Tandem addition of nucleophilic and electrophilic reagents to vinyl phosphinates: the stereoselective formation of organophosphorus compounds with congested tertiary carbons.

Carbon anions formed via the addition of Grignard reagents to SP-vinyl phosphinates were modified with electrophilic reagents to afford organophosphorus compounds with diverse carbon skeletons. The electrophiles included acids, aldehydes, epoxy groups, chalcogens and alkyl halides. When alkyl halides were used, bis-alkylated products were afforded. Substitution reactions or polymerization occurred when the reaction was applied to vinyl phosphine oxides.

[Soil fertility characteristics and their influencing factors in tea plantations of Jiangxi Pro-vince, China]. / æ±Ÿè¥¿çœèŒ¶å›­åœŸå£¤è‚¥åŠ›ç‰¹å¾åŠå ¶å½±å“å› å­.

To investigate soil fertility status and characteristics of typical tea plantations, we selec-ted 372 typical tea plantations of 21 areas across Jiangxi Province and analyzed the soil nutrient, spatial data, and their correlations with topography, soil type, elevation and plantation age. The results showed that soil pH, organic matter, alkaline nitrogen, available phosphorus, available potassium, total nitrogen, total phosphorus and total potassium of tea plantation in Jiangxi reached 53.9%, 60.1%, 56.1%, 22.9%, 38.5%, 43.7%, 11.1% and 95.5% of indices of high fertility, high efficiency and high yield tea plantation, respectively, with the available phosphorus showing a strong variation. Soil available copper, zinc, iron, manganese and boron reached 76.3%, 74.2%, 96.8%, 73.1% and 0.0% of the first-class standards for soil trace elements, respectively. Tea plantations with highest soil fertility located in central Jiangxi, followed by northeastern and northwestern Jiangxi, and lowest in southern Jiangxi. Soil pH was significantly positively correlated with organic matter, alkaline nitrogen, available phosphorus, available potassium, total nitrogen and total phosphorus but not for total potassium. For different topography, soil fertility was highest in the flat land, followed by the high mountains, and lowest in the mountains and hills. Across different soil types, soil fertility was higher in paddy soil, sandy soil and mountain yellow brown soil, followed by yellow soil, red-yellow soil and purple soil, and lowest in red soil. Soil pH, organic matter and total potassium increased while available phosphorus decreased with altitude. The organic matter, alkaline nitrogen, available phosphorus, total nitrogen and total phosphorus increased, but soil pH decreased with time. In summary, soil fertility of tea plantations in Jiangxi Province was generally good, with high organic matter, total potassium, available copper, zinc, iron and manganese. However, soil was acidic, available phosphorus and total phosphorus content was low, available boron was seriously limited. We suggest increase soil pH and potassium supply in central Jiangxi, increase potassium and nitrogen fertilizer supply in northeastern Jiangxi, increase organic matter and phosphorus fertilizer supply in northwestern Jiangxi, and increase nitrogen, phosphorus and potassium supply combined with organic fertilizers in southern Jiangxi. High mountain tea plantations should enhance available phosphorus and potassium supply. Mountain tea plantations should enhance nitrogen and phosphate supply. Tea plantations with red and yellow soil should increase pH and total potassium supply. Tea plantations with red soil should apply nitrogen, phosphorus and potassium fertilizers combined with organic fertilizers. Tea plantations with yellow soil and mountain yellow brown soil required additional phosphorus supply, and tea plantations with purple soil should increase soil organic matter supply. Tea plantations need to increase dolomite powder, physiological alkaline fertilizers and organic fertilizers to prevent soil acidification.

Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications.

