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361.
362.
Anusiewicz I Jasionowski M Skurski P Simons J 《The journal of physical chemistry. A》2005,109(49):11332-11337
Ab-initio electronic structure methods are used to explore potential energy profiles pertinent to the fragmentations of gas-phase radicals thought to be formed in the new negative-ion mode EDD mass spectroscopic studies of peptides. Barriers to fragmentation as well as the associated overall energy differences are computed for the observed Calpha-C backbone bond cleavage as well as for side-chain loss for a variety of side chains (valine, arginine, glutamic acid, and tyrosine). It is found that Calpha-C bond cleavage is favored over side-chain loss, although loss of a tyrosine side chain may compete with Calpha-C cleavage because the tyrosine radical formed can delocalize its unpaired electron over its aromatic ring. In addition, it is found that fragmentation of the nitrogen-centered radicals formed in EDD results in cleavage to produce so-called a*/x fragments rather than a/x* fragments both because producing the former involves a significantly smaller barrier and is nearly thermoneutral, while cleavage to yield a/x* is significantly endothermic. 相似文献
363.
Imine‐Based Architectures at Surfaces and Interfaces: From Self‐Assembly to Dynamic Covalent Chemistry in 2D
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Iwona Janica Prof. Violetta Patroniak Prof. Paolo Samorì Dr. Artur Ciesielski 《化学:亚洲杂志》2018,13(5):465-481
Within the last two decades, dynamic covalent chemistry (DCC) has emerged as an efficient and versatile strategy for the design and synthesis of complex molecular systems in solution. While early examples of supramolecularly assisted covalent synthesis at surfaces relied strongly on kinetically controlled reactions for post‐assembly covalent modification, the DCC method takes advantage of the reversible nature of bond formation and allows the generation of the new covalently bonded structures under thermodynamic control. These structurally complex architectures obtained by means of DCC protocols offer a wealth of solutions and opportunities in the generation of new complex materials that possess sophisticated properties. In this focus review we examine the formation of covalently bonded imine‐based discrete nanostructures as well as one‐dimensional (1D) polymers and two‐dimensional (2D) covalent organic frameworks (COFs) physisorbed on solid substrates under various experimental conditions, for example, under ultra‐high vacuum (UHV) or at the solid–liquid interface. Scanning tunneling microscopy (STM) was used to gain insight, with a sub‐nanometer resolution, into the structure and properties of those complex nanopatterns. 相似文献
364.
Porwolik-Czomperlik I Brandt K Clayton TA Davies DB Eaton RJ Shaw RA 《Inorganic chemistry》2002,41(19):4944-4951
31P NMR spectroscopy and added chiral shift reagent (CSR) or chiral solvating agent (CSA) have been used to show that unsymmetrically substituted singly bridged macrocyclic phosphazene compounds exist as 1:1 diastereoisomers of two racemic mixtures, in contrast to previous work (ref 2) on symmetrically substituted diastereoisomeric analogues, which exist as meso and racemic forms. The cis-ansa cyclotriphosphazatriene-macrocycle, 1, is meso and monosubstitution of the >P(O-macrocycle)Cl group with 2-naphthol gives a racemic product (7), in which the macrocyclic ring exists in a trans-ansa configuration. Reaction of 7 with the di-secondary amine, piperazine, gives an unsymmetrically disubstituted racemic compound (8) having a cis-ansa configuration of the macrocyclic ring. Reaction of 8 with a further quantity of 1 forms a singly bridged derivative (9) with the macrocyclic rings in cis-trans configurations, and further reaction of 9 with pyrrolidine gives compound 10 with the macrocyclic rings in cis-cis configurations. Both 9 and 10 have four stereogenic centers giving rise to diastereoisomeric compounds existing as mixtures of two racemates. The results are consistent with inversion of configuration at phosphorus at each step of the reaction of >P(OR)Cl groups with nucleophile Z (i.e., Z = naphthoxy, piperazino, pyrrolidino) to form >P(OR)Z derivatives. 相似文献
365.
The results of kinetic and equilibrium experiments with the set of reaction of proton abstraction from 4-nitrophenyl[bis(ethylsulphonyl)]methane
in acetonitrile are reported. Two strong organic bases are used: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene
(MTBD).
The rates of proton transfer reaction have been measured by T-jump method in the presence of perchlorate of the appropriate
base as a common cation BH+ and supporting electrolyte-tetrabutylammonium perchlorate (TBAP) in the temperature range between 20–40°C are: k
H
=1.32×107−2.00×107 and 2.82×107−4.84×107 dm 3mol−1s−1 for MTBD and TBD respectively. The enthalpies of activation ΔH
MTBD
≠
=13.5 and ΔH
TBD
≠
=18.1 kJmol−1. The entropies of activation are negative: ΔS
MTBD
≠
=−62.3 and ΔS
TBD
≠
=−40.3 Jmol−1K−1.
The change of the absorbance of the anion of 4-nitrophenyl[bis9ethylsulphonyl)]methane at the temperature 25°C in the presence
of common cation BH+ gives the equilibrium constants K=705 and 906 M−1 for MTBD and TBD respectively.
