An NMR study of the conformational mobility of steroid estrogen 7α-methyl-8α analogues

All the signals in the ¹H and ¹³C NMR spectra of some analogues of 7α-methyl-8α-and 6-oxa-8α-steroid estrogens were completely assigned. Considering the values of nuclear Overhauser effect and vicinal coupling constants, these steroids were shown to exhibit a fast, on the NMR time scale, conformational equilibrium arising due to the inversion of ring B. The conformer populations were obtained from a comparison of the experimental and theoretical values of the dihedral angles and the interproton distances. This conformational equilibrium was shown to depend on the nature of atom in position 6: for the 7α-methyl-6-oxa-8α analogues of the steroid estrogens, the population of the conformer with the pseudoaxial orientation of the 7α-methyl group was observed to be decreased compared with the 7α-methyl-8α analogue.     

人工扩繁管氏肿腿蜂的蜂种复壮研究

利用中间寄主黄粉甲Tenebrio molitor L.蛹大量扩繁管氏肿腿蜂Scleroderma guani Xiao et Wu经多代后寄生效果下降,系由蜂种退化所致:利用一种中间寄主导致蜂种的营养来源单一;采用同一种群的蜂及较低的蜂虫比造成近亲繁殖。据此设计复壮措施:利用自然寄主回接、杂交和控制交尾方式。结果表明:(1)回接1代,其子代蜂种的寄生率和寄生成功率分别提高26%和28%~33%。(2)用外缘蜂种与本群蜂种杂交,其子代蜂的发育历期比对照少4d,寄生率和寄生成功率分别提高22%和17%。(3)控制交尾方式促进蜂种复壮。     

SIMPLE estimate of the free energy change due to aliphatic mutations: superior predictions based on first principles

The bioinformatics revolution of the last decade has been instrumental in the development of empirical potentials to quantitatively estimate protein interactions for modeling and design. Although computationally efficient, these potentials hide most of the relevant thermodynamics in 5-to-40 parameters that are fitted against a large experimental database. Here, we revisit this longstanding problem and show that a careful consideration of the change in hydrophobicity, electrostatics, and configurational entropy between the folded and unfolded state of aliphatic point mutations predicts 20-30% less false positives and yields more accurate predictions than any published empirical energy function. This significant improvement is achieved with essentially no free parameters, validating past theoretical and experimental efforts to understand the thermodynamics of protein folding. Our first principle analysis strongly suggests that both the solute-solute van der Waals interactions in the folded state and the electrostatics free energy change of exposed aliphatic mutations are almost completely compensated by similar interactions operating in the unfolded ensemble. Not surprisingly, the problem of properly accounting for the solvent contribution to the free energy of polar and charged group mutations, as well as of mutations that disrupt the protein backbone remains open.     

Cinnamaldehyde—A potential antidiabetic agent

Cinnamonum zeylanicum (cinnamon) is widely used in traditional system of medicine to treat diabetes in India. The present study was carried out to isolate and identify the putative antidiabetic compounds based on bioassay-guided fractionation; the compound identified decreased the plasma glucose levels. The active compound was purified by repeat column and structure of cinnamaldehyde was determined on the basis of chemical and physiochemical evidence. The LD(50) value of cinnamaldehyde was determined as 1850+/-37 mg/kg bw. Cinnamaldehyde was administered at different doses (5, 10 and 20 mg/kg bw) for 45 days to streptozotocin (STZ) (60 mg/kg bw)-induced male diabetic wistar rats. It was found that plasma glucose concentration was significantly (p<0.05) decreased in a dose-dependent manner (63.29%) compared to the control. In addition, oral administration of cinnamaldehyde (20 mg/kg bw) significantly decreased glycosylated hemoglobin (HbA(1C)), serum total cholesterol, triglyceride levels and at the same time markedly increased plasma insulin, hepatic glycogen and high-density lipoprotein-cholesterol levels. Also cinnamaldehyde restored the altered plasma enzyme (aspartate aminotransferase, alanine aminotransferase, lactate dehydrogenase, alkaline phosphatase and acid phosphatase) levels to near normal. Administration of glibenclamide, a reference drug (0.6 mg/kg bw) also produced a significant (p<0.05) reduction in blood glucose concentration in STZ-induced diabetic rats. The results of this experimental study indicate that cinnamaldehyde possesses hypoglycemic and hypolipidemic effects in STZ-induced diabetic rats.     

