complex of patients with thromboembolic disease and a defective plasminogen activator response upon DDAVP may provide more insight into the role of the fibrinolytic system in the pathogenesis of thrombosis.


2019 ◽  
Vol 58 (2) ◽  
pp. 249-259
Author(s):  
Joseph Acquisto

This essay examines a polemic between two Baudelaire critics of the 1930s, Jean Cassou and Benjamin Fondane, which centered on the relationship of poetry to progressive politics and metaphysics. I argue that a return to Baudelaire's poetry can yield insight into what seems like an impasse in Cassou and Fondane. Baudelaire provides the possibility of realigning metaphysics and politics so that poetry has the potential to become the space in which we can begin to think the two of them together, as opposed to seeing them in unresolvable tension. Or rather, the tension that Baudelaire animates between the two allows us a new way of thinking about the role of esthetics in moments of political crisis. We can in some ways see Baudelaire as responding, avant la lettre, to two of his early twentieth-century readers who correctly perceived his work as the space that breathes a new urgency into the questions of how modern poetry relates to the world from which it springs and in which it intervenes.


2019 ◽  
Author(s):  
Shuyuan Zheng ◽  
Taiping Hu ◽  
Xin Bin ◽  
Yunzhong Wang ◽  
Yuanping Yi ◽  
...  

Pure organic room temperature phosphorescence (RTP) and luminescence from nonconventional luminophores have gained increasing attention. However, it remains challenging to achieve efficient RTP from unorthodox luminophores, on account of the unsophisticated understanding of the emission mechanism. Here we propose a strategy to realize efficient RTP in nonconventional luminophores through incorporation of lone pairs together with clustering and effective electronic interactions. The former promotes spin-orbit coupling and boost the consequent intersystem crossing, whereas the latter narrows energy gaps and stabilizes the triplets, thus synergistically affording remarkable RTP. Experimental and theoretical results of urea and its derivatives verify the design rationale. Remarkably, RTP from thiourea solids with unprecedentedly high efficiency of up to 24.5% is obtained. Further control experiments testify the crucial role of through-space delocalization on the emission. These results would spur the future fabrication of nonconventional phosphors, and moreover should advance understanding of the underlying emission mechanism.<br>


Letonica ◽  
2020 ◽  
Author(s):  
Māra Grudule

The article gives insight into a specific component of the work of Baltic enlightener Gotthard Friedrich Stender (1714–1796) that has heretofore been almost unexplored — the transfer of German musical traditions to the Latvian cultural space. Even though there are no sources that claim that Stender was a composer himself, and none of his books contain musical notation, the texts that had been translated by Stender and published in the collections “Jaunas ziņģes” (New popular songs, 1774) and “Ziņģu lustes” (The Joy of singing, 1785, 1789) were meant for singing and, possibly, also for solo-singing with the accompaniment of some musical instrument. This is suggested, first, by how the form of the translation corresponds to the original’s form; second, by the directions, oftentimes attached to the text, that indicate the melody; and third, by the genres of the German originals cantata and song. Stender translated several compositions into Latvian including the text of the religious cantata “Der Tod Jesu” (The Death of Jesus, 1755) by composer Karl Heinrich Graun (1754–1759); songs by various composers that were widely known in German society; as well as a collection of songs by the composer Johann Gottlieb Naumann (1741–1801) that, in its original form, was published together with notation and was intended for solo-singing (female vocals) with the accompaniment of a piano. This article reveals the context of German musical life in the second half of the 18th century and explains the role of music as an instrument of education in Baltic-German and Latvian societies.


Author(s):  
James Marlatt

ABSTRACT Many people may not be aware of the extent of Kurt Kyser's collaboration with mineral exploration companies through applied research and the development of innovative exploration technologies, starting at the University of Saskatchewan and continuing through the Queen's Facility for Isotope Research. Applied collaborative, geoscientific, industry-academia research and development programs can yield technological innovations that can improve the mineral exploration discovery rates of economic mineral deposits. Alliances between exploration geoscientists and geoscientific researchers can benefit both parties, contributing to the pure and applied geoscientific knowledge base and the development of innovations in mineral exploration technology. Through a collaboration that spanned over three decades, we gained insight into the potential for economic uranium deposits around the world in Canada, Australia, USA, Finland, Russia, Gabon, Namibia, Botswana, South Africa, and Guyana. Kurt, his research team, postdoctoral fellows, and students developed technological innovations related to holistic basin analysis for economic mineral potential, isotopes in mineral exploration, and biogeochemical exploration, among others. In this paper, the business of mineral exploration is briefly described, and some examples of industry-academic collaboration innovations brought forward through Kurt's research are identified. Kurt was a masterful and capable knowledge broker, which is a key criterion for bringing new technologies to application—a grand, curious, credible, patient, and attentive communicator—whether talking about science, business, or life and with first ministers, senior technocrats, peers, board members, first nation peoples, exploration geologists, investors, students, citizens, or friends.


2007 ◽  
Vol 2 (1) ◽  
Author(s):  
A. Ros ◽  
C. Canals-Batlle ◽  
M.A. Lillo-Ródenas ◽  
E. Fuente ◽  
M. A. Montes-Morán ◽  
...  

This paper focuses on the valorisation of solid residues obtained from the thermal treatment of sewage sludge. In particular, sewage sludge samples were collected from two waste water treatment plants (WWTPs) with different sludge line basic operations. After drying, sludges were heated up to 700 °C in appropriate ovens under diluted air (gasification) and inert (pyrolysis) atmospheres. The solids obtained, as well as the dried (raw) sludges, were characterised to determine their textural properties and chemical composition, including the speciation of their inorganic fraction. All the materials under study were employed as adsorbents/catalysts in H2S removal experiments at room temperature. It was found that, depending on the particular sludge characteristics, outstanding results can be achieved both in terms of retention capacities and selectivity. Some of the solids outperform commercially available sorbents specially designed for gaseous emissions control. In these adsorbents/catalysts, H2S is selectively oxidised to elemental sulphur most likely due to the presence of inorganic, catalytically active species. The role of the carbon-enriched part on these solids is also remarked.


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