Efecto del mal seco (Pythium myriotylum Drechs) en campo y sombreadero sobre la agromorfología de quince accesiones de quequisque (Xanthosoma spp) desarrollo de síntomas y detección microbiológica

El quequisque ( Xanthosoma spp.), familia Aráceae, es importante para el consumo interno y la exportación en Nicaragua, tiene como problema principal al mal seco ( Pythium myriotylum Drechs ) , que causa la pérdida total del rendimiento. Se establecieron cuatro ensayos para evaluar el efecto del mal seco sobre agromorfología de 15 accesiones de quequisque en suelos con (scams) y sin antecedentes de mal seco (ssams). Ensayo I: se evaluó el efecto del mal seco sobre la agromorfología de 15 accesiones en scams en Nueva Guinea. Se empleó el diseño BCA con tres bloques. Ensayo II: se estableció en DCA, se evaluó el comportamiento de 7 de las accesiones en ssams y se comparó con el rendimiento obtenido en scams. Ensayo III: se cultivó raíces de plantas infectadas en los medios de cultivo AN, V-8 y PARC y dilución en serie del scams para verificar la presencia de P myriotylum . Ensayo IV: se evaluó el desarrollo de síntomas de la enfermedad en las raíces, se establecieron 14 accesiones en scams en bolsas de polietileno (15 plantas por accesión) en sombreadero. Todas las accesiones desarrollaron mal seco, produjeron plantas débiles de 30-40 cm de altura, con tres hojas máximo y ningún rendimiento. Las accesiones en ssams reportaron 3-12 t ha -1 de rendimientos promedios. Las plantas en scams registrar on 91-100 % de pérdidas en el rendimiento. La infección en las raíces ocurre a partir de los 21 días después de la siembra, la planta genera nuevas raíces que también se infectan y muere por agotamiento de las reservas. La dilución en serie no resultó en el aislamiento del patógeno. Sembrar raíces recién infectadas resultó en la presencia de micelios del hongo en los medios V-8 y PARC.

A (des)confiança do cidadão no Poder Legislativo e a qualidade da democracia no Brasil

Apresenta reflexões sobre a democracia brasileira, abordando a representação, o impacto da imagem do Poder Legislativo sobre a participação popular e os efeitos dessas relações sobre a qualidade do regime democrático vivenciado. Enfoca a correlação entre a confiança da população no poder constituído, o pleno exercício da cidadania e o fortalecimento da democracia, enfatizando o papel da educação cidadã nesse processo.

Modelo de representação na legislação cubana

Com base em pesquisa histórico-documental com técnica comparativa, estuda a organização do Estado cubano, a partir de sua legislação. Expõe um relato histórico sobre o momento de construção da atual Constituição e apresenta as leis referentes ao processo eleitoral, revogação de mandatos e conselho popular. Constata que o modelo de representação do Estado cubano possui um alto grau de delegação, o que o torna mais participativo que o modelo de representação do Brasil, que é fortemente marcado pela independência dos eleitos.

[Discurso do Deputado João Agripino : Sessão da Câmara dos Deputados de 09 de agosto de 1956]

Discussão do Projeto de Lei nº 1.234, de 1956, que dispõe sobre a mudança da Capital Federal e dá outras providências. Reparos à natureza jurídica e aos plenos poderes dados à Companhia Urbanizadora da Nova Capital. Apresentação de emendas ao PL 1.234/56. Apartes: Emival Caiado, Wagner Estelita, Fonseca e Silva e Corrêa e Costa.

室温铁磁性半导体Mn_xGa_(1-x)Sb

采用离子注入、离子沉积及后期退火方法制备了稀磁半导体单晶Mn_xGa_(1-x)Sb，在室温下（300 K）获得了单晶的磁滞回线。用X射线衍射方法分析了铁磁性半导体单晶Mn_xGa_(1-x)Sb的结构，用电化学C-V法分析了单晶的载流子浓度分布。由X射线衍射得知，Mn_xGa_(1-x)Sb中Mn含量逐渐由近表面处的x = 0.09下降到晶片内部的x = 0。电化学C-V测得单晶的空穴浓度高达1 * 10~(21)cm~(-3)，表明Mn_xGa_(1-x)Sb单晶中大部分Mn原子占据Ga位，起受主作用。

A Model of Ischemia-Induced Neuroblast Activation in the Adult Subventricular Zone

12 p.

