两种新型希夫碱及其钴(Ⅱ)配合物的合成与表征

利用1-萘胺分别与邻香草醛和对甲氧基水杨醛反应合成两种新型希夫碱化合物L1和L2;用CoCl2.6H2O分别与L1和L2进行反应,获得了与其相对应两种新的配合物CoCl2L1(1)和CoCl2L22(2)。通过元素分析、红外光谱、1H-NMR及X射线粉末衍射等测试手段,对新型希夫碱及其配合物进行了表征。结果表明,两种希夫碱酚羟基上的H原子与N原子相吸均形成了分子内氢键,并以氢键连接构成了新的六元环。L1和L2作为配体与CoCl2形成配合物时,酚羟基上的H原子没有脱去。配合物1由L1和CoCl2以摩尔比1∶1组成,配体上酚羟基氧及甲氧基氧同时与中心原子Co配位,形成双齿螯合配位构型;配合物2由L2和CoCl2以摩尔比2∶1组成,配体上只有酚羟基氧参与中心原子Co的配位,而甲氧基氧未参与配位。配合物1,2中Co原子均为四配位的。     

硝酸稀土与二水杨酸二甘醇二酯的配位研究

本文用硝酸稀土与水杨酸二甘醇二酯(简写为SE02或L)在乙酸乙酯溶液中反应,合成了一系列新的固体配合物。以La、Gd、Lu的配合物为代表,用元素分析确定其组成为Ln(NO3)3C18H18O7·nH2O(n=2或3),用IR、UV光谱考察了配合物中稀土与配体间的配位情况,证明配体中的酚羟基氧、酯羰基氧和醚氧均参与了配位,其中以末端基的酚羟基氧和羰基氧的配位为主,与重稀土的配位强度明显高于轻、中稀土。配合物在空气、水及有机溶剂中稳定性好,加热时要到300℃左右才发生放热分解反应,且重稀土的稳定性明显高于轻、中稀土。     

邻香草醛缩5-氨基水杨酸Schiff碱稀土配合物的合成与表征

通过邻香草醛和5-氨基水杨酸的反应合成了一个新的四齿Sch iff碱配体HL,红外光谱和核磁共振氢谱证明配体中有四个配位原子,分别是酚羟基氧原子、亚甲胺基团上的氮原子以及两个羧基氧原子。通过REC l3与此配体的反应合成了六种新型Sch iff碱固体稀土配合物,并通过元素分析、IR、UV-V IS1、H-NM R、热分析和摩尔电导率等物理测试手段考察了配合物的组成。结果表明,配体通过其酚羟基氧原子、亚甲胺基团上的氮原子以及两个羧基氧原子与中心离子配位,C l-也参与了配位,中心离子的配位数是7。配合物的组成可能为:RE2L3C l3.nH2O(RE=L a,N d,G d,D y,Y b,Y)。     

Er(ONO)(C8H7O3)2(H2O)3配合物的合成、表征及热分解动力学机理研究

合成了亚硝酸根·二(4-羟基-3-甲氧基-苯甲醛)·三水合铒(Ⅲ)配合物Er(ONO)(C8H7O3)2(H2O)3,用元素分析、红外光谱、摩尔电导、热重分析等手段进行表征.配合物的中心金属离子Er(Ⅲ)与2个香兰素配体中的2个酚羟基氧和2个甲氧基氧、亚硝酸根中的1个氧及3个配位水分子中的3个氧原子发生配位,配位数为8.用热重法研究了配合物的热分解动力学机理.     

低温固相反应合成苯羟乙酸稀土配合物及其性质研究

利用低温固相反应合成了4种苯羟乙酸稀土配合物:RE(L)3·4H2O[RE＝La,Nd,Eu,Tb; L= C6H5CH(OH)COO-],并通过元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成.红外光谱、核磁共振氢谱表明,苯羟乙酸稀土配合物中配体通过羧基以羧基氧负离子和醇羟基同时参与稀土离子(Ⅲ)配位,两分子水也参与稀土的配位.铕(Ⅲ)、铽(Ⅲ)配合物的荧光光谱和配体的磷光光谱表明,配体对铕(Ⅲ)、铽(Ⅲ)的荧光具有一定的敏化作用.     

