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11. 发明授权

US07750172B2 High metathesis activity ruthenium and osmium carbene complexes 失效
标题翻译：高复分解活性钌和咔唑络合物
公开(公告)号：US07750172B2
公开(公告)日：2010-07-06
申请号：US11929358
申请日：2007-10-30
申请人： Robert H. Grubbs , Peter Schwab , Sonbinh T. Nguyen
发明人： Robert H. Grubbs , Peter Schwab , Sonbinh T. Nguyen
IPC分类号： C07F15/00 , B01J31/00 , C08F4/42
CPC分类号： C08F4/80 , B01J31/18 , B01J31/2265 , B01J31/24 , B01J31/2404 , B01J2231/14 , B01J2231/543 , B01J2531/821 , B01J2531/825 , C07F15/002 , C07F15/0046 , C08F32/00 , C08G61/08
摘要： Ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins are disclosed. Also disclosed are methods of making the carbene compounds. The carbene compounds are of the formula where M is Os or Ru; R1 is hydrogen; R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; X and X1 are independently selected from any anionic ligand; and L and L1 are independently selected from any neutral electron donor. The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors. The ruthenium and osmium carbene compounds of the present invention may be used to catalyze olefin metathesis reactions including, but not limited to, ROMP, RCM, depolymerization of unsaturated polymers, synthesis of telechelic polymers, and olefin synthesis.
摘要翻译：公开了在各种官能团存在下稳定并且可用于催化非限制性环状和无环烯烃上的烯烃复分解反应的钌和锇卡宾化合物。还公开了制备卡宾化合物的方法。卡宾化合物具有下式：其中M是Os或Ru; R1是氢; R选自氢，取代或未取代的烷基和取代或未取代的芳基; X和X 1独立地选自任何阴离子配体; L和L 1独立地选自任何中性给电子体。本发明的钌和锇卡宾化合物可以使用重氮化合物，通过中性电子给体配体交换，通过交叉复分解，使用乙炔，使用累积的烯烃，以及使用重氮化合物和中性电子给体的一锅法合成。本发明的钌和锇卡宾化合物可用于催化烯烃复分解反应，包括但不限于ROMP，RCM，不饱和聚合物的解聚，遥爪聚合物的合成和烯烃合成。

12. 发明授权

US07560499B2 Initiator and ultraviolet absorber blends for changing lens power by ultraviolet light 有权
标题翻译：用于通过紫外线改变透镜功率的引发剂和紫外线吸收剂混合物
公开(公告)号：US07560499B2
公开(公告)日：2009-07-14
申请号：US11149837
申请日：2005-06-10
申请人： Jagdish M. Jethmalani , Shiao H. Chang , Robert H. Grubbs
发明人： Jagdish M. Jethmalani , Shiao H. Chang , Robert H. Grubbs
IPC分类号： C08F2/50 , C08J3/28
CPC分类号： C08G77/388 , A61L27/14 , A61L27/50 , A61L2430/16 , C08F2/50 , C08G77/38 , C08K5/3475 , C08K5/5419 , C08L83/06 , C08L83/08 , C08L83/14 , G02C2202/14 , C08L83/00 , C08L2666/14
摘要： Novel blends of photo-initiators and photo-absorbers are disclosed. By the proper selection of the type and amount of absorber and initiator used in a composition, it is possible to regulate the conditions under which photo-induced reactions occur. In a specific embodiment, blends of UV initiators and photoabsorbers are used to control the conditions under which UV initiated polymerization occurs.
摘要翻译：公开了光引发剂和光吸收剂的新型共混物。通过适当选择组合物中使用的吸收剂和引发剂的类型和量，可以调节光诱导反应发生的条件。在一个具体实施方案中，UV引发剂和光吸收剂的共混物用于控制发生UV引发聚合的条件。

