Preferred conformers of proteinogenic glutamic acid

The molecular shape of proteinogenic glutamic acid has been determined for the first time. Vaporization of the solid amino acid by laser ablation in combination with Fourier transform microwave spectroscopy made possible the detection of five different structures in a supersonic jet. These structures have been identified through their rotational and (14)N quadrupole coupling constants. All conformers show hydrogen bonds linking the amino and alpha carboxylic group through N-H···O═C (type I) or N···H-O (type II) interactions. In three of them there are additional hydrogen bonds established between the amino group and the carboxylic group in the gamma position. Entropic effects related to the side chain have been found to be significant in determining the most populated conformations.     

AFM-based force-clamp monitors lipid bilayer failure kinetics

The lipid bilayer rupture phenomenon is here explored by means of atomic force microscopy (AFM)-based force clamp, for the first time to our knowledge, to evaluate how lipid membranes respond when compressed under an external constant force, in the range of nanonewtons. Using this method, we were able to directly quantify the kinetics of the membrane rupture event and the associated energy barriers, for both single supported bilayers and multibilayers, in contradistinction to the classic studies performed at constant velocity. Moreover, the affected area of the membrane during the rupture process was calculated using an elastic deformation model. The elucidated information not only contributes to a better understanding of such relevant process, but also proves the suitability of AFM-based force clamp to study model structures as lipid bilayers. These findings on the kinetics of lipid bilayers rupture could be extended and applied to the study of other molecular thin films. Furthermore, systems of higher complexity such as models mimicking cell membranes could be studied by means of AFM-based force-clamp technique.     

Different rotamer states of cytosine nucleobases in heteronuclear PtPd-, PtPd2, and Pt2Pd2Ag complexes derived from [Pt(2,2'-bpy)(1-MeC-N3)2]2+ (1-MeC = 1-methylcytosine): first examples of species with head-head oriented 1-MeC(-) ligands

[Pt(2,2'-bpy)(1-MeC-N3)(2)](NO(3))(2) (1) (2,2'-bpy = 2,2'-bipyridine; 1-MeC = 1-methylcytosine) exists in water in an equilibrium of head-tail and head-head rotamers, with the former exceeding the latter by a factor of ca. 20 at room temperature. Nevertheless, 1 reacts with (en)Pd(II) (en = ethylenediamine) to give preferentially the dinuclear complex [Pt(2,2'-bpy)(1-MeC(-)-N3,N4)(2)Pd(en)](NO(3))(2)·5H(2)O (2) with head-head arranged 1-methylctosinato (1-MeC(-)) ligands and Pd being coordinated to two exocyclic N4H(-) positions. Addition of AgNO(3) to a solution of 2 leads to formation of a pentanuclear chain compound [{Pt(2,2'-bpy)(1-MeC(-))(2)Pd(en)}(2)Ag](NO(3))(5)·14H(2)O (5) in which Ag(+) cross-links two cations of 2 via the four available O2 sites of the 1-MeC(-) ligands. 2 and 5 appear to be the first X-ray structurally characterized examples of di- and multinuclear complexes derived from a Pt(II) species with two cis-positioned cytosinato ligands adopting a head-head arrangement. (tmeda)Pd(II) (tmeda = N,N,N',N'-tetramethylethylenediamine) and (2,2'-bpy)Pd(II) behave differently toward 1 in that in their derivatives the head-tail orientation of the 1-MeC(-) nucleobases is retained. In [Pt(2,2'-bpy)(1-MeC(-))(2){Pd(2,2'-bpy)}(2)](NO(3))(4)·10H(2)O (4), both (2,2'-bpy)Pd(II) entities are pairwise bonded to N4H(-) and O2 sites of the two 1-MeC(-) rings, whereas in [Pt(2,2'-bpy)(1-MeC(-))(2){Pd(tmeda)}(2)(NO(3))](NO(3))(3)·5H(2)O (3) only one of the two (tmeda)Pd(II) units is chelated to N4H(-) and O2. The second (tmeda)Pd(II) is monofunctionally attached to a single N4H(-) site. On the basis of these established binding patterns, ways to the formation of mixed Pt/Pd complexes and possible intermediates are proposed. The methylene protons of the en ligand in 2 are special in that they display two multiplets separated by 0.64 ppm in the (1)H NMR spectrum.     

Electric field induced electron transfer at the adsorbate-surface interface. Effect of the type of metal surface

The ab initio two-state model for electron transfer induced by an external electric field has been applied to the chloride oxidation on Cu, Rh, Pd, Ag, Pt and Au (001) surface models. The two electronic states involved in the model represent physical situations where the electron transferred from the chloride anion to the metal surface lies either on the halide or on the metal substrate. The model assumes that electron transfer takes place when these two states become degenerate and this is achieved by applying an external electric field. Two different situations representing either ultrahigh vacuum or electrochemical conditions have been considered. For the former the present study shows that electric field necessary to achieve degeneracy of the two electronic states is directly related to the metal surface work function whereas for the latter, it is found to be rather insensitive to the metal surface.     