Nucleophilic substitutions at P centers are of high importance in biological processes and asymmetric synthesis. However, detailed studies on this topic are rare. P-Stereogenic compounds containing P-Cl, P-O, and P-S bonds were diastereoselectively prepared and then used to study the substitution of Cl, O, and S at phosphorus centers with organometallic reagents. It was proposed that with alkynyl metallic reagents an SN2-like mechanism (route A1) and a Berry pseudorotation (BPR) of pentacoordinated phosphorus intermediates (route B1) were involved and afforded P-inverted and P-retained products, respectively. The P-inverted conversion of a P-Cl functionality to a P-C functionality can be controlled by either the temperature or the order of addition of the starting materials. The introduction of a P-Cl bond using an alkyl metallic reagent proceeded through routes A2 and A2'. At higher temperatures, P-inverted products were predominantly afforded via SN2-like route A2. At lower temperatures, bis-substituted products were formed via route A2' and cleavage of the P-O bond. The P-S bonds were accompanied by the epimerization of the starting materials, triggered by the alkylthio anion, via route C. The epimerization can be suppressed by the use of a poorly soluble magnesium alkylthiolate, and the P-retained compounds will be formed as the major products via route B3 and BPR of the intermediates.

[Effect of the Food to Mass Ratio and Hydraulic Retention Time on Hydrogen Production from Fruit and Vegetable Waste].

Semi-continuous biogas production from fruit and vegetable waste by medium temperature anaerobic fermentation was conducted. Hydrogen production under different food-microorganism ratios (F/M 0.5, 0.75, 1.0, 1.5) and hydraulic retention times (HRT) (2, 3, 4 d) were investigated. The results show that in the case of a smaller F/M values (0.5 and 0.75), not all HRT stages were conducive to the continuous production of hydrogen, however, they were conducive to producing methane, especially when HRT was 3 or 4 d. Continuous hydrogen production was viable when the F/M ration was relatively higher (1.0 and 1.5), however, this was not conducive to the production of methane, with almost no methane production detected in this process. A F/M of 1.0 and a HRT of 3 d provided the best conditions for continuous hydrogen production from fruit and vegetable waste. Meanwhile, the highest and average daily volume of hydrogen production were 451.2 mL·(L·d)-1 and (186±29) mL·(L·d)-1 respectively, whereas the highest and average hydrogen production rate of volatile solids were 133 mL·g-1 and (27±5) mL·g-1 respectively. The hydrogen content was 20%-30%.

Stereospecific Preparations of P-Stereogenic Phosphonothioates and Phosphonoselenoates.

P-Stereogenic phosphonothioates and phosphonoselenoates were readily prepared utilizing RP-menthyl phenylphosphite 1 by two methods. The first method used elemental sulfur or selenium to react with 1, followed by alkylation of the intermediates with alkyl halides. The second used 1 to react with disulfide or diselenide. Both methods stereospecifically produced the title compounds in nearly quantitative yields under mild conditions. Stereospecific chalcogenation of the phosphoryl was proposed as the key step in these reactions.

X-ray therapy promotes structural regeneration after spinal cord injury in a rat model.

OBJECTIVE: This study aims to investigate the therapeutic effects and mechanisms of x-ray treatment on rats following spinal cord injury (SCI). METHODS: Forty-six female Sprague-Dawley rats were subjected to spinal cord injury using the modified Allen weight-drop method. The animals were randomly divided into six groups. Two of the animal groups were irradiated with 10 Gy at the lesion site; another two groups were irradiated with 20 Gy; and the last two groups without irradiation were regarded as the sham group. One of the each of two animal groups was euthanized at different time points at 4 and 12 weeks, respectively, after irradiation. Spinal cord calluses were assessed using kinology and electrophysiology and histology methods. RESULTS: In all of the groups, the neurofilament (NF) counts at 14 weeks were found to be higher than that at 6 weeks after SCI. Both 10-Gy irradiated and 20-Gy irradiated groups were higher than those of the sham group at each time point (P < 0.05). The myelin basic protein (MBP) count decreased at 14 weeks after SCI in the irradiated groups (P < 0.05) but increased at 14 weeks in the sham group (P < 0.05). Furthermore, the MBP count of the irradiated groups was lower than that of the sham group at 14 weeks (P < 0.05). The glial fibrillary acidic protein (GFAP) and Nogo-A counts at 14 weeks were higher than those at 6 weeks in all the groups (P < 0.05), and there was no statistical significance with kinology and electrophysiology tests in all groups. CONCLUSIONS: A self-repair mechanism exists after spinal cord injury, which lasts at least 14 weeks. X-ray therapy promotes the regeneration of the spinal cord system after injury.

