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401.
The regioselective reaction of 2,2′-dihydroxybiphenyl with terminal alkynes was found to be rapidly catalyzed by InCl3 and ZrCl4. The chemoselectivity of catalysts and alkynes for biphenol over water, together with the reaction mechanism are discussed in details. 相似文献
402.
Giacomo Proietti Michela Burico Claudio Marzio Quintiero Emiliano Giovagnoni Valentino Mercati Mattia Gianni Luisa Mattoli 《Journal of mass spectrometry : JMS》2023,58(10):e4924
Drugs are indispensable products with incontrovertible benefits to human health and lifestyle. However, due to their overuse and improper disposal, unwanted residues of active pharmaceutical ingredients (APIs) have been found in different compartments of the environment and now are considered as contaminants of emerging concern (CECs). Therefore, they are very likely to have a boomerang effect on human health, because they can enter into the food cycle. In the current legislation framework, one of the tests first used to evaluate biodegradation of APIs as well as chemical compounds is the ready biodegradability test (RBT). This test can be performed according to a series of protocols prepared by Organization for Economic Co-operation and Development (OECD) and usually is carried out on pure compounds. RBTs, largely used due to their relatively low cost, perceived standardization, and straightforward implementation and interpretation, are known to have a number of well-documented limitations. In this work, following a recently reported approach, we propose to improve the evaluation of the RBT results applying advanced analytical techniques based on mass spectrometry, not only to the APIs but also to complex formulated products, as the biodegradability can potentially be affected by the formulation. We evaluated the ready biodegradability of two therapeutic products, Product A —a drug based on Metformin—and Product B —Metarecod a natural substance-based medical device—through the acquisition of the fingerprint by ultra-high-performance chromatograph coupled to a quadrupole time of flight (UHPLC-qToF) of samples coming from the RBT OECD 301F. Untargeted and targeted evaluation confirmed the different behavior of the two products during the respirometry-manometric test, which showed a difficulty of the Metformin-based drug to come back in the life cycle, whereas Metarecod resulted ready biodegradable. The positive results of this research will hopefully be useful in the future for a better evaluation of the risk/benefit ratio of APIs extended to the environment. 相似文献
403.
404.
A persistent paramagnetic [1]rotaxane based on beta-cyclodextrin showing an increased persistency under reductive conditions has been prepared and characterized for the first time. 相似文献
405.
In this paper we study K3 surfaces with a non-symplectic automorphism of order 3. In particular, we classify the topological
structure of the fixed locus of such automorphisms and we show that it determines the action on cohomology. This allows us
to describe the structure of the moduli space and to show that it has three irreducible components. 相似文献
406.
Airborne particulate matter (PM) represents one of the most important sources of urban pollution due to its physical and chemical
properties. There is a great concern for PM dangerous effects on human health because particles can deeply penetrate into
the respiratory system, carrying the contaminants adsorbed onto their surface. Polycyclic aromatic hydrocarbons (PAHs) are
a class of organic contaminants that can be adsorbed onto PM and can have harmful effects on health, due to their particular
chemical structure. The International Agency for Research on Cancer (IARC) classified PAHs as potential carcinogenic agents
and benzo[a]pyrene (BaP) as carcinogenic to humans. In this paper, the development of a metrologically traceable procedure for the quantification
of BaP in airborne PM, performed at the Italian National Institute of Metrological Research (Istituto Nazionale di Ricerca
Metrologica—I.N.Ri.M.), is presented. The identification and quantification of BaP in PM samples were carried out by gas chromatography
coupled with mass spectrometry (GC–MS). Metrological traceability was established in all the procedure steps, after performing
the method validation. Suitable certified reference materials (CRMs) were used both to validate the analytical method and
to calibrate the GC–MS. The measurement uncertainty was evaluated by identifying and taking into account all the relevant
sources deriving from the whole procedure steps. 相似文献
407.
Zhou W Capello M Fredolini C Racanicchi L Piemonti L Liotta LA Novelli F Petricoin EF 《Electrophoresis》2012,33(12):1850-1854
L-lactate dehydrogenase (LDH) converts pyruvate to lactate when oxygen is absent or in short supply, and the enzyme plays a crucial role in cancer metabolism. The functions of many mammalian proteins are modulated by posttranslational modifications (PTMs), and it has been reported that LDH was subjected to several PTMs, including phosphorylation, acetylation, and methylation. In this present work, we characterized the PTMs of LDH from pancreatic ductal adenocarcinoma (PDAC) cells by electrophoresis and mass spectrometry, and identified 13 O-methylated residues from the enzyme. In addition, our qualitative analysis revealed differential methylation of LDH from normal duct cells. The preliminary findings from this study provide important biochemical information toward further understanding of the LDH modifications and their functional significance in pathophysiological processes of pancreatic cancer. 相似文献
408.