Encouraging them to come to us: changing the way that information is made available to farmers

Recommendations for changes to service provision and fisheries policy in support of poverty alleviation emerged recently in India from a process know as facilitated advocacy (see Case Study SI 2) that helped to negotiate and support a role for poor people and their service providers, to contribute to changes in services and policies. Two of the key recommendations to emerge from farmers and fishers, which were prioritized by Fisheries Departments, were to change the way that information is made available and to simplify procedures for accessing government schemes and bank loans. This case which identifies the origin of these recommendations to change the way that information is made available, shows how different models of the concept have emerged, and follows the development of the One-stop Aqua Shops (OAS) in the eastern Indian states of Jharkhand, Orissa and West Bengal, that represent a new and vital tier in communications in aquaculture. (12 p.)

Ecological condition of coastal ocean waters along the U.S. Western Continental Shelf: 2003

Executive Summary: The western National Coastal Assessment (NCA-West) program of EPA, in conjunction with the NOAA National Ocean Service (NOS), conducted an assessment of the status of ecological condition of soft sediment habitats and overlying waters along the western U.S. continental shelf, between the target depths of 30 and 120 m, during June 2003. NCA-West and NOAA/NOS partnered with the West Coast states (Washington (WA), Oregon (OR), and California (CA)), and the Southern California Coastal Water Research Project (SCCWRP) Bight ’03 program to conduct the survey. A total of 257 stations were sampled from Cape Flattery, WA to the Mexican border using standard methods and indicators applied in previous coastal NCA projects. A key study feature was the incorporation of a stratified-random sampling design with stations stratified by state and National Marine Sanctuary (NMS) status. Each of the three states was represented by at least 50 random stations. There also were a total of 84 random stations located within NOAA’s five NMSs along the West Coast including the Olympic Coast NMS (OCNMS), Cordell Bank NMS (CBNMS), Gulf of Farallones NMS (GFNMS), Monterey Bay NMS (MBNMS), and Channel Islands NMS (CINMS). Collection of flatfish via hook-and-line for fish-tissue contaminant analysis was successful at 50 EMAP/NCA-West stations. Through a collaboration developed with the FRAM Division of the Northwest Fisheries Science Center, fish from an additional 63 stations in the same region and depth range were also analyzed for fish-tissue contaminants. Bottom depth throughout the region ranged from 28 m to 125 m for most stations. Two slightly deeper stations from the Southern California Bight (SCB) (131, 134 m) were included in the data set. About 44% of the survey area had sediments composed of sands (< 20% silt-clay), about 47% was composed of intermediate muddy sands (20-80% silt-clay), and about 9% was composed of muds (> 80% silt-clay). The majority of the survey area (97%) had relatively low percent total organic carbon (TOC) levels of < 2%, while a small portion (< 1%) had high TOC levels (> 5%), in a range potentially harmful to benthic fauna. Salinity of surface waters for 92% of the survey area were > 31 psu, with most stations < 31 psu associated with the Columbia River plume. Bottom salinities ranged only between 31.6 and 34.4 psu. There was virtually no difference in mean bottom salinities among states or between NMS and non-NMS stations. Temperatures of surface water (range 8.5 -19.9 °C) and bottom water (range 5.8 -14.7 °C) averaged several degrees higher in CA in comparison to WA and OR. The Δσt index of watercolumn stratification indicated that about 31% of the survey area had strong vertical stratification of the water column. The index was greatest for waters off WA and lowest for CA waters. Only about 2.6 % of the survey area had surface dissolved oxygen (DO) concentrations ≤ 4.8 mg/L, and there were no values below the lower threshold (2.3 mg/L) considered harmful to the survival and growth of marine animals. Surface DO concentrations were higher in WA and OR waters than in CA, and higher in the OC NMS than in the CA sanctuaries. An estimated 94.3% of the area had bottom-water DO concentrations ≤ 4.8 mg/L and 6.6% had concentrations ≤ 2.3 mg/L. The high prevalence of DO from 2.3 to 4.8 mg/L (85% of survey area) is believed to be associated with the upwelling of naturally low DO water across the West Coast shelf. Mean TSS and transmissivity in surface waters (excluding OR due to sample problems) were slightly higher and lower, respectively, for stations in WA than for those in CA. There was little difference in mean TSS or transmissivity between NMS and non-NMS locations. Mean transmissivity in bottom waters, though higher in comparison to surface