Electron and light microscopy of neutrophil responses in mice vaccinated and challenged with third-stage infective hookworm (Ancylostoma caninum) larvae

The role of neutrophils in mediating host inflammation was examined in mice vaccinated with living third-stage infective hookworm larvae (L₃). Mice were vaccinated by oral immunization with 500 L₃ (Ancylostoma caninum) once every 2 weeks for a total of three immunizations. The vaccinated mice were then challenged intraperitoneally with 2000 L_3, 1 week after the final immunization. To stimulate peritoneal production of neutrophils, 2 ml of 2% glycogen were injected intraperitoneally at 16 h prior to the challenge infection. Neutrophils were found to comprise 85% of the peritoneal cell population. L₃ from the challenge infection were collected and then examined at timed intervals by inverted light microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Greater than a fivefold increase in the total numbers of peritoneal cells was noted in the vaccinated mice as compared to unvaccinated mice. In the peritoneal cavity of vaccinated mice, the neutrophils adhered to the L₃ within 2 h, and over 55% of the L₃ were surround by clusters of neutrophils to form a sausage-like sheath 4 h later. At 24–72 h after challenge, almost all of the L₃ recovered from the vaccinated mice were covered with thick clusters of cells. Both SEM and TEM demonstrated extensive ultrastructural damage to the L_3. In contrast, the L₃ recovered from the unvaccinated mice appeared to be unaffected by neutrophils. These studies suggest that neutrophils, like macrophages, can have an important role as effector cells in L₃-vaccinated mice.     

Immune modification of the pathogenesis of Streptococcus uberis mastitis in the dairy cow

Abstract Two groups of 4 cows were vaccinated subcutaneously with live Streptococcus uberis strain 0140J or a surface extract derived from the same strain, at 14 days prior to the cessation of lactation (drying off) and at calving. Both groups also received an intramammary administration of the surface extract 7 days after drying off. A third group of unvaccinated animals acted as controls. Following intramammary challenge of two quarters per cow with the vaccine strain, all quarters on control cows and those vaccinated only with surface extract developed clinical mastitis. However, only 12.5% of challenged quarters on cows which were vaccinated with live bacteria developed clinical mastitis. In addition, the numbers of bacteria in the milk following challenge were 10⁵ times higher from the control and extract vaccinated cows than those which received live vaccine. Serum levels of S. uberis specific IgG₂ were elevated in the animals vaccinated with the live organism when compared to that of either extract-vaccinates or controls, whilst S. uberis specific levels of IgG₁ and IgM were similar in all groups throughout the experiment. Specific antibody levels in milk were unaffected by vaccination. Despite increased levels of IgG₂, no increase in opsonic activity was detected in any serum or milk samples. Peripheral blood lymphocytes from animals vaccinated with live organisms showed a considerable increase in proliferative response to S. uberis antigen in vitro when compared with lymphocytes from control and extract-vaccinated animals. These results suggest that neutrophils and specific opsonising antibody may not form the major defence against infection with S. uberis .     

不同施氮水平下杨树-苋菜间作系统对土壤氮素流失的影响

采用田间试验方法,研究了杨树 苋菜间作系统,即株行距2 m×5 m(L₁)和2 m×15 m(L₂)在0(N₀)、91(N₁)、137(N₂)和183(N₃) kg·hm^-2施氮水平下的土壤氮素流失特征.结果表明: 不同施氮水平对地表径流量、淋溶量和土壤侵蚀量的控制效果均为L₁＞L₂＞L₃ (单作苋菜);L₁、L₂地表径流量分别比L₃降低65.1%、55.9%;L₁、L₂距林带0.5 m处淋溶量比L₃降低30.0%、28.9%,距林带1.5 m处淋溶量比L₃降低25.6%、21.9%;L₁、L₂土壤侵蚀量分别比L₃降低65.0%、55.1%.对地表径流和淋溶损失中TN、NO₃^--N、NH₄⁺-N流失量的控制效果均为L₁＞L₂＞L₃;常规施氮(91 kg·hm^-2)水平下,L₁地表径流中TN、NO₃^--N、NH₄⁺-N流失量较L₃分别降低62.9%、45.1%、69.2%,L₂较L₃分别降低23.4%、6.9%、46.2%;杨树间作密度越大、距离林带越近,对土壤NO₃^--N、NH₄⁺-N的淋溶损失削减作用越强.同一间作密度下,随着施氮量的增加,地表径流中NO₃^--N流失比例减少,NH₄⁺-N流失比例增加;淋溶流失中
NO₃^--N、NH₄⁺-N浓度变化趋势一致,均为 N₃＞N₂＞N₁＞N₀.     