Density functional theory studies of model complexes for molybdenum-dependent nitrate reductase active sites

Molybdenum and tungsten complexes as models for the active sites of assimilatory or dissimilatory nitrate reductases (NR) were computed at the CPCM-B98/SDDp//B3LYP/Lanl2DZp* plus zero point energy level of density functional theory. The ligands were chosen on the basis of available experimental protein or small chemical model structures. A water molecule is found to bind to assimilatory NR models [(Me₂C₂S₂)MO(YMe)]⁻ (−11.5 kcal mol⁻¹ for M is Mo, Y is S) and may be replaced by nitrate (−4.5 kcal mol⁻¹) (but a hydroxy group may not). Nature’s choice of M is Mo and Y is S for NR has the largest activation energy for protein-free models (13.3 kcal mol⁻¹) and the least exothermic reaction energy for the nitrate reduction (−14.9 kcal mol⁻¹) compared with M is W and Y is O or Se alternatives. Water binding to dissimilatory NR model complexes [(Me₂C₂S₂)₂M(YR)]⁻ is considerably endothermic (10.3 kcal mol⁻¹); nitrate binding is only slightly so (1.5 kcal mol⁻¹ for RY⁻ is MeS⁻). The exchange of an oxo ligand (assimilatory NR) for a dithiolato ligand (dissimilatory NR model) reduces the exothermicity (−8.6 kcal mol⁻¹ relative to the fivefold-coordinate reduced complex) and raises the barrier for oxygen atom transfer (OAT) in the nitrate complex (19.2 kcal mol⁻¹). Not for the mono but only for the bisdithiolato complexes hydrogen bonding involving the coordinated substrate may significantly lower the OAT barrier as shown by explicitly adding water molecules. Substitution of tungsten for molybdenum generally lowers OAT activation energies and makes nitrate reduction reaction energies more negative. Bidentate carboxylato binding identified in Escherichia coli NarGHI is the preferred binding mode also for an acetato model. However, one dithiolato ligand folds when the Mo^VI center is bare of a good π-donor ligand, e.g., an oxo group. Computations on [(mnt)₂Mo^IV(YR)(PPh₃)]⁻ [mnt is (CN)₂C₂S₂ ²⁻] gave a smaller nitrate reduction activation energy for RY⁻ is Cl⁻, compared with RY⁻ is PhS⁻, although experimentally only the phenyl thiolato complex and not the chloro complex was found to be a functional NR model. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Interactions between soil and tree roots accelerate long-term soil carbon decomposition

Decomposition of soil organic carbon (SOC) is the main process governing the release of CO₂ into the atmosphere from terrestrial systems. Although the importance of soil–root interactions for SOC decomposition has increasingly been recognized, their long-term effect on SOC decomposition remains poorly understood. Here we provide experimental evidence for a rhizosphere priming effect, in which interactions between soil and tree roots substantially accelerate SOC decomposition. In a 395-day greenhouse study with Ponderosa pine and Fremont cottonwood trees grown in three different soils, SOC decomposition in the planted treatments was significantly greater (up to 225%) than in soil incubations alone. This rhizosphere priming effect persisted throughout the experiment, until well after initial soil disturbance, and increased with a greater amount of root-derived SOC formed during the experiment. Loss of old SOC was greater than the formation of new C, suggesting that increased C inputs from roots could result in net soil C loss.     

Impact of ploughing on soil seed bank dynamics in temporary pools

We examined the impact of ploughing on soil seed banks of plant communities living in temporary marshes located in agricultural fields. The quantity, quality and vertical distribution of seeds were quantified under ploughed or unploughed treatment at community level. We also focussed on a typical semi-aquatic species, Damasonium alisma, to investigate the impact of ploughing at population level. We used two complementary techniques to study seed banks: hand sorting and seedling emergence. We found that species richness of seeds, seed abundance and germination ability were strongly affected by ploughing at community level. Concerning D. alisma, most of the seeds (56%) were stored in the two deepest soil layers among the four considered in ploughed pools. Moreover, the germination rate was higher for buried seeds (84%) than for seeds collected at the surface (33.6%). These patterns were almost inverted in unploughed pools. Our results agree with the temporal storage effect generally suggested to describe the seed bank property of plant communities. But in addition, we showed that ploughing induces a spatial storage effect in accumulating species and individuals in the seed banks that favourably influence community dynamics. We conclude that, in contrast to what is usually thought, ploughing disturbance can be of benefit for such ephemeral wetland vegetation.     

