Synthesis,Structure, and Fluxionality of Strained Hypercoordinate Silicon‐Bridged [1]Ferrocenophanes

The first hypercoordinate sila[1]ferrocenophanes [fcSiMe(2‐C₆H₄CH₂NMe₂)] ( 5 a ) and [fcSi(CH₂Cl)(2‐C₆H₄CH₂NMe₂)] ( 5 b ) (fc=(η⁵‐C₅H₄)Fe(η⁵‐C₅H₄)) were synthesized by low‐temperature (?78 °C) reactions of Li[2‐C₆H₄CH₂NMe₂] with the appropriate chlorinated sila[1]ferrocenophanes ([fcSiMeCl] ( 1 a ) and [fcSi(CH₂Cl)Cl] ( 1 d ), respectively). Single‐crystal Xray diffraction studies revealed pseudo‐trigonal bipyramidal structures for both 5 a and 5 b , with one of the shortest reported Si???N distances for an sp³‐hybridized nitrogen atom interacting with a tetraorganosilane detected for 5 a (2.776(2) Å). Elongated Si? C_ipso bonds trans to the donating NMe₂ arms (1.919(2) and 1.909(2) Å for 5 a and 5 b , respectively) were observed relative to both the non‐trans bonds ( 5 a : 1.891(2); 5 b : 1.879(2) Å) and the Si? C_ipso bonds of the non‐hypercoordinate analogues ([fcSiMePh] ( 1 b ): 1.879(4), 1.880(4) Å; [fcSi(CH₂Cl)Ph] ( 1 e ): 1.881(2), 1.884(2)). Solution‐state fluxionality of 5 a and 5 b , suggestive of reversible coordination of the NMe₂ group to silicon, was demonstrated by means of variable‐temperature NMR studies. The ΔG^≠ of the fluxional processes for 5 a and 5 b in CD₂Cl₂ were estimated to be 35.0 and 37.6 kJ mol^?1, respectively (35.8 and 38.3 kJ mol^?1 in [D₈]toluene). The quaternization of 5 a and 5 b by MeOTf, to give [fcSiMe(2‐C₆H₄CH₂NMe₃)][OTf] ( 7 a‐ OTf) and [fcSi(CH₂Cl)(2‐C₆H₄CH₂NMe₃)][OTf] ( 7 b‐ OTf), respectively, supported the reversibility of NMe₂ coordination at the silicon center as the source of fluxionality for 5 a and 5 b . Surprisingly, low room‐temperature stability was detected for 5 b due to its tendency to intramolecularly cyclize and form the spirocyclic [fcSi(cyclo‐CH₂NMe₂CH₂C₆H₄)]Cl ( 9 ‐Cl). This process was observed in both solution and the solid state, and isolation and Xray characterization of 9 ‐Cl was achieved. The model compound, [Fc₂Si(2‐C₆H₄CH₂NMe₂)₂] ( 8 ), synthesized through reaction of [Fc₂SiCl₂] with two equivalents of Li[2‐C₆H₄CH₂NMe₂] at ?78 °C, showed a lack of hypercoordination in both the solid state and in solution (down to ?80 °C). This suggests that either the reduced steric hindrance around Si or the unique electronics of the strained sila[1]ferrocenophanes is necessary for hypercoordination to occur.     

An approach to sequence-specific antibody proteases

We describe here a novel strategy for the isolation of antibodies with sequence-specific protease activity: the synthesis of dipeptide haptens in which the targeted peptide bond has been replaced by a ring-strained or torsionally strained hydroxyethylene transition-state analog. Thus, the analogs mimic both a peptide bond in a distorted, reactive conformation and the transition state for peptide bond hydrolysis. In order to obtain sequence-specific antibody proteases, these analogs have been flanked with additional amino acid residues in preparation for immunization. In particular, we have synthesized peptides containing analogs such as 2-cis-amino-3-cis-hydroxycyclobutane carboxylic acid andendo-(3-amino-2-hydroxy)bicyclo[2.2.1]heptane-7-anti-carboxylic acid. We have also prepared a series of peptide derivatives containing analogs, such as 2-[3-amino-2-oxo-1-azetidinyl]-3-methylbutanoic acid, in which the targeted peptide bond has been incorporated into a β-lactam ring. Since the “peptide bond” has been left intact, these species mimic only a distorted ground state. At present, antibodies are being elicited against a number of the above peptide derivatives.     

Ring strain energies: substituted rings, norbornanes, norbornenes and norbornadienes

Ring strain energies (RSEs) are predicted using homodesmotic reactions at the B3LYP/6-31G^* level of theory. Substituents are conserved in the acyclic reference and any difference in energy between the ring and the acyclic reference corresponds exclusively to RSE. Small rings are stabilized by alkyl substituents and this stabilization decreases as the size of the ring increases. There is a destabilization of medium sized rings. Greater stabilization is found upon alkyl substitution at a double bond in an unsaturated ring and this stabilization decreases as ring size increases. The effects of cis-1,2-disubstitution on RSEs have been evaluated and indicate stabilization for both small and medium sized rings. RSEs of saturated and unsaturated polycyclic systems agree well with the RSEs derived from experimental thermochemical data. RSEs are reported for substituted norbornanes, norbornenes, and norbornadienes to complement experimental studies.     