waters, showed little difference among geographic regions or between NMS and non-NMS locations. Concentrations of nitrate + nitrite, ammonium, total dissolved inorganic nitrogen (DIN) and orthophosphate (P) in surface waters tended to be highest in CA compared to WA and OR, and higher in the CA NMS stations compared to CA non-sanctuary stations. Measurements of silicate in surface waters were limited to WA and CA (exclusive of the SCB) and showed that concentrations were similar between the two states and approximately twice as high in CA sanctuaries compared to OCNMS or nonsanctuary locations in either state. The elevated nutrient concentrations observed at CA NMS stations are consistent with the presence of strong upwelling at these sites at the time of sampling. Approximately 93% of the area had DIN/P values ≤ 16, indicative of nitrogen limitation. Mean DIN/P ratios were similar among the three states, although the mean for the OCNMS was less than half that of the CA sanctuaries or nonsanctuary locations. Concentrations of chlorophyll a in surface waters ranged from 0 to 28 μg L-1, with 50% of the area having values < 3.9 μg L-1 and 10% having values > 14.5 μg L-1. The mean concentration of chlorophyll a for CA was less than half that of WA and OR locations, and concentrations were lowest in non-sanctuary sites in CA and highest at the OCNMS. Shelf sediments throughout the survey area were relatively uncontaminated with the exception of a group of stations within the SCB. Overall, about 99% of the total survey area was rated in good condition (<5 chemicals measured above corresponding effect range low (ERL) concentrations). Only the pesticides 4,4′-DDE and total DDT exceeded corresponding effect range-median (ERM) values, all at stations in CA near Los Angeles. Ten other contaminants including seven metals (As, Cd, Cr, Cu, Hg, Ag, Zn), 2-methylnaphthalene, low molecular weight PAHs, and total PCBs exceeded corresponding ERLs. The most prevalent in terms of area were chromium (31%), arsenic (8%), 2-methylnaphthalene (6%), cadmium (5%), and mercury (4%). The chromium contamination may be related to natural background sources common to the region. The 2-methylnaphthalene exceedances were conspicuously grouped around the CINMS. The mercury exceedances were all at non-sanctuary sites in CA, particularly in the Los Angeles area. Concentrations of cadmium in fish tissues exceeded the lower end of EPA’s non-cancer, human-health-risk range at nine of 50 EMAP/NCA-West and nine of 60 FRAM groundfish-survey stations, including a total of seven NMS stations in CA and two in the OCNMS. The human-health guidelines for all other contaminants were only exceeded for total PCBs at one station located in WA near the mouth of the Columbia River. Benthic species richness was relatively high in these offshore assemblages, ranging from 19 to 190 taxa per 0.1-m2 grab and averaging 79 taxa/grab. The high species richness was reflected over large areas of the shelf and was nearly three times greater than levels observed in estuarine samples along the West Coast (e.g NCA-West estuarine mean of 26 taxa/grab). Mean species richness was highest off CA (94 taxa/grab) and lower in OR and WA (55 and 56 taxa/grab, respectively). Mean species richness was very similar between sanctuary vs. non-sanctuary stations for both the CA and OR/WA regions. Mean diversity index H′ was highest in CA (5.36) and lowest in WA (4.27). There were no major differences in mean H′ between sanctuary vs. nonsanctuary stations for both the CA and OR/WA regions. A total of 1,482 taxa (1,108 to species) and 99,135 individuals were identified region-wide. Polychaetes, crustaceans and molluscs were the dominant taxa, both by percent abundance (59%, 17%, 12% respectively) and percent species (44%, 25%, 17%, respectively). There were no major differences in the percent composition of benthic communities among states or between NMSs and corresponding non-sanctuary sites. Densities averaged 3,788 m-2, about 30% of the average density for West Coast estuaries. Mean density of benthic fauna in the present offshore survey, averaged by state, was highest in CA (4,351 m-2) and lowest in OR (2,310 m-2). Mean densities were slightly higher at NMS stations vs. non-sanctuary stations for both the CA and OR/WA regions. The 10 most abundant taxa were the polychaetes Mediomastus spp., Magelona longicornis, Spiophanes berkeleyorum, Spiophanes bombyx, Spiophanes duplex, and Prionospio jubata; the bivalve Axinopsida serricata, the ophiuroid Amphiodia urtica, the decapod Pinnixa occidentalis, and the ostracod Euphilomedes carcharodonta. Mediomastus spp. and A. serricata were the two most abundant taxa overall. Although many of these taxa have broad geographic distributions throughout the region, the same species were not ranked among the 10 most abundant taxa consistently across states. The closest similarities among states were between OR and WA. At least half of the 10 most