Kinetic and equilibrium results are discussed. The possible mechanism of proton transfer reaction between 4-nitrophenyl[bis(ethylsulphonyl)]methane
and cyclic organic bases: MTBD and TBD in acetonitrile is proposed. 相似文献
366.
Zdzis?aw B?aszczak Iwona Iwaszkiewicz-Kostka Miros?aw Drozdowski 《Journal of Molecular Structure》2005,737(1):11-15
Selected dimethacrylates forming multifunctional monomers have been studied using Brillouin spectroscopy. The hypersound wave propagation velocity and adiabatic compressibility of the compounds studied have been determined. It has been revealed that these quantities depend on both temperature and the structure of the molecule chain of the monomer. Some characteristic features obtained from the Brillouin study have been discussed in terms of molecular interactions. 相似文献
367.
Jerzy Cieplik Janusz Pluta Tadeusz Lis Iwona Bryndal 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):o259-o261
Two polymorphic forms of the title compound, C24H20Cl2N4, were obtained and characterized using X‐ray crystal structure analysis. Colourless crystals of polymorph (Ia) were obtained from the oily mother residue. Recrystallization of polymorph (Ia) from an acetone–methanol mixture resulted in pale‐yellow crystals of polymorph (Ib). The major feature distinguishing the two polymorphic forms is their interaction modes, and hence their packing arrangements. In the crystal structure of polymorph (Ia), there are N—H⋯N hydrogen bonds and also aromatic π–π stacking interactions between molecules. The molecules of polymorph (Ib) are linked by N—H⋯Cl hydrogen bonds only. 相似文献
368.
The chiral oxazolidinone 1 (=[(3aS,6R,7aR)‐tetrahydro‐8,8‐dimethyl‐2‐oxo‐4H‐3a,6‐methano‐1,3‐benzoxazol‐3‐yl](oxo)acetaldehyde) was found to react stereoselectively with simple nitro compounds in the presence of Al2O3 or Bu4NF?3 H2O (TBAF) as catalysts, affording the diastereoisomeric nitro alcohols 3 – 6 with good asymmetric induction. When Al2O3 was used, the (S)‐configuration at the center bearing the OH group was generated, with the relative syn‐configuration for the major diastereoisomers. In the case of the nitro‐aldol reaction catalyzed by TBAF, an opposite asymmetric induction was found for two nitro compounds. In contrast to 1 , compound 12 (=((4R,5S)‐4‐methyl‐2‐oxo‐5‐phenyl‐1,3‐oxazolidin‐3‐yl)(oxo)acetaldehyde), a derivative of Evans auxiliary, gave rise to poor asymmetric induction in Henry reactions. 相似文献
369.
Iwona akomska Magdalena Barwioek Edward Szyk Boenna Golankiewicz 《Transition Metal Chemistry》2007,32(1):70-73
The preparation and spectroscopic study (1H, 13C, 15NNMR, 13CP MAS NMR, IR) of new PdII complexes with 6,8-dimethylimidazo[1,5-a]-1,3,5-triazin-4(3H)-one (6,8-DiMe-4-O-IMT) (1) and 6,8-dimethyl-2-thioxo-2,3-dihydroimidazo[1,5-a]-1,3,5-triazin-4(1H)-one (6,8-DiMe-4-O-2-S-IMT) (2) is reported. The spectroscopic data indicate a square planar geometry with two N(7) bonded heterocycles and two cis-chloride anions. The final product of the thermal decomposition of cis-PdCl2(6,8-DiMe-4-O-IMT)2
(3) is metallic Pd, whereas for cis-PdCl2(6,8-DiMe-4-O-2-S-IMT)2
(4) it is metallic Pd plus C. 相似文献
370.
Karolina Grabowska Dagmara Wróbel Paweł Żmudzki Irma Podolak 《Natural product research》2020,34(11):1581-1585
AbstractTwo triterpene saponins (IPS-1, IPS-2) for the first time were isolated from the roots of Impatiens parviflora DC. (Balsaminaceae). Their anti-inflammatory activity was evaluated by means of two in vitro models: anti-hyaluronidase and anti-denaturation assays. Both saponins were shown to be potent hyaluronidase inhibitors that affect the enzyme in a dose-dependent manner. The anti-hyaluronidase effect of IPS-2 (IC50?=?286.7?µg/mL) was higher than that of the reference drug: escin (IC50?=?303.93?µg/mL). Both saponins protected bovine serum albumin from heat-induced denaturation in a dose-dependent manner. IPS-1 demonstrated higher anti-denaturation effect (IC50?=?86.7?µg/ml) than IPS-2 (IC50?=?109.76?µg/mL) or the standard drug: acetylsalicylic acid (IC50?=?262.22?µg/mL). In conclusion, potent activity of IPS-1, IPS-2 in both in vitro assays shows that saponins from I. parviflora have anti-inflammatory activity. The obtained results allow to suggest that such compounds may be beneficial in inflammatory conditions, especially associated with excessive degradation of hyaluronic acid. 相似文献