Evolution of host-parasite adaptation in nematodes of vertebrates

An analysis was attempted of the factors which determine the adaptation of Nematodes to their vertebrate hosts. A further analysis was carried out on the adaptation to the intermediate host or hosts. A distinction was made between the intermediate host harbouring pre-infective stages (L₁, L₂ and the beginning of L₃) and those harbouring post-infective larvae (the end of L₃ and L₄).     

遮荫对香果树叶片生理特性及叶肉细胞超微结构的影响

设置全光照（L₀）、透光率60%（L₁）、透光率25%（L₂）、透光率10%（L₃）4种光环境,通过遮荫试验研究不同光照条件对香果树幼苗生理特性及叶肉细胞超微结构的影响。结果表明：遮荫影响叶片含水量及叶片形态。随着遮荫强度的加大,叶片含水量（LWC）递增,单叶面积（SLA）增加,单叶干重（SLW_d）和比叶重（LAM）减小,比叶面积（LAM）增大。遮荫条件下幼苗光合作用效率呈现显著变化。全光和L₁处理的P_n和T_r日变化呈明显的双峰曲线,出现了明显的"午休",其余处理的变化相对缓和,双峰和"午休"现象不明显;G_s的日变化与P_n类似。P_n和T_r的日均大小排序为L₁ > L₀ > L₂ > L₃。轻度遮光有利于香果树光合作用效率的提高。遮荫条件下叶片叶绿素和类胡萝卜素含量均有一定程度增加,且随着遮荫强度的加大其含量递增,提高了叶片的捕光能力。遮荫条件下MDA变化较为缓和,SOD、POD活性呈现先升后降的变化,但遮荫下的MDA含量始终小于全光照,可溶性糖也呈现类似的变化。全光下叶绿体与细胞壁平行分布,呈梭形,类囊体排列均匀,淀粉粒和嗜锇颗粒较少;遮荫条件下细胞内叶绿体数量有所增加,在整个细胞中占有比例显著增大,淀粉粒含量增多,类囊体排列紧密,堆叠程度增高,提高了弱光下的光合效率。适度遮荫香果树幼苗能维持正常的生理活动,但有效辐射光强须为自然光强的60%以上。     

不同灌溉畦长对小麦光合特性、干物质积累及水分利用效率的影响

以高产冬小麦品种济麦22为材料,研究不同灌溉畦长对小麦旗叶水势、光合特性和干物质积累与分配的影响.2010—2011年小麦生长季设置畦长为10(L₁₀)、20(L₂₀)、40(L₄₀)、60(L₆₀)、80(L₈₀)和100 m(L₁₀₀)的6个处理,2011—2012年和2012—2013年设置畦长为40(L₄₀)、60(L₆₀)、80(L₈₀)和100 m(L₁₀₀)的4个处理.结果表明: 2010—2011年生长季开花期0～200 cm土层平均土壤相对含水量为L₈₀、L₆₀>L₁₀₀>L₄₀>L₂₀>L₁₀,2011—2012年和2012—2013年为L₈₀、L₆₀>L₁₀₀>L₄₀.开花后11 d和21 d,旗叶水势、净光合速率和蒸腾速率均为L₈₀、L₁₀₀>L₆₀>L₄₀>L₂₀、L₁₀;花后31 d为L₈₀>L₆₀、L₁₀₀>L₄₀、L₂₀、L₁₀.L₈₀各区间开花期和成熟期干物质积累量及籽粒产量变异系数小于L₁₀₀,平均干物质积累量及开花后干物质积累量和对籽粒产量的贡献率显著高于L₁₀₀、L₄₀、L₂₀和L₁₀,平均籽粒产量和水分利用效率显著高于其他处理,是本试验条件下节水高产的最优畦长处理.     