Facilitation and interference underlying the association between the woody invaders Pyracantha angustifolia and Ligustrum lucidum

Questions: 1. Is there any post‐dispersal positive effect of the exotic shrub Pyracantha angustifolia on the success of Ligustrum lucidum seedlings, as compared to the effect of the native Condalia montana or the open herbaceous patches between shrubs? 2. Is the possible facilitation by Pyracantha and/or Condalia related to differential emergence, growth, or survival of Ligustrum seedlings under their canopies? Location: Córdoba, central Argentina. Methods: We designed three treatments, in which ten mature individuals of Pyracantha, ten of the dominant native shrub Condalia montana, and ten patches without shrub cover were involved. In each treatment we planted seeds and saplings of Ligustrum collected from nearby natural populations. Seedlings emerging from the planted seeds were harvested after one year to measure growth. Survival of the transplanted saplings was recorded every two month during a year. Half of the planted seeds and transplanted saplings were cage‐protected from rodents. Results: Ligustrum seedling emergence did not differ among treatments while growth was significantly higher in the absence of shrub cover. Sapling survival was significantly higher under the canopy of Pyracantha, intermediate under Condalia, and lowest in the absence of shrub cover. Caging did not affect growth but enhanced seedling emergence and sapling survival. Conclusion: The differential sapling survival in the shrub canopy treatments is consistent with natural sapling distribution. Pyracantha and, less so, Condalia, has a nurse‐plant effect on Ligustrum. This results from contrasting effects of the shrubs on different stages of the life cycle of Ligustrum: no effect on seedling emergence, negative on seedling growth, and positive on sapling survival. This suggests that efforts to control the expansion of Ligustrum over the landscape should tackle Pyracantha as well.     

A meta-analysis of the interactive effects of UV and drought on plants

Interactions between climate change and UV penetration in the biosphere are resulting in the exposure of plants to new combinations of UV radiation and drought. In theory, the impacts of combinations of UV and drought may be additive, synergistic or antagonistic. Lack of understanding of the impacts of combined treatments creates substantial uncertainties that hamper predictions of future ecological change. Here, we compiled information from 52 publications and analysed the relative impacts of UV and/or drought. Both UV and drought have substantial negative effects on biomass accumulation, plant height, photosynthesis, leaf area and stomatal conductance and transpiration, while increasing stress-associated symptoms such as MDA accumulation and reactive-oxygen-species content. Contents of proline, flavonoids, antioxidants and anthocyanins, associated with plant acclimation, are upregulated both under enhanced UV and drought. In plants exposed to both UV and drought, increases in plant defense responses are less-than-additive, and so are the damage and growth retardation. Less-than-additive effects were observed across field, glasshouse and growth-chamber studies, indicating similar physiological response mechanisms. Induction of a degree of cross-resistance seems the most likely interpretation of the observed less-than-additive responses. The data show that in future climates, the impacts of increases in drought exposure may be lessened by naturally high UV regimes.     

Antimicrobial effect of radiant catalytic ionization

The main purpose of micro-organisms elimination from the air and surfaces is to ensure microbiological safety in health care facilities or food production plants. Currently, many disinfection methods are used, both physical, chemical and, increasingly, biological. Scientists seek new solutions with high antimicrobial effectiveness (especially against the drug-resistant strains of bacteria), low production and operating costs, and, above all, the safety of patients and food consumers. The limitation of the methods used so far is primarily the micro-organisms acquire the resistance, mainly to antimicrobial agents. One of the new and alternative methods of disinfection is radiant catalytic ionization (RCI). RCI is an active method of air and surface purification. The technology proved high efficiency against viruses, Gram-positive and -negative bacteria, and fungi, both in the air and on surfaces (planktonic forms and biofilm). RCI has many advantages as well as some minor limitations. This overview summarizes the current knowledge about RCI technology.