Competition between tetrel bond and pnicogen bond in complexes of TX3-ZX2 and NH3

Journal of Molecular Modeling - The discovery or development of thermoalkalophilic lipases that show high levels of catalytic activity in organic solvents would have important industrial...     

Modulating the strength of tetrel bonding through beryllium bonding

Quantum chemical calculations were performed to investigate the stability of the ternary complexes BeH₂···XMH₃···NH₃ (X?=?F, Cl, and Br; M?=?C, Si, and Ge) and the corresponding binary complexes at the atomic level. Our results reveal that the stability of the XMH₃···BeH₂ complexes is mainly due to both a strong beryllium bond and a weak tetrel–hydride interaction, while the XMH₃···NH₃ complexes are stabilized by a tetrel bond. The beryllium bond with a halogen atom as the electron donor has many features in common with a beryllium bond with an O or N atom as the electron donor, although they do exhibit some different characteristics. The stability of the XMH₃···NH₃ complex is dominated by the electrostatic interaction, while the orbital interaction also makes an important contribution. Interestingly, as the identities of the X and M atoms are varied, the strength of the tetrel bond fluctuates in an irregular manner, which can explained by changes in electrostatic potentials and orbital interactions. In the ternary systems, both the beryllium bond and the tetrel bond are enhanced, which is mainly ascribed to increased electrostatic potentials on the corresponding atoms and charge transfer. In particular, when compared to the strengths of the tetrel and beryllium bonds in the binary systems, in the ternary systems the tetrel bond is enhanced to a greater degree than the beryllium bond.

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Graphical Abstract A tetrel bond can be strengthened greatly by a beryllium bond

     

Carbamodithioate‐based fluorescent chemosensor for Hg(II): a staged response approach and investigation into the sensing mechanism

Carbamodithioate‐based compound C1 was designed and synthesized as a new fluorescent probe for Hg²⁺ ions. Upon the addition of Hg²⁺ ions, it displayed a rare staged response: the emission spectra of C1 first showed an apparent red‐shift, followed by a dramatic decrease. To investigate the sensing mechanism, control compounds C2 with the same phenanthroimidazole unit and C3 with the same carbamodithioate functionality were synthesized. On comparison, the first step sensing process was ascribed to decreasing photoinduced electron transfer on the coordination of Hg²⁺ with the lone pair electrons of the nitrogen atom on the phenanthroimidazole ring. The affinity of Hg²⁺ and the carbamodithioate unit with four sulfur atoms then induced changes in intramolecular charge transfer efficiency and the second step fluorescent response.     

基于不同方法的毛茛族(毛茛科)导管穿孔板比较研究

导管分子的演化与植物的进化相关联.毛茛科是联系基部被子植物和核心真双子叶植物的关键类群,对其导管穿孔板的研究具有重要的系统学意义.为研究毛茛科毛茛族不同属植物导管穿孔板类型及其与环境的相关性,该文利用新的扫描电子显微镜和半薄切片技术,对该族7属8种植物次生木质部导管状分子进行了比较观察.结果表明:木质部管状分子以单穿孔...     

An AB initio investigation of molecules with a disulfide bond: (HS)2, (CH3S)2 and cystine

ab initio Calculations at the Gaussian-70 STO-3G and 4-31G basis levels have been carried out for (HS)2 and (CH3S)2. Cystine was investigated at the STO-3G level. The STO-3G energy minimized geometry agrees well with experiments for (HS)2 and (CH3S)2. The barriers to internal rotation are predicted to be (at the 4.31G level): (HS)2, cis 8.5 kcal, trans 3.03 kcal; (CH3S)2, cis 18.47 kcal, trans 6.04 kcal.     

利用叶绿体DNA trnL-F序列初步探讨菊科风毛菊属的系统发育

风毛菊属Saussurea DC.是菊科物种分化十分剧烈和分类处理十分困难的一个属。该属的单系起源性质、属下分类系统以及一些独特形态物种的系统位置尚不清楚,有待进一步验证。本文测定了代表该属5个亚属37种植物43个样品和川木香属Dolomiaea DC.的１种样品的叶绿体DNA trnL-F序列,并调取菜蓟族Cardueae Cass.与风毛菊属具有一定亲缘关系的13属的该序列,一起进行了分支分析,重点验证该属的属下形态分类系统以及形态特殊、青藏高原地区特有的雪兔子亚属subgen. Eriocoryne     

A preliminary investigation on the phylogeny of Saussurea (Asteraceae: Cardueae) based on chloroplast DNA trnL-F sequences

Saussurea DC., a highly diversified genus with about 400 species in the Asteraceae, has been an extremely difficult group in both taxonomical and phylogenetic studies. The monophyletic origin, infrageneric classification and systematic positions of some s     