Syntheses and properties of organocyanamide, cyanoguanidine and dinitrogen complexes of rhenium. Crystal structure of mer-[ReCl2(NCNEt2) (PMePh2)3]

Treatment of a THF solution of trans-[ReCl(N₂)L₄] (L = PMePh₂) with a cyanamide, NCNR₂ (R = Me, Et or H) or with cyanoguanidine, NCNC(NH₂)₂ , yields mer-[ReCl(N₂)(NCNR₂)L₃] (1) or mer-[Re(N₂)[Re(N₂){NCNC(NH₂)₂}₂L₃]Cl (2), respectively, which, to our knowledge, are the first mixed dinitrogen-cyanamide-type complexes to be reported. The former products (1, R=Me or Et) can also be obtained from reaction of the benzoyldiazenido complex [ReCl₂(NNCOPh)L₃] with NCNR₂ in refluxing methanol; the Re(II) complex mer-[ReCl₂(NCNEt₂)L₃] (3) is also formed (conceivably via an unusual homolysis of the C---N bond of the benzoyldiazenido ligand) and its crystal structure is reported. It shows an unusual pyramidal conformation at the amine N atom of the diethylcyanamide ligand which also exhibits a significant structural trans influence on the phosphine, behaving as a stronger net electron donor than the latter ligand.     

Synthesis, characterization and reactivity of platinum-substituted ketenes [PtX{η-C(PPh3)CO}L2]BF4, (X=Me, Cl; L2=1,5-cyclooctadiene, 1,2-bis(diphenylphosphino)ethane, cis-1,2-bis(diphenylphosphino)ethene). Steric and electronic effects of the ancillary ligands

Ketenylidenetriphenylphosphorane, Ph₃PC=C=O, 1, has been used to synthesize platinum-substituted ketenes [PtMe{η¹-C(PPh₃)CO}L₂]BF₄, 2a, b (L₂=1,5-cyclooctadiene, cod (a), 1,2-bis(diphenylphosphino)ethane, diphos (b)). Parent compound [PtCl{η¹-C(PPh₃)CO}L₂]BF₄, 3, with L₂=cis-1,2-bis(diphenylphosphino)ethene, diphoe, was also synthesized, which is stable only at low temperature. The stability of 2 and 3 and the reactivity of the C=C=O moiety have been examined and discussed in terms of the electronic and steric characteristics of the ancillary ligands, also taking into account the reactivity of the ‘PtXL₂’ fragment with other carbonyl stabilized phosphorus ylides, Ph₃PCHCOR (R=Me, Ph, OMe, OEt).     

Palladium (II)-catalyzed alternating copolymerization of alkenes with sulfur dioxide

Cationic palladium(II) complexes of the type [L₂Pd(CH₃)(CH₃CN)]BF₄ (L₂ = 1,3-bis(diphenylphosphino)propane (Dppp) or 1,2-bis(2,5-dimethylphospholano)benzene (Me-Duphos)) were found to catalyze the alternating copolymerization of ethene, propene and cyclopentene with sulfur dioxide, as well as the terpolymerization of ethene, propene and sulfur dioxide. The resultant materials are high melting solids with an alternating alkene-SO₂ structure and an exclusive head-to-tail enchainment for propene.     