双水杨醛1,6-己二胺希夫碱轻稀土配合物的合成和表征

合成并表征了双水杨醛缩 1,6 己二胺希夫碱配体 (C2 0 H2 4 N2 O2 ,以L表示 )与轻稀土Ln3 的 7种新的固体配合物 [LnL2 ](NO3) 3(Ln =La、Ce、Pr、Nd、Sm、Eu、Gd)。利用元素分析、摩尔电导、红外光谱、电子光谱、X射线衍射物相分析、热分析方法进行表征。中心金属离子Ln3 与希夫碱配体中的亚胺氮和酚羟基中的氧发生配位 ,配位数为 8。     

钐(Ⅲ)在二苯甲酰基甲基亚砜体系中的发光

合成并表征了钐(Ⅲ)的高氯酸盐与二苯甲酰基甲基亚砜(C6H5COCH2SOCH2COC6H5)的固态配合物,对配合物进行了摩尔电导率、元素分析和稀土络合滴定,确定了配合物的组成为SmL5(ClO4)3·3H2O( L=C6H5COCH2SOCH2COC6H5).配合物的红外光谱表明,配体通过一个亚砜基氧原子与稀土离子配位,而羰基氧未参与配位.配体的磷光光谱和配合物的荧光光谱表明,二苯甲酰基甲基亚砜配体对钐(Ⅲ)的荧光具有较好的敏化作用.还对钐(Ⅲ)配合物分子内能量传递及发光机理进行了讨论.     

2-2-吡啶基-4-羟基喹唑啉锌配合物的合成、结构及荧光性质

利用 2-（2-吡啶基 ）-4-羟基喹唑啉和醋酸锌在水热法条件下合成了一个新型锌配合物 [（Zn（phdq）·2H₂O）] （1） （phdq=2-（2-吡啶基）-4-羟基喹唑啉）.结构分析表明配合物 1 为单分子结构,结晶于单斜晶系,P-1 空间群.在配合物 1 中存在着丰富氢键和 π…π 作用力,通过分子间氢键和 π…π 堆积作用力使得配合物 1 形成三维网状结构.对配合物 1 和配体的固体荧光研究表明配合物的荧光明显增强,其原因可能是配体与金属 ZnII离子配位后增加了结构中的刚性.这对于开发新型荧光材料具有一定的指导与借鉴意义.      

系列Schiff配体及其Eu(Ⅲ),Tb(Ⅲ)配合物的合成、表征及荧光性质

为了研究Schiff类稀土配合物的组成和荧光性质,合成了N,N’-二(2-羟基-1-萘酚醛)-4,4’-二氨基二苯基甲烷(L1),N,N’-二(2-羟基-1-萘酚醛)-4,4’-二氨基二苯基甲烷(L2),N,N’-二(2-羟基-1-萘酚醛)-4,4’-二氨基二苯醚(L3)3种配体及其Eu(Ⅲ),Tb(Ⅲ)配合物。通过对配体和配合物的红外吸收、核磁共振、紫外吸收、元素分析、差热—热重、摩尔电导率及荧光光谱的测定分析了配合物的组成和性质。结果表明,配合物的组成为RE2(NO3)4.L4.2H2O(RE=Tb3+,Eu3+;L=L1,L2,L3),每个稀土离子与5个O、4个N配位,配位数为9,还有2个结晶水。室温下,Eu(Ⅲ),Tb(Ⅲ)配合物均有荧光发射,且Eu(Ⅲ)配合物发射出更强的Eu3+特征荧光,说明该类配体敏化Eu3+发光比Tb3+发光程度更大。     

一维链状镍配合物[Ni(C14H10N2O2)(Mf)]n的合成和晶体结构

合成了含水杨醛缩苯甲酰腙的一维链状镍配合物[Ni(C14H10N2O2)(Mf)]n(Mf=C4H9NO,即吗啡啉),通过元素分析,红外、电子光谱和X-射线单晶衍射进行了表征.晶体属单斜晶系,空间群为P21/c,a=0.9708(4)nm,b=1.4783(7)nm,c=1.2275(4)nm,β=95.728(14)°,V=1.7528(12)nm3,Z=4,Mr=384.07,Dc=1.455 g·cm-3,μ=1.129mm-1,F(000)=800,R=0.0759,wR=0.2155.中心镍离子与水杨醛缩苯甲酰腙配体提供的2个氧原子与1个氮原子以及1个配位吗啡啉的氮原子配位,形成了N2O2的平面四边形的配位构型.晶体内每个配合物分子通过分子间氢键与相邻另一个配合物分子缔合成一个沿c轴方向的一维链状结构,N…N氢键键长为0.3239(10)nm,N-H…N氢键键角为173.56 °.     