13. 发明授权

US07229634B2 Engineered proteins, and methods of making and using 有权
标题翻译：工程蛋白质，以及制造和使用方法
公开(公告)号：US07229634B2
公开(公告)日：2007-06-12
申请号：US11040130
申请日：2005-01-21
申请人： David A. Tirrell , Daniel M. Schwartz , Paul J. Nowatzki , Robert H. Grubbs
发明人： David A. Tirrell , Daniel M. Schwartz , Paul J. Nowatzki , Robert H. Grubbs
IPC分类号： A61F2/16 , A61F2/14 , A61K38/39
CPC分类号： C07K14/78 , A01K2217/05 , A01K2227/105 , A61F9/007 , A61L27/227 , A61L27/34 , A61L2430/16 , C07K2319/20 , C07K2319/21 , G02C7/02 , C08L89/00
摘要： The present invention provides engineered proteins and biomedical products made from the engineered proteins. The biomedical products include lenses useful for ophthalmic purposes.
摘要翻译：本发明提供由工程蛋白质制成的工程化蛋白质和生物医学产品。生物医学产品包括可用于眼科用途的镜片。

14. 发明授权

US07175885B2 Compositionally different polymer-based sensor elements and methods for preparing same 失效
标题翻译：组分不同的基于聚合物的传感器元件及其制备方法
公开(公告)号：US07175885B2
公开(公告)日：2007-02-13
申请号：US09770089
申请日：2001-01-24
申请人： Nathan S. Lewis , Robert H. Grubbs , Robert D. Sanner , Eric J. Severin
发明人： Nathan S. Lewis , Robert H. Grubbs , Robert D. Sanner , Eric J. Severin
IPC分类号： B05D1/02
CPC分类号： G01N27/126 , B01J19/0046 , B01J2219/00351 , B01J2219/00524 , B01J2219/00596 , B01J2219/00605 , B01J2219/00612 , B01J2219/00637 , B01J2219/00659 , B01J2219/00707 , B01J2219/00722 , C40B40/14 , C40B60/14 , G01N21/77 , G01N33/0031 , G01N2021/773 , Y10T436/2575
摘要： The present invention provides a combinatorial approach for preparing arrays of chemically sensitive polymer-based sensors which are capable of detecting the presence of a chemical analyte in a fluid in contact therewith. The described methods and devices comprise combining varying ratios of at least first and second organic materials which, when combined, form a polymer or polymer blend that is capable of absorbing a chemical analyte, thereby providing a detectable response. The detectable response of the sensors prepared by this method is not linearly related to the mole fraction of at least one of the polymer-based components of the sensors, thereby making arrays of these sensors useful for a variety of sensing tasks.
摘要翻译：本发明提供了一种用于制备化学敏感聚合物基传感器阵列的组合方法，其能够检测与其接触的流体中化学分析物的存在。所描述的方法和装置包括组合至少第一和第二有机材料的变化比例，其在组合时形成能够吸收化学分析物的聚合物或聚合物共混物，由此提供可检测的响应。通过该方法制备的传感器的可检测响应与传感器的至少一种基于聚合物的组分的摩尔分数没有线性关系，从而使得这些传感器的阵列可用于各种感测任务。

15. 发明授权

US07074840B2 Light adjustable lenses capable of post-fabrication power modification via multi-photon processes 有权
标题翻译：能够通过多光子过程进行后制造功率修改的光调节透镜
公开(公告)号：US07074840B2
公开(公告)日：2006-07-11
申请号：US10914378
申请日：2004-08-09
申请人： Shiao H. Chang , Robert H. Grubbs , Julia A. Kornfield , Axel Brait
发明人： Shiao H. Chang , Robert H. Grubbs , Julia A. Kornfield , Axel Brait
IPC分类号： G03C1/73 , C08L33/04 , C08F2/50
CPC分类号： A61L27/14 , A61F2/1627 , A61F2/1635 , A61F2/1659 , A61L27/18 , C08F2/50 , C08F290/00 , C08F290/148 , C08F293/005 , C08G77/045 , C08G77/14 , C08G77/24 , C08L53/00 , C08L83/04 , G02C7/04 , G02C2202/14 , G03C1/733 , Y10S522/904 , C08L2666/02
摘要： The invention relates to novel photoinitiators and their use in light adjustable compositions. The initiatives comprise two or more multiphoton chromophores linked by a bridging compound. The bridging compound consists of a material that is compatible with the base material of the light adjustable composition. The novel photoinitiator permit the readjustment of light adjustable material without the need for significant amounts of photoabsorbers.
摘要翻译：本发明涉及新型光引发剂及其在光调节组合物中的用途。这些举措包括由桥连化合物连接的两个或更多个多光子发色团。桥接化合物由与光可调组合物的基材兼容的材料组成。新型光引发剂允许重新调节光可调材料，而不需要大量的光吸收剂。