The response of immune sheep to challenge with Trichostrongylus colubriformis: enteric plasma loss and secretion of biogenic amines

Sheep were challenged with a single large dose of larvae after vaccination with irradiated Trichostrongylus colubriformis larvae. Worm counts performed on vaccinated sheep 6 or 7 days after challenge (DAC) showed that they were solidly immune and only retarded L3 larvae were recovered at this time. Enteric plasma loss (EPL) in vaccinated animals increased immediately after challenge to peak 4–6 DAC and then decreased to pre-challenge levels. In contrast, a substantial rise in EPL did not occur in unvaccinated sheep until 10 DAC. Secretion of histamine into the duodenum of immunized sheep increased significantly from 2 to 7 DAC with the highest value at 6 DAC which corresponded with a lower duodenal tissue histamine level at this time. Histamine and 5HT secretion into the small intestine of previously uninfected sheep gradually increased during 12 weeks of a trickle infection of 3000 normal T. colubriformis larvae per week. The results indicate that rejection of incoming larvae by immune sheep is accompanied by an intestinal inflammatory response involving secretion of biogenic amines and a concurrent plasma loss.     

Protective effect of recombinant tumor necrosis factor-alpha in murine salmonellosis

The enhancement of resistance by i.p. administration of murine rTNF-alpha into mice against i.p. challenge with virulent Salmonella typhimurium was studied. Administration of TNF-alpha (5 x 10(4) U/mouse) into mice at 6 or 12 h before the challenge with S. typhimurium organisms enhanced the bactericidal capacity in the peritoneal cavities of the mice. The diminution of the infecting organism in the peritoneal cavities of the TNF-alpha-treated mice was not due to the systemic spread of the organism inasmuch as few organism were recovered from other areas such as the spleen and liver. The TNF-alpha treatment effected a slight increase of neutrophils in the peritoneal cavity, but did not effect an increase of macrophages, including Ia-bearing macrophages. The survival rate of mice infected with Salmonella was improved by the i.p. injection of TNF-alpha before infection. Co-administration of smaller doses of TNF-alpha (5 x 10(3) U) and murine rIFN-gamma (10(2) U) at 6 h before the challenge also effectively enhanced bactericidal activity and protectivity. The cooperative effect of TNF-alpha and IFN-gamma was only seen when these recombinant cytokines were injected together at the proper time before the challenge. Injection of rabbit anti-TNF-alpha serum abolished the effects of TNF-alpha and the cooperative effect of TNF-alpha and IFN-gamma. Furthermore, the serum could abolish the cooperative effect of IFN-gamma and LPS on bactericidal activity, suggesting participation of LPS-induced TNF-alpha in the cooperation.     

Chemistry of vinylidene complexes XI. Synthesis of trinuclear MnFePt complexes by means of consecutive assembling out of mono- and dimetal vinylidene precursors

The dimetal μ-vinylidene complexes Cp(CO)₂MnPt(μ-C = CHPh)L₂ (L = tert.-phosphine or -phosphite), which have been obtained by coupling of the mononuclear complex Cp(CO)₂Mn=C=CHPh and unsaturated PtL₂ unit, add smoothly the Fe(CO)₄ moiety to produce trimetal MnFePt compounds. The μ₃-vinylidene cluster CpMnFePt(μ₃-C=CHPh)(CO)₆(PPh₃) was prepared in quantitative yields from the reactions of Cp(CO)₂MnPt(μ-C=CHPh)(PPh₃)L (L = PPh₃ or CO) with Fe₂(CO)₉ in benzene at 20 °C. The phosphite-substituted complexes Cp(CO)₂Mnpt(μ-C=CHPh)L₂ (L = P(OEt)₃ or P(OPrⁱ)₃) react under analogous conditions with Fe₂(CO)₉ to give mixtures (2:3) of the penta- and hexacarbonyl clusters, CpMnFePt(μ₃-C = CHPh)(CO)₅L₂ and CpMnFePt(μ₃-C = CHPh)(CO)₆L, respectively. The similar reaction of the dimetal complex Cp(CO)₂MnPt(μ-C = CHPh)(dppm), in which the Pt atom is chelated by dppm = Ph₂PCH₂PPhPin2 ligand, gives only a 15% yield of the analogous trimetal μ₃-vinylidene hexacarbonyl product CpMnFePt(μ₃-C = CHPh)(CO)(dppm), but the major product (40%) is the tetranuclear μ₄-vinylidene cluster (dppm)PtFe₃(μ₄-C = CHPh)(CO)₉. The IR and ¹H, ¹³C and ³¹P NMR data for the new complexes are reported and discussed.     