abundant taxa in NMSs were also dominant in corresponding nonsanctuary waters. Many of the abundant benthic species have wide latitudinal distributions along the West Coast shelf, with some species ranging from southern CA into the Gulf of Alaska or even the Aleutians. Of the 39 taxa on the list of 50 most abundant taxa that could be identified to species level, 85% have been reported at least once from estuaries of CA, OR, or WA exclusive of Puget Sound. Such broad latitudinal and estuarine distributions are suggestive of wide habitat tolerances. Thirteen (1.2%) of the 1,108 identified species are nonindigenous, with another 121 species classified as cryptogenic (of uncertain origin), and 208 species unclassified with respect to potential invasiveness. Despite uncertainties of classification, the number and densities of nonindigenous species appear to be much lower on the shelf than in the estuarine ecosystems of the Pacific Coast. Spionid polychaetes and the ampharetid polychaete Anobothrus gracilis were a major component of the nonindigenous species collected on the shelf. NOAA’s five NMSs along the West Coast of the U.S. appeared to be in good ecological condition, based on the measured indicators, with no evidence of major anthropogenic impacts or unusual environmental qualities compared to nearby nonsanctuary waters. Benthic communities in sanctuaries resembled those in corresponding non-sanctuary waters, with similarly high levels of species richness and diversity and low incidence of nonindigenous species. Most oceanographic features were also similar between sanctuary and non-sanctuary locations. Exceptions (e.g., higher concentrations of some nutrients in sanctuaries along the CA coast) appeared to be attributable to natural upwelling events in the area at the time of sampling. In addition, sediments within the sanctuaries were relatively uncontaminated, with none of the samples having any measured chemical in excess of ERM values. The ERL value for chromium was exceeded in sediments at the OCNMS, but at a much lower percentage of stations (four of 30) compared to WA and OR non-sanctuary areas (31 of 70 stations). ERL values were exceeded for arsenic, cadmium, chromium, 2- methylnaphthalene, low molecular weight PAHs, total DDT, and 4,4′-DDE at multiple sites within the CINMS. However, cases where total DDT, 4,4′-DDE, and chromium exceeded the ERL values were notably less prevalent at CINMS than in non-sanctuary waters of CA. In contrast, 2-methylnaphthalene above the ERL was much more prevalent in sediments at the CINMS compared to non-sanctuary waters off the coast of CA. While there are natural background sources of PAHs from oil seeps throughout the SCB, this does not explain the higher incidence of 2-methylnaphthalene contamination around CINMS. Two stations in CINMS also had levels of TOC (> 5%) potentially harmful to benthic fauna, though none of these sites exhibited symptoms of impaired benthic condition. This study showed no major evidence of extensive biological impacts linked to measured stressors. There were only two stations, both in CA, where low numbers of benthic species, diversity, or total faunal abundance co-occurred with high sediment contamination or low DO in bottom water. Such general lack of concordance suggests that these offshore waters are currently in good condition, with the lower-end values of the various biological attributes representing parts of a normal reference range controlled by natural factors. Results of multiple linear regression, performed using full model procedures to test for effects of combined abiotic environmental factors, suggested that latitude and depth had significant influences on benthic variables regionwide. Latitude had a significant inverse influence on all three of the above benthic variables, i.e. with values increasing as latitude decreased (p< 0.01), while depth had a significant direct influence on diversity (p < 0.001) and inverse effect on density (p <0.01). None of these variables varied significantly in relation to sediment % fines (at p< 0.1), although in general there was a tendency for muddier sediments (higher % fines) to have lower species richness and diversity and higher densities than coarser sediments. Alternatively, it is possible that for some of these sites the lower values of benthic variables reflect symptoms of disturbance induced by other unmeasured stressors. The indicators in this study included measures of stressors (e.g., chemical contaminants, eutrophication) that are often associated with adverse biological impacts in shallower estuarine and inland ecosystems. However, there may be other sources of humaninduced stress in these offshore systems (e.g., bottom trawling) that pose greater risks to ambient living resources and which have not been captured. Future monitoring efforts in these offshore areas should include indicators of such alternative sources of disturbance. (137pp.) (PDF contains 167 pages)