16. 发明授权

US06884859B2 Ring-opening metathesis polymerization of bridged bicyclic and polycyclic olefins containing two or more heteroatoms 有权
标题翻译：含有两个或多个杂原子的桥连双环和多环烯烃的开环易位聚合
公开(公告)号：US06884859B2
公开(公告)日：2005-04-26
申请号：US10232105
申请日：2002-08-29
申请人： Robert H. Grubbs , Oren A. Scherman , Hyunjin M. Kim
发明人： Robert H. Grubbs , Oren A. Scherman , Hyunjin M. Kim
IPC分类号： C08F4/26 , C08F4/44 , C08F4/64 , C08F4/70 , C08F8/04 , C08G61/06 , C08G61/08 , B01J31/22
CPC分类号： C08F8/04 , C08G61/06 , C08G61/08 , C08G2261/3324 , C08G2261/418
摘要： A method is provided for synthesizing a polymer in a controlled fashion using a ring-opening metathesis polymerization (ROMP) reaction, wherein polymerization is carried out using a catalytically effective amount of an olefin metathesis catalyst and a bridged bicyclic or polycyclic olefin monomer that contains at least two heteroatoms directly or indirectly linked to each other. Preferred catalysts are Group 8 transition metal complexes, particularly complexes of Ru and Os. Such complexes include the ruthenium bisphosphine complex (PCy3)2(Cl)2Ru═CHPh (1) and the ruthenium carbene complex (IMesH2)(PCy3)(Cl)2Ru═CHPh (2). The invention also provides novel regioregular polymers synthesized using the aforementioned methodology, wherein the polymers may be saturated, unsaturated, protected, and/or telechelic. An exemplary polymer is poly((vinyl alcohol)2-alt-methylene)(MVOH).
摘要翻译：提供了一种使用开环易位聚合（ROMP）反应以受控的方式合成聚合物的方法，其中使用催化有效量的烯烃复分解催化剂和桥连的双环或多环烯烃单体进行聚合，至少两个直接或间接连接的杂原子。优选的催化剂是第8族过渡金属络合物，特别是Ru和Os的络合物。这样的络合物包括钌双膦络合物（PCy 3 N 2）（Cl）2 Ru-CHPh（1）和钌卡宾络合物（IMesH （C 3）（Cl）2 Ru-CHPh（2）。本发明还提供了使用上述方法合成的新的区域规整聚合物，其中聚合物可以是饱和的，不饱和的，保护的和/或遥爪的。示例性聚合物是聚（（乙烯醇）2 - 亚甲基）（MVOH）。

