Temperature effect on the conversions of phthalato and maleato manganese(II) complexes with diamine ligands

1,10-Phenanthroline hydrogen phthalato manganese(II) dimer [Mn₂(Hphth)₂(phen)₄] · 2Hphth · 6H₂O (1), monomeric phenanthroline phthalato manganese(II) monomer [Mn(phth)(phen)₂(H₂O)] · 2.5H₂O (2), 2,2′-bipyridine phthalato manganese(II) polymer [Mn(phth)(bpy)(H₂O)₂]_n (3) and 1,10-phenanthroline maleato polymer [Mn(male)(phen)(H₂O)₂]_n · 2nH₂O (4) (H₂phth = o-phthalic acid, male = maleic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine) have been synthesized and characterized spectroscopically and structurally. Each Mn(II) atom in dimeric 1 is octahedrally coordinated by two oxygen atoms of phthalate anions and by two cis-phenanthroline ligands. The hydrogen phthalato anion bridges the Mn(II) ions through the deprotonated carboxyl groups, while the carboxylic acid group remains free. In the monomeric 2, the Mn(II) ion is octahedrally surrounded by four nitrogen atoms from two cis-phen ligands, one carboxyl oxygen from a monodentate phth ion, and one coordinated water molecule. The dimeric phthalato complex 1 can be cleaved into monomer 2 under heating with deprotonation, and the course of the reaction can be qualitatively traced by IR spectra. The phthalate group in the complex 3 binds to two manganese atoms through the vicinal carboxyl-oxygen atoms in syn-syn bridging mode. The Mn(II) atoms are linked by the phthalate group to yield a one-dimensional chain running along the a-axis. The coordination polymer 3 can be obtained from the reaction of dichloro dibipyridine manganese with phthalate under heating. In polymer 4, the manganese atom is six-coordinated by two nitrogen atoms from phen, two oxygen atoms from the coordinated water molecules and two oxygen atoms from two different maleate dianions. Each maleato unit links two neighboring manganese atoms to yield one-dimensional chain along b-axis in bis-monodentate mode. The single-chain polymer 4 prepared at low temperature can be converted to double-chain coordination polymer [Mn(male)(phen)]_n · nH₂O (5) with dehydration in warm solution.     

马来酸氟伏沙明片联合氨磺必利治疗精神分裂症患者的疗效及安全性分析

目的:分析马来酸氟伏沙明片联合氨磺必利治疗精神分裂症患者的临床疗效及安全性。方法:选择我院2014年2月~2018年2月收治的182例精神分裂症患者,按随机数字表法分为对照组99例和研究组83例。对照组采用氨磺必利治疗,研究组在对照组基础上联合马来酸氟伏沙明片治疗。比较两组临床疗效,治疗前后血脂代谢、总胆汁酸(TBA)水平,阳性与阴性症状量表(PANSS)评分,生活质量,及不良发生情况。结果:治疗后,研究组总有效率为91.57%,显著高于对照组(P<0.05);两组治疗前后空腹血糖(FPG)、糖化血红蛋白(HbA1c)、甘油三酯(TG)、总胆固醇(TC)、低密度脂蛋白-C(LDL-C)、高密度脂蛋白-C(HLD-C)、总胆汁酸(TBA)水平比较均无统计学意义(P>0.05);两组治疗后PANSS评分均较治疗前显著下降,生活质量评分较治疗前均明显上升,且研究组PANSS评分显著低于对照组,而生活质量评分明显高于对照组,差异均有统计学意义(P<0.05)。治疗过程中,两组均有体重增加、口渴及便秘发生,两组不良反应发生情况比较差异无统计学意义(P>0.05)。结论:马来酸氟伏沙明片联合氨磺必利治疗能够提高精神分裂症患者疗效,对机体糖脂代谢及肝功能影响较小,有良好的用药安全性。     