Voices of fear and anxiety and sadness and depression: The effects of speech rate and loudness on fear and anxiety and sadness and depression.

Two studies investigated the role of expressive vocal behavior (specifically, speech rate and loudness) in fear and anxiety and in sadness and depression. In the 1st study, participants spoke about personally experienced fear and anxiety-arousing and neutral events using 3 different voice styles: fast and loud, normal, and slow and soft. In the 2nd study, participants spoke about personally experienced sad or depressing and neutral events using the same 3 voice styles. In both studies, the participants' highest levels of subjective affective and cardiovascular (CV) arousal occurred when they spoke about the emotional events in a mood-congruent voice style: fast and loud in the case of fear and anxiety, and slow and soft in the case of sadness or depression. Mood-incongruent voice styles canceled the heightened levels of CV arousal normally associated with these negative emotions. The voice-style manipulation had no significant effect on the participants' levels of CV arousal during the neutral discussions. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Synthesis and analysis of mixed chlorinated-fluorinated dibenzo-p-dioxins and dibenzofurans and assessment of formation and occurrence of the fluorinated and chlorinated-fluorinated dibenzo-p-dioxins and dibenzofurans

Despite the use of multimodal therapy, higher-grade glioma is still uniformly fatal in the adult population. There is a considerable difference between the length of survival in each given patient, even within the same tumor type and malignancy grade group, suggesting that there are factors that might differentially influence outcome. To identify such factors, 107 patients with anaplastic or malignant glioma were retrospectively investigated. Clinical parameters and paraclinical data on the p53, mdm2, and EGFR genes at the DNA or protein level were evaluated by univariate analysis and Cox proportional hazards regression modeling. Kaplan-Meier survival estimation demonstrated that immunohistochemical positivity for mdm2 protein in patients with anaplastic astrocytoma or with glioblastoma multiforme was associated with a shorter survival time (p = 0.02). P53 gene mutations and immunopositivity for the epidermal growth factor receptor (EGFR) protein were not significantly related to poor prognosis. The Cox proportional hazards model revealed immunohistochemical positivity for p53, mdm2, or for both of them, the presence of postoperative irradiation, and the extent of surgical resection of tumor to be variables significantly associated with prolonged survival. EGFR overexpression, age over 60 years, and Karnofsky performance score below 40 points did not significantly shorten survival time. In conclusion, the present study identified immunohistochemically detected mdm2-protein overexpression as a statistically significant negative prognostic parameter in patients bearing anaplastic or malignant glioma. Association analysis of variables revealed a possible correlation between mdm2 and p53, which is also consistent with the biological interaction mode of both proteins in vivo.     

Sexuality and aging--usual and successful

BACKGROUND: As aging research increasingly reflects an effort to dissociate true time-driven changes from those that can be improved, sexuality in later life remains largely unexplored. Several problems are evident. There is a lack of normative data, a lack of a conceptual framework relating to the biology, psychology, and sociology of sex, and an attitudinal resistance that obscures the entire topic. METHODS: We conducted a three-part instructional series on major topics involved with sexuality and aging. We surveyed our group of attendees (n 158, average age 68 for males, 65 for females) before and after the series. RESULTS: A remarkably robust sex life was evidenced by both the men and the women, even until advanced old age. Yet, a substantially decreased involvement was reported from 10 years earlier. Despite current activities, people of both sexes wished they were participating even more than they currently were. Impotency was identified as the major negative feature for the men; relationship problems were for the women. A questionnaire 6 months after the series reported improved sexual attitudes, but no change in sexual activities from the earlier survey. CONCLUSION: Sexuality is a major quality-of-life issue which persists into old age. Our study showed that the usual sexual practices reported by our group were not considered by them to be ideal. The intervention of this instructional series provided improved sexual attitudes but not performance. Additional studies are encouraged.     