17. 发明授权

US06426419B1 Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity 失效
标题翻译：与显示高烯烃复分解活性的三亚唑基配体配位的钌金属亚烷基络合物
公开(公告)号：US06426419B1
公开(公告)日：2002-07-30
申请号：US09539840
申请日：2000-03-31
申请人： Robert H. Grubbs , Tina M. Trinka
发明人： Robert H. Grubbs , Tina M. Trinka
IPC分类号： C07F1500
CPC分类号： C07F15/0046
摘要： The invention discloses ruthenium alkylidene complexes of the type (PCy3)(L)Cl2Ru(CHPh), where L is a triazolylidene ligand of the general formula: These catalysts have been found to be considerably more active for olefin metathesis at elevated temperatures than the parent catalyst (PCy3)2Cl2Ru(CHPh)(2). For example, complex 14 (L=1,3,4-triphenyl-4.5-dihydro-1H-triazol-5-ylidene) is able to catalyze the ring-closing metathesis of substituted dienes to give tetra-substituted cyclic olefins in good yield. In addition, this complex demonstrates the analogous stability towards oxygen and moisture exhibited by ruthenium alkylidene 2.
摘要翻译：本发明公开了类型（PCy3）（L）Cl2Ru（CHPh）类型的钌亚烷基络合物，其中L是具有以下通式的三亚唑基亚配体：已经发现这些催化剂在高于母体的温度下对烯烃复分解更有活性催化剂（PCy3）2Cl2Ru（CHPh）（2）。例如，络合物14（L = 1,3,4-三苯基-4,5-二氢-1H-三唑-5-亚基）能够催化取代的二烯的闭环复分解，得到四取代的环状烯烃，产率良好。此外，该复合物证明了亚烷基钌亚烷基2表现出的对氧气和水分的稳定性。

18. 发明授权

US06414097B1 Methods for cross-methathesis of terminal olefins 有权
标题翻译：端烯烃的交叉拟合方法
公开(公告)号：US06414097B1
公开(公告)日：2002-07-02
申请号：US09919658
申请日：2001-07-31
申请人： Robert H. Grubbs , Daniel J. O'Leary , Helen E. Blackwell
发明人： Robert H. Grubbs , Daniel J. O'Leary , Helen E. Blackwell
IPC分类号： C08F426
CPC分类号： C07C269/06 , C07C41/30 , C07C67/475 , C07C69/78 , C07C69/007 , C07C69/16 , C07C43/166 , C07C43/1787
摘要： A method for the cross-metathesis of terminal olefins is disclosed. The method describes making disubstituted internal olefin products by contacting a first terminal olefin with another first terminal olefin to form a dimer and then contacting the dimer with a second terminal olefin in the presence of a catalyst having the formula where M may be Os or Ru, R and R1 may be the same or different and may be hydrogen or a substitutent group selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20alkynyl, aryl, C1C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl. X and X1 may be the same or different and may be any anionic ligand. L and L1 may be the same or different and may be any neutral electron donor.
摘要翻译：公开了一种用于末端烯烃交叉复分解的方法。该方法描述了通过使第一末端烯烃与另一个第一末端烯烃接触以形成二聚体制备二取代的内烯烃产物，然后在具有式I的催化剂存在下使二聚体与第二末端烯烃接触，M可以是Os或Ru，R 并且R 1可以相同或不同，并且可以是氢或选自C 1 -C 20烷基，C 2 -C 20烯基，C 2 -C 20炔基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20 炔氧基，芳氧基，C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基和C 1 -C 20烷基亚磺酰基。 X和X 1可以相同或不同，并且可以是任何阴离子配体。 L和L1可以相同或不同，并且可以是任何中性电子给体。