Flow-injection spectrofluorimetric determination of ethylenethiourea

A flow-injection configuration is proposed for the fluorimetric determination of ethylenethiourea. The procedure is based on the inhibitory effect of ethylenethiourea on the oxidation of thiamine to thiochrome by mercury(II). A linear calibration graph was obtained between 0.1 and 2.0 μg mL^–1, with a sampling rate of 40 samples per hour and a relative standard deviation of about 1.11%. The usefulness of the method was tested for the determination of ethylenethiourea residues in water, milk, potatoes, pear, grape and apple. Received: 26 January 1998 / Revised: 6 April 1998 / Accepted: 9 April 1998     

手性Schiff Base-Ti(OR)4配合物催化醛的不对称硅腈化反应

设计合成了新型手性Salen-Ti(OR)₄配合物催化剂,用其催化一系列醛的不对称硅腈化反应,得到了e.e.值为22.4%～87.1%的氰醇.催化剂中抗衡离子的Lewis碱强烈地影响催化活性,但对反应的对映选择性影响很小,并探讨了其不对称催化反应机理.     

Intermolecular spin–spin coupling constants between P atoms

This paper reports the study by NMR spectroscopy and ab initio methods of the structure of 3,4-dimethyl-1-cyanophosphole and its dimer. The dimer presents a P···P interaction of the pnictogen type due to the presence of σ-holes. NMR of the monomer was recorded in CDCl₃ solution while NMR of the dimer corresponds to the solid state (CPMAS) experiments. The ^2pJ_PP spin–spin coupling constant has not been measured, but calculated at the B3LYP level. AIM, NBO and ELF methodologies have been used to describe the electronic structure of the dimer.     

Disk-shaped Symmetric Hexa-substituted Triphenylene Derivatives: Synthesis,Physical Properties and Self-assembly

A series of triphenylene derivatives with six symmetric substituents was synthesized from hexabromotriphenylene. The synthesis was conducted by six-fold palladium-catalyzed Hagihara-Sonogashira cross- coupling reactions to yield the hexa-alkynyl substituted triphenylene derivatives of HTP1, HTP2, HTP3 and HTP4. The six symmetric substituents can not only endow the triphenylene the longer π-conjugated range, but also increase the solubility of the compounds. Their photophysical, electrochemical, thermal properties were investigated respectively. With the comparison of their properties, the structure-property relationships were established which demonstrated the influences of different substituents on the electronic nature and the mesomorphic phase of these disk-shaped molecules. In addition, with the scanning electron microscopy(SEM) and polarized optical microscopy(POM) characterization, the self-assembly behaviors of the compounds were also investigated.     

An [FeIII34] Molecular Metal Oxide

The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe₃₄] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral Fe^III ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe?O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe₃₄], bulk iron oxides, previous Fe^III–oxo cages, and polyoxometalates (POMs), hints that much larger molecular Fe^III oxides can be made.     

Identification of bioactive peptides in hypoallergenic infant milk formulas by CE‐TOF‐MS assisted by semiempirical model of electromigration behavior

Biologically active peptides derived from complex bovine milk protein hydrolysates are of particular interest in food science and nutrition because they have been shown to play different physiological roles, providing benefits in human health. In this study, we used CE‐TOF‐MS for separation and identification of bioactive peptides in three hypoallergenic infant milk formulas. An appropriate sample cleanup using a citrate buffer with DTT and urea followed by SPE with Sep‐Pack® C18 and StrataX^TM cartridges allowed the detection of a large number of low molecular mass bioactive peptides. This preliminary identification was solely based on the measured experimental monoisotopic molecular mass values (M_exp). Later, we evaluated the classical semiempirical relationships between electrophoretic mobility and charge‐to‐mass ratio (m_e vs. q/M^α, α = 1/2 for the classical polymer model) to describe their migration behavior. The assistance of migration prediction proved to be useful to improve reliability of the identification, avoiding misinterpretations and solving some identity conflicts. After revision, the identity of 24, 30, and 38 bioactive peptides was confirmed in each of the three infant milk formulas. A significant number of these peptides were reported as inhibitors of angiotensin‐converting enzyme, however, the presence of sequences with other biological activities such as antihypertensive, antithrombotic, hypocholesterolemic, immunomodulation, cytotoxicity, antioxidant, antimicrobial, antigenic, or opioid was also confirmed.