One-pot process that efficiently generates single stereoisomers of 1,3-bisphosphinylpropanes having five chiral centers.

P,C-stereogenic 1,3-bisphosphinylpropanes 3 that have up to five stereogenic centers could be obtained stereoselectively in high yields by a one-step reaction of (RP)-menthylphenylphosphine oxide 1 with α,ß-unsaturated aldehydes 2 catalyzed by KOH at room temperature. A mechanism was proposed as to involve a stereoselective intermolecular 1,3'-phosphorus migration from the 1,2-adduct of 1 with 2 to another 2 generating a 1,4-adduct that subsequently reacts with 1 to produce 3.

Addition of optically pure H-phosphinate to ketones: selectivity, stereochemistry and mechanism.

Aromatic methyl ketones and cyclic asymmetric ketones underwent hydrophosphorylation with P-stereogenic H-P species in the presence of potassium carbonate to produce P,C-stereogenic tertiary α-hydroxyl phosphinates in excellent yields with up to 99 : 1 dr. The diastereoselectivity was induced by a reversible conversion of less stable stereomer of product to that of a more stable one via an equilibrium, which was confirmed by aldehyde/ketone exchanging reaction. Toward the exchange, aliphatic or aldehyde carbonyl were more active than aromatic or ketone carbonyls, respectively. The stability difference between the two diastereomers was controlled by the sizes of substituents linking to phosphorus or α-carbon.

Stereogenic phosphorus-induced diastereoselective formation of chiral carbon during nucleophilic addition of chiral H-P species to aldehydes or ketones.

P,C-stereogenic α-hydroxyl phosphinates or phosphine oxides were prepared from the additions of (RP)-phosphinate to ketones or (RP)-phosphine oxide to aldehydes, respectively, catalyzed by bases at room temperature in up to >99:1 diasteromeric ratio (d.r.P/d.r.C) and 99 % yields. The diastereoselectivity was induced by reversible equilibrium and different stabilities between two diastereomers of adduct, which was caused by the spatial interaction between menthoxyl or menthyl to alkyl groups of aldehydes or ketones.

Enhancement of bioelectricity generation by cofactor manipulation in microbial fuel cell.

Microbial fuel cells (MFCs) are promising for harnessing bioenergy from various organic wastes. However, low electricity power output (EPT) is one of the major bottlenecks in the practical application of MFCs. In this study, EPT improvement by cofactor manipulation was explored in the Pseudomonas aeruginosa-inoculated MFCs. By overexpression of nadE (NAD synthetase gene), the availability of the intracellular cofactor pool (NAD(H/(+))) significantly increased, and delivered approximately three times higher power output than the original strain (increased from 10.86 µW/cm(2) to 40.13 µW/cm(2)). The nadE overexpression strain showed about a onefold decrease in charge transfer resistance and higher electrochemical activity than the original strain, which should underlie the power output improvement. Furthermore, cyclic voltammetry, HPLC, and LC-MS analysis showed that the concentration of the electron shuttle (pyocyanin) increased approximately 1.5 fold upon nadE overexpression, which was responsible for the enhanced electrochemical activity. Thus, the results substantiated that the manipulation of intracellular cofactor could be an efficient approach to improve the EPT of MFCs, and implied metabolic engineering is of great potential for EPT improvement.

Enhancement of bioelectricity generation by manipulation of the electron shuttles synthesis pathway in microbial fuel cells.

Microbial fuel cells (MFCs) are promising for generating bioenergy and treating organic waste simultaneously. However, low extracellular electron transfer (EET) efficiency between electrogens and anodes remains one of the major bottlenecks in practical applications of MFCs. In this paper, pyocyanin (PYO) synthesis pathway was manipulated to improve the EET efficiency in Pseudomonas aeruginosa-inoculated MFCs. By overexpression of phzM (methyltransferase encoding gene), the maximum power density of P. aeruginosa-phzM-inoculated MFC was enhanced to 166.68 µW/cm(2), which was four folds of the original strain. In addition, the phzM overexpression strain exhibited an increase of 1.6 folds in PYO production and about a onefold decrease in the total internal resistance than the original strain, which should underlie the enhancement of the EET efficiency and the electricity power output (EPT). On the basis of these results, the manipulation of electron shuttles synthesis pathways could be an efficient approach to improve the EPT of MFCs.