Induction of immunity against experimental tuberculosis with mycobacterial mannophosphoinositides encapsulated in liposomes containing lipid A

Abstract Mycobacterial mannophosphoinositides (PIMs) encapsulated in liposomes made of egg phosphatidylcholine (EPC) and cholesterol (CH) (2:1.5 molar ratio) were able to induce humoral and delayed type hypersensitivity (DTH, foot-pad swelling reaction) responses in mice without the help of any carrier protein. Animals immunized with this glycophospholipid antigen demonstrated enhanced percent survival on intravenous challenge with virulent M. tuberculosis . On fractionation of PIMs, pentamannophosphoinositide (PIM₅) was found to induce higher antibody and DTH reaction and proved to be more immunoprotective than other fractions. Inclusion of lipid A as immunomodulator in liposomes containing PIMs or PIM₅ resulted in a significantly increased immune response. Further, mice immunized with PIMs or PIM₅ in lipid A-containing liposomes exhibited decreased mortality on challenge with M. tuberculosis H₃₇Rv, which was comparable to BCG vaccinated animals.     

减量施氮下基肥后移对南方冬小麦产量和氮素利用效率的影响

过量施用氮肥导致氮肥利用率降低,环境风险加大.合理降低施氮量、优化氮肥运筹对于小麦高产高效栽培具有重要意义.本研究采用大田试验,以常规施氮方式(240 kg N·hm^-2, 基肥∶拔节肥∶孕穗肥=5∶3∶2)为对照,研究了不同施氮量(240、180、150 kg N·hm^-2,分别用N₂₄₀、N₁₈₀、N₁₅₀表示)及基苗肥施用时期(基施、4叶期施、6叶期施,分别用L₀、L₄、L₆表示)对小麦产量和氮素利用效率的影响.结果表明: 小麦籽粒产量随施氮量的降低而降低,但N₁₈₀与N₂₄₀处理相比无显著差异,而N₁₅₀处理显著降低;氮肥农学效率和吸收效率均以N₁₈₀处理最高.不同施肥时期间,L₄处理的籽粒产量和氮肥利用率最高.N₁₈₀四叶施肥(N₁₈₀L₄)处理的产量与对照无显著差异,但氮肥利用率显著提高.N₁₈₀L₄处理叶面积指数、旗叶光合速率、叶片氮含量、旗叶硝酸还原酶和谷氨酰胺合成酶活性、拔节后干物质和氮素积累量较对照未显著降低.适量降低氮肥用量配合基肥后移能够提高生育后期光合生产能力和氮素吸收同化能力,在保持高产的条件下实现氮素利用效率的同步提高.     

不同养殖密度下鱼粉水平对青鱼幼鱼生长及免疫的影响

为研究鱼粉水平和养殖密度对青鱼(Mylopharyngodon plceus)幼鱼生长及免疫的影响, 试验采用鱼粉水平(10%、20%)×养殖密度(50、100和200尾/箱)的双因素设计, 将青鱼幼鱼(2.50±0.02) g分为L₅₀、L₁₀₀、L₂₀₀、H₅₀、H₁₀₀和H₂₀₀ 6组, 每组3个重复, 养殖试验在水库网箱(1.5 m×1.5 m×1.5 m)中进行。结果显示: (1)生长性能: 实验中期(第8周), 青鱼的增重率随养殖密度的增加呈先上升后下降趋势, 且H₂₀₀组的青鱼增重率在养殖中期与L₂₀₀组相比有提高的趋势, 但差异不显著(P>0.05), 在实验后期(第16周)显著低于L₂₀₀组(P<0.05); L₂₀₀的存活率低于L₅₀组(P>0.05), 养殖密度和鱼粉水平对青鱼存活率与增重率有交互效应(P<0.05)。(2)免疫应激指标: 在实验中期, 低鱼粉组青鱼的溶菌酶(LSZ)、血糖(GLU)随密度的升高先下降后上升, 肠道分泌性免疫球蛋白A (S-IgA)有提高的趋势; H₂₀₀组的LSZ、补体4 (C4)、免疫球蛋白M (IgM)、S-IgA和皮质醇(COR)含量均高于L₂₀₀组, GLU低于L₂₀₀组(P>0.05)。在实验后期, 高低鱼粉组的C4随密度的增加均呈下降后上升的趋势(P>0.05)。H₂₀₀组的IgM和COR含量均高于L₂₀₀组, GLU低于L₂₀₀组(P>0.05)。综上所述, 在本实验条件下, 实验中期高密度养殖会使青鱼幼鱼生长性能有降低趋势, 对机体免疫、抗应激能力产生负面影响, 增加鱼粉水平有一定改善作用, 实验后期高密度养殖降低了低鱼粉饲料组青鱼的存活率, 提高鱼粉水平对高密度组青鱼生长性能和免疫功能无改善作用。     