Spondylolysis and spondylolisthesis and sports

Spondylolysis and spondylolisthesis occur predominantly in the lower lumbar spine. Besides congenital defects such as predisposition of spondylolysis the correlation between competitive sports activities and an increased incidence of spondylolysis is proved. In early stages, complete healing can be achieved by conservative treatment (abstinence from sports activities for 3 months, orthesis). Persistence of pain, neurologic symptoms and progression of vertebral slipping are indications for operative treatment (reconstruction of the isthmus, dorso-ventral spondylodesis). The exercise tolerance depends on the extent of instability, progression of vertebral slipping and clinical symptoms. The limits of exercise tolerance vary among the individual athletes and require the decision of the physician. Backstroke swimming, abdominal and back muscle strengthening exercises, and types of sport involving smooth movements are advisable. Sports education in school is possible without restriction in patients with stable spondylolysis and in those with spondylolisthesis without unfavourable concomitant factors.     

Larks and owls and health, wealth, and wisdom

OBJECTIVE: To test the validity of Benjamin Franklin's maxim "early to bed and early to rise makes a man healthy, wealthy, and wise." DESIGN: Cross sectional analysis of sleeping patterns in a nationally representative group of elderly people, and longitudinal investigation of mortality. SETTING: Eight areas in Britain (five in England, two in Scotland, and one in Wales). SUBJECTS: 1229 men and women aged 65 and over who in 1973-4 had taken part in a survey funded by the Department of Health and Social Security and for whom data on sleeping patterns, health, socioeconomic circumstances, and cognitive function had been recorded. MAIN OUTCOME MEASURES: Self reported income, access to a car, standard of accommodation, performance on a test of cognitive function, state of health and mortality during 23 years of follow up. RESULTS: 356 people (29%) were defined as larks (to bed before 11 pm and up before 8 am) and 318 (26%) were defined as owls (to bed at or after 11 pm and up at or after 8 am). There was no indication that larks were richer than those with other sleeping patterns. On the contrary, owls had the largest mean income and were more likely to have access to a car. There was also no evidence that larks were superior to those with other sleeping patterns with regard to their cognitive performance or their state of health. Both larks and owls had a slightly reduced risk of death compared with the rest of the study sample, but this was accounted for by the fact that they spent less time in bed at night. In the study sample as a whole, longer periods of time in bed were associated with increased mortality. After adjustment for age, sex, the presence of illness, and other risk factors, people who spent 12 or more hours in bed had a relative risk of death of 1.7 (1.2 to 2.5) compared with those who were in bed for 9 hours. The lowest risk occurred in people who spent 8 hours in bed (adjusted relative risk 0.8; 0.7 to 1.0). CONCLUSION: These findings do not support Franklin's claim. A "late to bed and late to rise" lifestyle does not seem to lead to socioeconomic, cognitive, or health disadvantage, but a longer time spent in bed may be associated with increased mortality.     

Craniometaphyseal and craniodiaphyseal dysplasia, head and neck manifestations and management

Mechanical allodynia (MA) following hand injury is a well-documented clinical problem. The purpose of this pilot study was to examine the relationship between hand MA and the upper limb tension test (ULTT). The ULTT mechanically stresses the neural structures from the C5/6/7 neural foramina to the median nerve distally. This study examined 29 subjects with unilateral hand MA before and after a 2-week neural self-mobilization programme. There was a significant difference between the subjects' affected and unaffected sides when tested using the ULTT, both in reproduction of symptoms and in reduced range of motion of the ULTT. Following the self-mobilization program, there was an improvement in the range of the ULTT, and subjects reported a reduction in their symptoms. Complete recovery was not obtained in all cases. The results of this study suggest that the ULTT is a useful tool both in assessment and treatment of subjects with hand MA.     

深云立交桥梁检测及加固改造

根据深云立交桥梁的检测结果，对该桥目前的整体状况、工作状态，及其使用情况做出综合评价，对桥的病害原因进行了分析，并提出合理的加固方案。     

关于摩尔浓度及其与硬度转换关系问题的讨论

众所周知，国际单位制物质的量采用摩尔(mol)表示，近几年出版的给排水专业书籍，为了与国际单位制接轨，逐渐将摩尔的使用频率不断提高，被给排水技术人员广泛应用的新版给排水设计手册，将表示物质浓度的单位“当量／升”或“毫克当量／升”．改为mol／l或mmol／l，虽然编者对其基本单元定义作了说明，但在实际运用上仍会出现误解，     

《儿子与情人》的语码转换与男女二元对立

劳伦斯小说《儿子与情人》一个鲜明的语言特色就是标准英语和当地方言频繁的语码转换。莫瑞尔用方言来对抗妻子,而妻子坚持用标准英语,偶尔也用方言来讽刺、挖苦丈夫。语码转换反映了劳伦斯男女二元对立的哲学思想。