Use of blowing catalysts for integral skin polyurethane applications in a controlled molecular architectural environment: Synthesis and impact on ultimate physical properties

Polyurethane elastomers of a controlled molecular architecture were synthesized using a two‐step polymerization technique. The building blocks of the elastomeric materials included urea–urethane prepolymers end‐capped with diisocyanate groups and had an exact number of urea groups at both ends. Two‐dimensional bifurcated hydrogen‐bonding networks incorporating the urea groups were, with differential scanning calorimetric and dynamic mechanical thermal analyzer techniques, responsible for the increase in the glass‐transition temperature (T_g) of the hard block and sharp interface morphology between the pure “hard” domains and pure “soft” domains. The higher extent of the phase separation between the two phases contributed to higher elastic moduli for the hard blocks and higher tensile strength for the elastomeric samples. Higher elongation values were attributed to the liberation of the elastomeric chain ends that otherwise would have been constrained in the interface region. The higher T_g values of the hard blocks corresponded to an increase in the hardness values and a decrease in the tear‐strength values. The increase in the amount of urea groups within the hard segments, as a result of the increased amount of water and blowing catalyst, resulted in elastomeric foams with higher open‐cell content. This resulted in lower resilience values as measured using the pendulum rebound test and was attributed to the ability of the open cells to absorb and dissipate energy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2526–2536, 2002     

Glucose utilization by lysine-producing fluoroacetate-sensitive mutants ofCorynebacterium glutamicum

A fluoroacetate-sensitive mutant was isolated fromCorynebacterium glutamicum, ATCC 21513, following mutagenesis with NTG. Batch fermentations show that in terms of growth kinetics, glucose utilization, and lysine formation, there are significant differences between the mutant and the parent. The mutant’s specific growth rate (0.22/h) is lower than that for the parent (0.34/h). Also, the yield expressed as lysine/glucose consumed does not alter as a function of the glucose concentration for the mutant, and is about 0.22, whereas for the parent, this coefficient decreases with increasing glucose concentration. The maximum specific rate of lysine production for the mutant is 1.3 g/L/h that is about two-fold higher than that for the parent.     

Thermochemistry of Amines: Experimental Standard Molar Enthalpies of Formation of N-Alkylated Piperidines

The standard molar enthalpies of formation _f H _m ^° (l) at the temperature T = 298.15 K were determined using combustion calorimetry for N-methylpiperidine (A), N-ethylpiperidine (B), N-propylpiperidine (C), N-butylpiperidine (D), N-cyclopentylpiperidine (E), N-cyclohexylpiperidine (F), and N-phenylpiperidine (G). The standard molar enthalpies of vaporization _l ^g H ^{m °} of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. From these data the following standard molar enthalpies of formation in gaseous phase _f H _m ^° (g) were derived for: A –(61.39 ± 0.88); B –(88.1 ± 1.3); C –(105.81 ± 0.66); D –(126.2 ± 1.3); E ( –88.21 ± 0.75); F –(135.21 ± 0.94); G (70.3 ± 1.4) kJ · mol^–1. They are used to determine the strain enthalpies of the cyclic amines A–G. The N-alkylated piperidine rings have been found to be about strainless.     

结构损伤识别的模态应变能方法探讨

分析了模态应变能用于结构损伤识别的可行性，并进行了有限元和实验验证．结果表明，模态应变能对损伤较为敏感，能够反映结构的局部状态变化，可以用来检测结构损伤位置。     

复合型加载下缺口前应力应变分布的有限元分析

用有限元法计算了一种低合金高强钢缺口试样在非对称四点弯曲加载(Ⅰ Ⅱ型复合加载)下缺口前端的变形和应力应变分布.研究结果表明:纯Ⅰ型加载时,缺口前端变形和塑性区形状对称分布.Ⅰ Ⅱ型复合加载下缺口前端的变形为一侧钝化,另一侧锐化,塑性区顺时针旋转一个角度θ,且θ随Ⅱ型载荷比例的增加而增大.表征缺口前端变形程度的d/b0值,随外加载荷P/Pgy的增加和Ⅱ型载荷比例的增加而增大.另外,对缺口前端最小塑性区路径上的最大切向正应力σθθ、三相应力度σm/和等效塑性应变εp的分布,以及它们随外加载荷P/Pgy和Ⅱ型载荷比例的变化规律也进行了分析,发现缺口试样的开裂遵循最大切应力判据.     

ZK31+0.3Yb镁合金的热力模拟

通过热压缩变形实验, 利用光学显微镜观察, 对ZK31 0.3Yb镁合金变形过程的流变应力和组织演变进行研究. 研究结果表明: 663 K/0.1 s-1是最佳的变形条件, 在此条件下, 合金的流变应力低, 动态再结晶充分激发, 合金的塑性好;当变形温度降至623 K和573 K时, 动态再结晶不能充分激发, 合金变形的流变应力明显提高, 尤其是573 K变形时流变应力达到185 Mpa;而变形温度提高到723 K时, 晶界处形成楔形裂纹, 合金的塑性差;在663 K时变形, 尽管应变速率降低至0.001 s-1, 合金的动态再结晶充分激发, 流变应力下降, 但变形的进程被减缓;当变速率提高到1.000 s-1时, 晶粒间的协调变形不能发挥作用, 合金的塑性最差.     

Al2O3陶瓷的动态响应特性及Hugoniot本构关系研究

利用VISAR系统测量技术和Lagrange测量技术,研究YB AD90陶瓷的动态响应特性,给出了该材料的Hugoniot弹性极限σHEL,动态屈服强度及各实验点的Hugoniot状态量。结果表明:YB AD90陶瓷的Hugoniot形变过程是一个典型的弹塑性形变过程;当冲击应力在σHEL为11.0GPa附近的范围内,此材料在塑性区的压缩特性表现出较明显的弥散行为。由实验结果拟合得到了材料的应力σ和比容V关系的拟合曲线及一个比较简单的应力σ和比容V的Hugoniot动态本构关系。