A Single Intramuscular Vaccination of Mice with the HSV-1 VC2 Virus with Mutations in the Glycoprotein K and the Membrane Protein UL20 Confers Full Protection against Lethal Intravaginal Challenge with Virulent HSV-1 and HSV-2 Strains

Herpes Simplex Virus type-1 (HSV-1) and type-2 (HSV-2) establish life-long infections and cause significant orofacial and genital infections in humans. HSV-1 is the leading cause of infectious blindness in the western world. Currently, there are no available vaccines to protect against herpes simplex infections. Recently, we showed that a single intramuscular immunization with an HSV-1(F) mutant virus lacking expression of the viral glycoprotein K (gK), which prevents the virus from entering into distal axons of ganglionic neurons, conferred significant protection against either virulent HSV-1(McKrae) or HSV-2(G) intravaginal challenge in mice. Specifically, 90% of the mice were protected against HSV-1(McKrae) challenge, while 70% of the mice were protected against HSV-2(G) challenge. We constructed the recombinant virus VC2 that contains specific mutations in gK and the membrane protein UL20 preventing virus entry into axonal compartments of neurons, while allowing efficient replication in cell culture, unlike the gK-null virus, which has a major defect in virus replication and spread. Intramuscular injection of mice with 10⁷ VC2 plaque forming units did not cause any significant clinical disease in mice. A single intramuscular immunization with the VC2 virus protected 100% of mice against lethal intravaginal challenge with either HSV-1(McKrae) or HSV-2(G) viruses. Importantly, vaccination with VC2 produced robust cross protective humoral and cellular immunity that fully protected vaccinated mice against lethal disease. Quantitative PCR did not detect any viral DNA in ganglionic tissues of vaccinated mice, while unvaccinated mice contained high levels of viral DNA. The VC2 virus may serve as an efficient vaccine against both HSV-1 and HSV-2 infections, as well as a safe vector for the production of vaccines against other viral and bacterial pathogens.     

Ruthenium complexes containing tertiary phosphines and imidazole or 2,2′-bipyridine ligands

Complexes RuCl₃(PPh₃)L₂ (L = MeIm (1a, Im (1b)) and [RuCl₂(PPh₃)₂(bipy)]Cl·4H₂O (2) have been synthesized via the ruthenium(III) precursor RuCl₃(PPh₃)₂ (DMA), and characterized, including an X-ray structural analysis for 1a (MeIm = N-methylimidazole, Im = imidazole, bipy = 2,2′-bipyridyl, and DMA = N, N′-dimethylacetamide). Crystals of 1a are monoclinic, space group P2₁/n, A = 10.5491(5), B = 20.4934(9), C = 12.8285(4) Å, β = 90.166(4)°, Z = 4. The structure, which reveals a mer configuration for the chlorides, and cis-methylimidazoles, was solved by conventional heavy atom methods and was refined by full-matrix least-square procedures to R = 0.041 and R_w = 0.042 for 3328 reflections with I 3σ(I). From the RuCl₂(PPh₃)₃ precursor, the ruthenium(II) complexes RuCl₂(PPh₃)₂L₂ and [RuCl(PPh₃)L₄]Cl have been made (L = Im or MeIm), while [RuCl(dppb)Im₃]Cl has been made from [RuCl₂(dppb)]₂(μ-dppb) (dppb = Ph₂P(CH₂)₄PPh₂).     