PSGL-1酪氨酸变异体的动力学分析

<正>在炎症反应过程中,选择素/配体相互作用介导了白细胞在血管内皮表面的滚动和结合。选择素/配体相互作用的化学反应速率、反应亲和性和力学强度对白细胞的滚动起决定性作用。选择素家族的所有成员(P-、E-、和L-选择素)都有一个共同的配体PSGL-1(P-selectinglycoproteinligand-1)——一种白细胞表面的同源双体粘液素蛋白。PSGL-1与P-或L-选择素发生粘附需要同时含有两个必要结构:46、48和51位酪氨酸的硫酸化;57位苏氨酸的0型糖苷,并经过sLe~x(sialyl

微/纳米力学测试技术及其应用

    本书系统地介绍了微／纳米力学测试技术中最常用的压入和划入技术及其典型应用。全书共分13章。测试技术方面，内容涉及接触力学、测试原理、方法、校准、仪器、力学参量、影响因素。典型应用方面，内容涉及在表面工程、微机电系统、生物、高聚物和金属玻璃等领域内的微／纳米力学行为的测试。本书可供力学、材料、物理、电子、机械、生物和化学等领域的研究人员、工程技术人员以及大专院校相关专业的师生参考。

目录

前言

第1章 绪论

1.1硬度的定义和分类

1.2纳米压入和划入技术的发展

1.3纳米压入和划入技术的特点

参考文献

第2章 压入接触力学

2.1弹性接触

2.1.1 Soeddon解

2.1.2锥形压针

2.1.3球形压针

2.1.4圆柱压针

2.2弹塑性接触

2.2.1塑性发生

2.2.2完全塑性

2.2.3材料响应

参考文献

第3章 纳米压入测试原理

3.1压入硬度和模量

3.2连续刚度测量

3.3载荷一深度数据确定的材料参数

3.3.1马氏硬度

3.3.2压入蠕变

3.3.3压入松弛

3.3.4压入弹性功和塑性功

参考文献

第4章 纳米压入测试方法

4.1压针类型

4.1.1玻氏压针

4.1.2立方角压针

4.1.3维氏压针

4.1.4努氏压针

4.1.5圆锥压针

4.1.6球形压针

4.1.7圆柱压针

4.1.8楔形压针

4.1.9考虑因素

4.2测试环节

4.2.1样品准备

4.2.2环境控制

4.2.3间距选择

4.2.4表面探测

4.2.5驱动方式

4.2.6测试步骤

4.2.7测试报告

参考文献

第5章 纳米压入的确认和校准

5.1直接确认和校准

5.2间接校准

5.3测试和校准的实例

参考文献

第6章 纳米压入和划入的测量仪器

6.1仪器技术指标的定义

6.2美国Mrs公司

6.3美国Hysitmn公司

6.4瑞士CSM公司

6.5英国MML公司

6.6澳大利亚CSIRO公司

6.7测量仪器的发展趋势

参考文献

第7章 力学参量的测量

7.1压入方式

7.1.1硬度和模量

7.1.2断裂韧度

7.1.3蠕变和粘弹行为

7.1.4压入应力??应变曲线

7.1.5加卸载曲线涉及的

部分现象

7.2划人方式

7.2.1块体材料

7.2.2薄膜材料

7.2.3粗糙度

7.3弯曲方式

7.3.1微悬臂梁静载弯曲

7.3.2微桥静载弯曲

7.3.3微结构疲劳

7.4吸引方式

7.5声发射测试

7.6温度测试

参考文献.