19. 发明授权

US06376690B1 Method of removing transition metals 有权
标题翻译：去除过渡金属的方法
公开(公告)号：US06376690B1
公开(公告)日：2002-04-23
申请号：US09386205
申请日：1999-08-30
申请人： Robert H. Grubbs , Heather D. Maynard , David M. Lynn
发明人： Robert H. Grubbs , Heather D. Maynard , David M. Lynn
IPC分类号： C07F1500
CPC分类号： C07F15/0046 , C08G61/08
摘要： The present invention generally relates to the discovery that the solubility of metal complexes may be readily manipulated by the addition of one or more solubility-enhancing compounds. This manipulation of the solubilities allows for the preparation of suitable samples for precise quantitative analysis and for the facile purification of the desired products from the reaction mixture containing one or more metal complexes. In one embodiment of the invention, the relative solubilities between two solutions are manipulated so as cause the metal complex found in a first solution to transfer to a second solution that is generally immiscible with the first solution. The metal complex is thus separated from the reaction mixture which comprises the first solution by the removal of the second solution. In another embodiment, the solubility-enhancing compounds of the present invention is used to prepare samples containing metal complexes for precise quantitative analysis such as inductively coupled plasma mass spectroscopy.
摘要翻译：本发明一般涉及金属配合物的溶解度可以容易地通过加入一种或多种溶解度增强化合物来操作的发现。这种溶解度的操作允许制备合适的样品以进行精确的定量分析，并且从含有一种或多种金属络合物的反应混合物中容易地纯化所需产物。在本发明的一个实施方案中，操作两种溶液之间的相对溶解度，使得在第一溶液中发现的金属络合物转移到通常与第一溶液不混溶的第二溶液。因此，金属络合物通过除去第二溶液与包含第一溶液的反应混合物分离。在另一个实施方案中，本发明的溶解度增强化合物用于制备含有金属络合物的样品以进行精确的定量分析，例如电感耦合等离子体质谱法。

20. 发明授权

US06313332B1 Synthesis of ruthenium or osmium metathesis catalysts 有权
标题翻译：钌或锇复分解催化剂的合成
公开(公告)号：US06313332B1
公开(公告)日：2001-11-06
申请号：US09672585
申请日：2000-09-28
申请人： Robert H. Grubbs , Tomas R. Belderrain , Seth N. Brown , Thomas E. Wilhelm
发明人： Robert H. Grubbs , Tomas R. Belderrain , Seth N. Brown , Thomas E. Wilhelm
IPC分类号： C07F1500
CPC分类号： B01J31/2404 , B01J31/2265 , B01J31/2295 , B01J31/24 , B01J2231/14 , B01J2231/54 , B01J2231/543 , B01J2531/821 , B01J2531/825 , C07F15/002 , C07F15/0046
摘要： The present invention relates to the synthesis of highly active ruthenium and osmium carbene metathesis catalyst in good yield from readily available starting materials. The catalysts that may be synthesized are of the general formula wherein: M is ruthenium or osmium; X and X1 are independently any anionic ligand; L and L1 are any neutral electron donor ligand; and, R and R1 are each hydrogen or one of the following substituent groups: C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl. Optionally, the substituent group may be substituted with one or more groups selected from C1-C5 alkyl, halogen, C1-C5 alkoxy, and aryl. When the substitute aryl group is phenyl, it may be further substituted witn one or more groups selected from a halogen, a C1-C5 alkyl, or a C1-C5 alkoxy. Specific synthetic protocols for vinyl alkylidene catalysts wherein R is hydrogen and R1 is —CHCR12R13 and non-vinyl alkylidene catalysts are also disclosed. In addition to the ease of synthesis (typically a one-step synthesis), the reactions generally may be run at or above room temperature and the resulting products usually may be used without extensive post synthesis purification.
摘要翻译：本发明涉及从容易获得的原料合成高活性钌和碳卡因复分解催化剂的良好产率。可以合成的催化剂是通式为：M是钌或锇; X和X 1独立地是任何阴离子配体; L和L 1是任何中性电子给体配体; C 1 -C 20烷基，C 1 -C 20烷基，C 1 -C 20烷基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20炔基， C20炔氧基，芳氧基，C2-C20烷氧基羰基，C1-C20烷硫基，C1-C20烷基磺酰基和C1-C20烷基亚磺酰基。任选地，取代基可以被一个或多个选自C 1 -C 5烷基，卤素，C 1 -C 5烷氧基和芳基的基团取代。当取代芳基为苯基时，可以进一步被一个或多个选自卤素，C 1 -C 5烷基或C 1 -C 5烷氧基的基团取代。还公开了其中R为氢且R 1为-CHCR 12 R 13的乙烯基亚烷基催化剂和非乙烯基亚烷基催化剂的具体合成方案。除了易于合成（通常是一步合成）之外，反应通常可以在室温或更高的温度下进行，所得产物通常可以在没有广泛的后合成纯化的情况下使用。

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