Response of vaccinated and unvaccinated bighorn sheep (Ovis canadensis canadensis) to experimental respiratory syncytial virus challenge

Five Rocky Mountain bighorn sheep (Ovis canadensis canadensis), approximately 5 mo old and without detectable antibody titers to respiratory syncytial virus (RSV), were assigned to two groups to study the effects of RSV challenge inoculation in vaccinated (n = 3) and unvaccinated (n = 2) bighorns. The three lambs vaccinated with a modified live bovine RSV vaccine developed a detectable antibody response to the vaccine. Vaccinated and unvaccinated lambs challenged with an ovine isolate of RSV developed increased levels of neutralizing antibody, but clinical signs of disease were not observed. Neutralizing antibody titers to RSV remained higher (2-4-fold) in vaccinated lambs over time when compared to unvaccinated lambs.     

Polymeric low-valence platinum-phenanthroline complexes as precursors of platinum colloids

It was found that the reduction of Pt(II), Pt(III) and Pt(I,III) acetates with H₂ in the presence of 1,10-phenanthroline (phen), according to the standard procedure for the synthesis of palladium-561 giant clusters, resulted, unexpectedly, in the high-nuclear Pt(I) complex of the empirical composition Pt₈phen₃(OAc)₄(OH)₄(H₂O)₆ instead of the expected platinum colloid. Data of electron microscopy (TEM, HREM), small-angle X-ray scattering (SAXS), EXAFS and thermal analysis (DTA-TG) combined with elemental microanalysis all point to a loose structure of the obtained complex, with a minor Pt---Pt bonding (average coordination number for the Pt---Pt bonds is about 1). Variation of the preparation procedure resulted in a series of polymeric phen-platinum complexes, containing Pt atoms in oxidation states ranging from (+1) to (+0.3), and whose main structural features were established by the above-mentioned techniques. Giant clusters with dense Pt/PtO_x cores (coordination number for the Pt---Pt bonds is about 6) were obtained by gradual heating of the precursor Pt complex to about 200°C as well as by a modified preparation procedure at 20°C.     

Electrophilic abstractions on Os(H)2X(NO)L2: selective access to new unsaturated cationic Os(II) hydrides

Nitrosylation of Os(H)₃ClL₂ (L = P¹Pr₃) affords the known Os(H)₂Cl(NO)L₂ (2). Soft electrophiles (Ag⁻, Na⁻) react with complex 2 by chloride abstraction to ultimately yield truly 16-electron dihydride Os(H)₂(NO)(P¹Pr₃)₂⁻ (4a), characterized by variable-temperature NMR. Complex 4a reversibly binds H₂, forming Os(H)₂(H₂)(NO)(P¹Pr₃)⁻ with an unusually high barrier for intramolecular hydride exchange. Under kinetic conditions, protonation of 2 with strong acids follows the selectivity for chloride abstraction. Thermodynamically, protonation at the hydride is preferred, quantitatively producing cationic OsHCl(NO)L₂⁺, isolated and characterized by X-ray diffraction as the BAr₄^F− salt (7) (Ar^F=3,5−(CF₃)₂C₆H₃). Structures of isoelectronic OsHCl(NO)(PH₃)₂ and OsHCl(CO)(PH₃)₂ were optimized with ab initio DFT (Becke3LYP) methods and compared to show the greater unsaturation of the metal in the cationic species. Both complexes, 4a and 7, are highly electrophilic and reversibly coordinate dichloromethane in solution. The observed reactivity patterns of the synthesized unsaturated hydrides are rationalized in terms of the determining influence of the ‘push-pull’ π-stabilization of the metal center.