第8章 影响纳米压入测试的因素

8.1测试仪器的影响

8.1.1压针缺陷

8.1.2测试方法

8.1.3接触零点的确定

8.1.4载荷和位移的分辨力

8.2样品的表面状态和性质

8.2.1表面吸湿

8.2.2表面粗糙度

8.2.3残余应力

8.2.4凹陷和凸起变形

8.3纳米压入和划入测试所面临的问题

参考文献

第9章 在表面工程中的应用

9.1金属材料表面激光强化的力学表征

9.2硬质膜的力学和摩擦学性能评估

9.2.1显微硬度测试

9.2.2纳米压人测试

9.2.3纳米划入测试

9.2.4膜材的影响

参考文献

第10章 在微机电系统中的应用

10.1薄膜测试

10.1.1典型薄膜材料的硬度和模量

10.1.2薄膜疲劳

10.1.3淀积工艺对二氧化硅薄膜力学性质的影响

10.2微结构弯曲

10.2.1微结构的静态弯曲

10.2.2微结构的动态弯曲

参考文献

第11章 在生物及其相关材料中的应用

11.1人工林杉木管胞细胞壁

11.2人体腰椎骨

11.3存储液对人体牙齿微力学性能的影响

参考文献

第12章 在高聚物中的应用

12.1PMMA单轴拉伸和弯曲力学行为

12.2划入测试的理论分析

12.3韧性行为的描述

12.4脆性行为的描述

12.4.1温度效应

12.4.2应变率效应

参考文献

第13章 在金属玻璃中的应用

13.1硬度和屈服应力的关系

13.2不连续的塑性变形

13.3压痕形貌和微结构变化

13.4应变率效应

13.5钕基金属玻璃的变形行为

参考文献

附录 常见问题的回答

1测试数量

2压入间距

3压入深度

4泊松比的选择

5典型材料的参数

6断裂韧度测试压针的选择

7纳米薄膜的测试

8典型材料的压入变形行为

9显微硬度和纳米压入硬度的关系

10压入影响区及其边界效应

10.1压入影响区的有限元模拟

10.2边界距离影响的有限元模拟

10.3压人间距影响的测试

参考文献

USP1 deubiquitinase: cellular functions, regulatory mechanisms and emerging potential as target in cancer therapy

12 p.

Medida Provisória Nº 675, de 2015

Visa a esclarecer as disposições constantes da Medida Provisória nº 675, de 21 de maio de 2015, que “Altera a Lei nº 7.689, de 15 de dezembro de 1988, para elevar a alíquota da Contribuição Social sobre o Lucro Líquido – CSLL em relação às pessoas jurídicas de seguros privados e de capitalização e às referidas nos incisos I a VII, IX e X do § 1º do art. 1º da Lei Complementar nº 105, de 10 de janeiro de 2001”.

Os Impactos do PL 5069/2013 sobre os Direitos das Mulheres

Estuda os efeitos do PL 5069/2013, que altera a Lei 12.845, de 1º de agosto de 2013, que dispõe sobre o atendimento obrigatório e integral de pessoas em situação de violência sexual e as consequências para as mulheres atendidas nos hospitais da rede do SUS.

2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Tunable heparan sulfate glycomimetics for modulating chemokine activity

Heparan sulfate (HS) glycosaminoglycans participate in critical biological processes by modulating the activity of a diverse set of protein binding partners. Such proteins include all known members of the chemokine superfamily, which are thought to guide the migration of distinct subsets of immune cells through their interactions with HS proteoglycans on endothelial cell surfaces. Animal-derived heparin polysaccharides have been shown to reduce inflammation levels through the inhibition of HS-chemokine interactions; however, the clinical usage of heparin as an anti-inflammatory drug is hampered by its anticoagulant activity and potential risk for side effects, such as heparin-induced thrombocytopenia (HIT).

Here, we describe an expedient, divergent synthesis to prepare defined glycomimetics of HS that recapitulate the macromolecular structure and biological activity of natural HS glycosaminoglycans. Our synthetic approach uses a core disaccharide precursor to generate a library of four differentially sulfated polymers. We show that a trisulfated glycopolymer antagonizes the chemotactic activities of pro-inflammatory chemokine RANTES with similar potency as heparin polysaccharide, without potentiating the anticoagulant activities of antithrombin III. The same glycopolymer also inhibited the homeostatic chemokine SDF-1 with significantly more efficacy than heparin. Our work offers a general strategy for modulating chemokines and dissecting the pleiotropic functions of HS/heparin through the presentation of defined sulfation motifs within multivalent polymeric scaffolds.