Factors affecting the performance of a single-chamber microbial fuel cell-type biological oxygen demand sensor.

Microbial fuel cells (MFCs) are devices that exploit microorganisms as biocatalysts to degrade organic matter or sludge present in wastewater (WW), and thereby generate electricity. We developed a simple, low-cost single-chamber microbial fuel cell (SCMFC)-type biochemical oxygen demand (BOD) sensor using carbon felt (anode) and activated sludge, and demonstrated its feasibility in the construction of a real-time BOD measurement system. Further, the effects of anodic pH and organic concentration on SCMFC performance were examined, and the correlation between BOD concentration and its response time was analyzed. Our results demonstrated that the SCMFC exhibited a stable voltage after 132 min following the addition of synthetic WW (BOD concentration: 200 mg/L). Notably, the response signal increased with an increase in BOD concentration (range: 5-200 mg/L) and was found to be directly proportional to the substrate concentration. However, at higher BOD concentrations (>120 mg/L) the response signal remained unaltered. Furthermore, we optimized the SCMFC using synthetic WW, and tested it with real WW. Upon feeding real WW, the BOD values exhibited a standard deviation from 2.08 to 8.3% when compared to the standard BOD5 method, thus demonstrating the practical applicability of the developed system to real treatment effluents.

(R(P))-5-Methyl-2-(propan-2-yl)cyclo-hexyl phen-yl{phen-yl[(1-phenyl-eth-yl)amino]-meth-yl}phosphinate.

In the title compound, C(31)H(40)NO(2)P, the P atom has a distorted tetra-hedral stereochemistry [bond-angle range about P = 103.33 (6)-115.24 (15)°] and has R(P) chirality, which was confirmed crystallographically. The dihedral angles between the P-bonded phenyl ring and the other two phenyl rings are 40.4 (3) and 12.2 (2)°. In the crystal, a C-H⋯O inter-action links mol-ecules into chains which extend along [100].

(1-Methyl-1H-imidazol-3-ium-2-yl)(phen-yl)phosphinate monohydrate.

The title compound, C(10)H(11)N(2)O(2)P·H(2)O, contains a tetra-coordinate penta-valent P atom. The phosphinate group plays a predominant role in the cohesion of the crystal structure by forming chains along the b axis via inter-molecular C-H⋯O hydrogen bonds. These chains are connected by O-H⋯O and N-H⋯O hydrogen bonding involving the lattice water.

[Local X-irradiation promotes regeneration of spinal cord central nervous system in a rat model].

OBJECTIVE: To evaluate the effect of local X-irradiation on spinal cord injury by using physiology, kinology, electrophysiology and histology method. METHODS: 46 female Sprague-Dawley rats were subjected to spinal cord injury by weight dropping on T(11-12). All animals were divided into 3 groups randomly. One of the animal groups was irradiated with 10 Gy at the lesion site; another was irradiated with 20 Gy, the other without irradiation is regarded as sham-group. The animals were euthanized at different time points at 4 and 12 weeks after irradiation. Spinal cord callus was assessed by using physiology, kinology, and electrophysiology and histology method. RESULTS: In all the groups, the NF at 14 weeks were found higher than that of 6 weeks. Both 10 Gy irradiated and 20 Gy irradiated groups were higher than those of group at each time point (P < 0.05). The MBP decreased at 14 weeks in irradiated groups (P < 0.05), but increased at 14 weeks in sham-group (P < 0.05), the MBP of irradiated groups was lower than that sham-group at 14 weeks (P < 0.05). The GFAP and Nogo-A at 14 weeks were higher than that in 6 weeks in all the groups (P < 0.05), and there was no statistical significance with physiology, kinology, electrophysiology test in all groups. CONCLUSION: A self-repair mechanism exists after SCI, which will last at least 14 weeks. Local irradiation promotes the regeneration of spinal cord system after injury to some extent.