Pisani M Bruni P Caracciolo G Caminiti R Francescangeli O 《The journal of physical chemistry. B》2006,110(26):13203-13211
Multilamellar liposomes of dipalmitoylphosphatidylcholine (DPPC) in solution with DNA and bivalent metal cations (Ca2+, Mn2+, Mg2+) self-assemble into a ternary DPPC-DNA-Me2+ complex. The supramolecular structure of the complex consists of an ordered multilamellar assembly where hydrated DNA helices are sandwiched between the lipid bilayers and the metal cations bind the phosphate groups of DNA to the lipid polar heads. In the range of explored incubation times, the complex coexists with the uncomplexed DPPC over the whole temperature range investigated (20-55 degrees C). Accordingly, two distinct coexisting lamellar phases are observed, one corresponding to the ternary complex and the other to the uncomplexed lipid. The structure and thermotropic phase behavior of both of these have been investigated by means of synchrotron X-ray diffraction, and the relevant structural data are deduced from experimental electron density profiles. While the uncomplexed lipid exhibits the same phase behavior as pure DPPC, that is, L beta'-P beta'-L alpha, the thermotropic behavior of the bound lipid in the complex is partially altered. This is manifested as an increase in the main transition temperature and the disappearance of the ripple phase leading to the single -phase transition. The role of the different metal cations in promoting and stabilizing the DNA condensation into the ternary complex is also discussed. 相似文献
409.
Galarneau A Cangiotti M di Renzo F Sartori F Ottaviani MF 《The journal of physical chemistry. B》2006,110(41):20202-20210
The EPR spectra of radical surfactant probes embedded in cetyltrimethylammonium bromide (CTAB) and trimethylbenzene (TMB) stable water emulsions (TMB/CTAB = 13) were analyzed to provide information on the kinetics of formation of micelle-templated silicoaluminas (MTSA) at 343 K, obtained by means of silica and alumina, solved in alkaline solutions, at different Si/Al ratios. Textural (surface area, pore volume, pore size, surfactant content) and structural characterization of both as-synthesized and calcined MTSA were performed by means of nitrogen sorption isotherms, TEM, and chemical analysis. This analysis showed that TMB worked as a swelling agent of the CTAB micelles, providing large-pore homogeneous and stable MTSA at TMB/CTAB = 13 for Si/Al from infinity to 10. A demixing of the emulsion occurs at Si/Al < 10: at Si/Al = 7, a double wide-and-narrow pore structure was formed; then, at Si/Al = 5, an amorphous material was obtained. At Si/Al > or = 10, the computer-aided analysis of the EPR spectra as a function of the synthesis time indicated the distribution of the probes in two different environments: "micellar" probes inserted in the surfactant aggregates, whose mobility decreases over the synthesis time, thus reporting on the progressive modification of the surfactant aggregates structure and the solid condensation, and "interacting" probes due to probe-surfactant heads electrostatically interacting with the charged surface sites induced by alumina incorporation in the silica network. This last fraction increases its relative amount over the synthesis time, informing about the condensation and structuration of the MTSA. Without alumina, the "interacting" component is absent in the EPR spectra because TMB preferentially interacts with the surfactant headgroups by cation-pi interactions, thus preventing the interactions of these headgroups with silanols. When alumina is added, the negatively charged silicoaluminate at the surface promotes the interaction of the ammonium headgroups with the surface, and some Na+ cations also interact with TMB by cation-pi interaction and contribute to decreasing the interaction of the headgroups with TMB. Therefore, increasing alumina contents promote electrostatic interactions between the positively charged surfactant heads and the negatively charged silicoaluminate groups. The strong interaction of the surfactants with the silicoaluminate surface allows the formation of a monolayerlike structure of surfactant, which is not observed in the absence of alumina. The synthesis is slowed by increasing alumina contents due to a destructuration effect of alumina in the MTSA formation. 相似文献
410.
Begala M Tocco G Delogu G Meli G Picciau C Podda G 《Journal of mass spectrometry : JMS》2006,41(5):577-585
The mass spectrometric behaviour of a series of 6,6-disubstituted dibenzo(d,f)(1,3)dioxepine derivatives have been studied. The fragmentation patterns were described and discussed in detail with the aid of labelled compounds, accurate mass measurements and collisionally induced dissociation experiments performed using an ion trap. 相似文献