Proteomic approach for investigation of cytoplasmic male sterility (CMS) in Brassica

The alloplasmic ‘Tournefortii’ CMS system fromB. napus was chosen for a comprehensive investigation of the protein content of the mitochondrial compartment in male sterile and fertile near isogenic lines. As proteins involved in the male sterile phenotype may be expressed in a tissue-specific manner, mitochondrial preparations were made from different tissues and checked for the purity of the organelles with a new and highly sensitive method (BN-PAGE). InBrassica, only mitochondrial preparations from 4-5-day-old seedlings and from flower buds were found to be sufficiently pure. High resolution, two-dimensional gel electrophoresis of total protein from anthers and from mitochondrial protein of male sterile and fertile seedlings of near isogenic lines revealed distinct differences in the protein patterns. Several explanations for the occurrence of these differences, which may be the starting point for a detailed molecular analysis and a better understanding of the CMS syndrome, are discussed.     

Quantum-mechanical study of model molecules in relation to collagen structure. II. (Gly-Phe-Pro) and (Gly-Pro-Phe) repeating units

A conformational quantum-mechanical study of (Gly-Phe-Pro) and (Gly-Pro-Phe) repeating tripeptide sequences has been carried out with the PCILO method. Using appropriate molecules as a model, we investigated the conformational possibilities of each in situ residue. Computations have been done taking into account the two typical pyrrolidine ring puckering and the most favorable orientations of the phenylalanyl side chain. Major conclusions drawn from this study are that the phenylalanyl can be accommodated at both second and third positions in the sequence without preventing the formation of triple-helix conformation. However, the analogy observed between the rotational possibilities around the second residue of Gly-Pro-Pro and Gly-Phe-Pro indicates that phenylalanyl in the second position favors the triple-helix formation.     

An investigation of the growth characteristics of oil-palm (Elaeis guineensis) suspension cultures using31P NMR

High-resolution³¹P nuclear-magnetic-resonance (NMR) spectra are reported for oil-palm (Elaeis guineensis) cells in suspension culture. The spectra are a signicant improvement on the results that have appeared for other cultures and they are comparable with the spectra of the meristematic tissue in seedling roots. The NMR technique was used in parallel with other analytical methods to investigate the growth characteristics of the suspension culture, indluding the effect of 2,4-dichlorophenoxyacetic acid.     

The disulfide bond formation (Dsb) system

In oxidative folding of proteins in the bacterial periplasmic space, disulfide bonds are introduced by the oxidation system and isomerized by the reduction system. These systems utilize the oxidizing and the reducing equivalents of quinone and NADPH, respectively, that are transmitted across the cytoplasmic membrane through integral membrane components DsbB and DsbD. In both pathways, alternating interactions between a Cys-XX-Cys-containing thioredoxin domain and other regulatory domain lead to the maintenance of oxidized and reduced states of the specific terminal enzymes, DsbA that oxidizes target cysteines and DsbC that reduces an incorrect disulfide to allow its isomerization into the physiological one. Molecular details of these remarkable biochemical cascades are being rapidly unraveled by genetic, biochemical, and structural analyses in recent years.     

Using palynomorphological characteristics for the identification of species of Alsinoideae (Caryophyllaceae): a systematic approach

Palynological characters of 18 species belonging to seven genera of the traditional subfamily Alsinoideae including Arenaria, Cerastium, Eremogone, Lepyrodiclis, Minuartia, Sabulina and Stellaria were studied in detail using light and scanning electron microscopy. Pollen grains of subfamily Alsinoideae are subspheroidal or prolate, pantoporate and 20.04 to 51.4 µm in size, prominent and sunken apertures uniformly distributed on the pollen surface. Two types of pollen grain ornamentation were observed, i.e. microechinate-punctate or microechinate-perforate. Echini are present on the surface of the pollen of all investigated species with medium, dense, or sparse echinodensity. These species exhibit variation in polar view, equatorial diameter, number of apertures, exine thickness, diameter of pore, appendages per pore, pore ornamentation, echini arrangement, echinidensity and shape of pollen. Based on qualitative characters, a dichotomous key has been developed for quick and easy identification. The present investigation contributes to the systematic approach using palynological characteristics and correct identification of species for members of subfamily Alsinoideae (Caryophyllaceae).     

A new approach for fluorescence correlation spectroscopy (FCS) based immunoassays

Fluorescence correlation spectroscopy (FCS) is a powerful technique for measuring physicochemical properties, such as concentration and diffusion constant, of bio-molecules in complex mixtures. Although, as such, FCS is well suited for development of homogeneous immunoassays, a major obstacle lies in the relatively high molecular weight of antibodies. This is because in FCS discrimination between unbound fluorescently-labelled antibodies and the same antibodies bound to immune complexes is based on the difference of their respective diffusion coefficients. To overcome this limitation we here propose to use a fluorescently-labelled tag which has two crucial properties: (a) its molecular weight is significantly lower than that of an antibody and (b) it is capable to discriminate between free antibodies and immune complexes. We have evaluated the feasibility of this approach in a model system consisting of mouse monoclonal IgG directed against the Lewis X antigen, and Protein A as a low molecular weight tag.     