依那普利叶酸片对高血压伴高同型半胱氨酸血症大鼠左室肥厚干预的研究

目的:观察高同型半胱氨酸对高血压大鼠心肌内质网应激相关因子GRP94、caspase12表达的影响,及依那普利叶酸片(简称依叶片)对其表达的干预作用。方法:30只雄性成年自发性高血压大鼠(SHR),随机分为对照组、模型组和依叶片组,每组10只。对照组给予普通颗粒饲料喂养同时给予双蒸水灌胃,模型组给予含3%蛋氨酸的颗粒饲料喂养同时给予双蒸水灌胃,依叶片组给予含3%蛋氨酸的颗粒饲料喂养同时给予依叶片粉剂20 mg/kg/d灌胃。实验第8周末,用颈动脉插管法测各组大鼠平均动脉压(MAP),同型半胱氨酸检测仪检测血清同型半胱氨酸(homocystein,Hcy)浓度,称取体质量、全心质量及左心室质量计算大鼠心肌肥厚指数HWI及LVEI,通过HE染色观察心肌细胞形态学改变,免疫组化检测大鼠心肌组织中GRP94及caspase12表达水平。结果:①大鼠血清Hcy水平的变化。对照组大鼠血清Hcy值在正常值范围。与对照组相比,模型组大鼠血清Hcy值显著增高(P0.01);与模型组相比,依叶片组大鼠血清Hcy值明显降低(P0.01)。②大鼠HWI、LVEI及MAP的变化。模型组大鼠的HWI及LVEI均明显高于对照组(P0.05);依叶片干预后大鼠的HWI及LVEI均明显降低(P0.05)。对照组与模型组大鼠的MAP均明显增高,但两组大鼠的MAP差异无统计学意义(P0.05);与模型组相比,依叶片干预后大鼠的MAP明显降低(P0.01)。③大鼠心肌细胞内质网应激(endoplasmic reticulum stress,ERS)相关因子GRP94及caspase12表达。对照组及模型组大鼠心肌细胞GRP94及caspase12表达均增高。与对照组相比,模型组大鼠心肌细胞GRP94、caspase12表达增高更为明显(P0.05)。依叶片干预后大鼠心肌细胞GRP94、caspase12表达明显降低(P0.05)。结论:高Hcy通过ERS途径使高血压大鼠左室肥厚程度加重;依叶片可有效降低血清Hcy及血压水平,抑制心肌细胞ERS,从而有效逆转左室肥厚,其对左室肥厚干预的分子机制为"H型"高血压的预防及治疗提供了新的理论依据。     

Zinc maleate and fumarate coordination polymers containing hydrogen-bonding capable organodiimines featuring ligand dependent in situcis-trans isomerization

Solution phase reaction at ambient temperature of zinc nitrate, maleic acid and 4,4′-dipyridylamine (dpa) afforded {[Zn₂(maleate)₂(dpa)₂]·5H₂O}_n (1), which displayed parallel (4,4)-grid like coordination polymer layers interdigitated into double layer slab motifs via hydrogen bonding. A similar reaction employing bis(4-pyridylmethyl)piperazine (bpmp) caused in situcis-trans isomerization of maleic acid to fumarate, and generation of [Zn(fumarate)(bpmp)(H₂O)₂]_n (2). Compound 2 also manifested (4,4)-grid coordination polymer layers similar to those in 1; however, the larger apertures in 2 permit 2d + 2d → 3D mutually inclined interpenetration. Thermogravimetric and luminescence studies are also reported for 1 and 2.     

Fumaric acid production by fermentation

The potential of fumaric acid as a raw material in the polymer industry and the increment of cost of petroleum-based fumaric acid raises interest in fermentation processes for production of this compound from renewable resources. Although the chemical process yields 112% w/w fumaric acid from maleic anhydride and the fermentation process yields only 85% w/w from glucose, the latter raw material is three times cheaper. Besides, the fermentation fixes CO₂. Production of fumaric acid by Rhizopus species and the involved metabolic pathways are reviewed. Submerged fermentation systems coupled with product recovery techniques seem to have achieved economically attractive yields and productivities. Future prospects for improvement of fumaric acid production include metabolic engineering approaches to achieve low pH fermentations.     

Fermentation of maleate by a gram-negative strictly anaerobic non-spore-former,Propionivibrio dicarboxylicus gen. nov., sp. nov.

Three strains of maleate-fermenting anaerobic curved rods were isolated in pure culture from anaerobic freshwater mud samples. Among the isolates, strain CreMal1 was studied in detail. It was a mesophilic non-sporing gram-negative strict anaerobe, and grew not only on maleate but also on fumarate and l-malate, producing propionate and acetate stoichiometrically as end products. Succinate was an intermediate in the degradation of maleate. Nitrate, sulfate, and other sulfur compounds were not utilized as electron acceptors. It had 61 mol% guanine-plus-cytosine content, but possessed a single polar flagellum and did not utilize carbohydrates and lactate, unlike the genus Selenomonas. Therefore, strain CreMal1 is described as a member of Propionivibrio dicarboxylicus gen. nov., sp. nov., in the family Bacteroidaceae. Strain CreMal1 was deposited as type strain in the Japan Collection of Microorganisms and in Deutsche Sammlung von Mikroorganismen.Dedicated to Professor Dr. Norbert Pfennig on the occasion of his 65th birthday     

Reprogramming Escherichia coli pyruvate-forming reaction towards chorismate derivatives production

Microbial metabolic pathway engineering is a potent strategy used worldwide to produce aromatic compounds. We drastically rewired the primary metabolic pathway of Escherichia coli to produce aromatics and their derivatives. The metabolic pathway of E. coli was compartmentalized into the production and energy modules. We focused on the pyruvate-forming reaction in the biosynthesis pathway of some compounds as the reaction connecting those modules. E. coli strains were engineered to show no growth unless pyruvate was synthesized along with the compounds of interest production. Production of salicylate and maleate was demonstrated to confirm our strategy's versatility. In maleate production, the production, yield against the theoretical yield, and production rate reached 12.0 g L⁻¹, 67%, and up to fourfold compared to that in previous reports, respectively; these are the highest values of maleate production in microbes to our knowledge. The results reveal that our strategy strongly promotes the production of aromatics and their derivatives.