An analysis of the viability of clonal plants based on a morphometric approach (exemplified by Calamagrostis langsdorffii)

Clonal plants viability has been studied on the basis of morphostructure variability of clone modules. The research has been carried out on the Calamagrostis langsdorffii (Poaceae) in the flood-lands of the Amur River Basin (Khabarovsk Territory). Plants vitality has been evaluated by 26 morphometric parameters, characterizing their growth, productivity and reproduction. Clone ramets differed from each other by considerable variability and plasticity. Significant changes of all morphometric parameters according to humidity and alluvion gradients were very specific. Reproductive parameters were the most stable ones. Parameters of growth and dimension were characterised by increased variability. Wide reaction of morphometric parameters of C. langsdorffii to the changes in ecological conditions can be considered as an adaptation to the existence in dynamical environment of the flood-land.     

Ionic strength and pH effect on the Fe(III)-imidazolate bond in the heme pocket of horseradish peroxidase: an EPR and UV-visible combined approach

The effects of chloride, dihydrogenphosphate and ionic strength on the spectroscopic properties of horseradish peroxidase in aqueous solution at pH=3.0 were investigated. A red-shift (lambda=408 nm) of the Soret band was observed in the presence of 40 mM chloride; 500 mM dihydrogenphosphate or chloride brought about a blue shift of the same band (lambda=370 nm). The EPR spectrum of the native enzyme at pH 3.0 was characterized by the presence of two additional absorption bands in the region around g=6, with respect to pH 6.5. Chloride addition resulted in the loss of these features and in a lower rhombicity of the signal. A unique EPR band at g=6.0 was obtained as a result of the interaction between HRP and dihydrogenphosphate, both in the absence and presence of 40 mM Cl-. We suggest that a synergistic effect of low pH, Cl- and ionic strength is responsible for dramatic modifications of the enzyme conformation consistent with the Fe(II)-His170 bond cleavage. Dihydrogenphosphate as well as high chloride concentrations are shown to display an unspecific effect, related to ionic strength. A mechanistic explanation for the acid transition of HRP, previously observed by Smulevich et al. [Biochemistry 36 (1997) 640] and interpreted as a pure pH effect, is proposed.     

Cost of flight in the zebra finch ( Taenopygia guttata): a novel approach based on elimination of (13)C labelled bicarbonate

On three separate occasions, five zebra finches ( Taenopygia guttata) were injected intraperitoneally with 0.2 ml 0.29 M NaH(13)CO(3)solution and placed immediately into respirometry chambers to explore the link between (13)C elimination and both O(2) consumption (VO(2)) and CO(2) production (VCO(2)). Isotope elimination was best modelled by a mono-exponential decay. The elimination rate (k(c)) of the (13)C isotope in breath was compared to VO(2) (ml O(2)/min) and VCO(2) (ml CO(2)/min) over sequential 5-min time intervals following administration of the isotope. Elimination rates measured 15-20 min after injection gave the closest relationships to VO(2) ( r(2) =0.82) and VCO(2) ( r(2)=0.63). Adding the bicarbonate pool size (N(c)) into the prediction did not improve the fit. A second group of birds ( n=11) were flown for 2 min (three times in ten birds and twice in one) between 15 min and 20 min following an injection of 0.2 ml of the same NaH(13)CO(3) solution. Breath samples, collected before and after flight, were used to calculate k(c) over the flight period, which was converted to VO(2) and VCO(2) using the equation generated in the validation experiment for the corresponding time period. The energy expenditure (watts) during flight was calculated from these values using the average RQ measured during flight of 0.79. The average flight cost measured using the bicarbonate technique was 2.24+/-0.11 W (mean+/-SE). This average flight cost did not differ significantly from predictions generated by an allometric equation formulated by Masman and Klaassen (1987 Auk 104:603-616). It was however substantially higher than the predictions based on the aerodynamic model of Pennycuick (1989 Oxford University Press), which assumes an efficiency of 0.23 for flight. The flight efficiency in these birds was 0.11 using this model. Flight cost was not related to within-individual variation [general linear model (GLM) F(1,31)=1.16, P=0.29] or across-individual variations in body mass (GLM F(1,31)=0.26, P=0.61), wingspan (regression F(1,10)=0.01, P=0.94) or wing loading (regression F(1, 31)=0.001, P=0.99) in this sample of birds.