2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物 | 3068-32-4

• 物质功能分类: 生物化工 - 糖类化合物 - 单糖
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物
• 中文别名: 2,3,4,6-四乙酰基-Α-D-溴代吡喃半乳糖；Α-溴代-2,3,4,6-四乙酰吡喃半乳糖；2,3,4,6-O-四乙酰基-Α-D-溴代半乳糖；溴代半乳糖；1-溴代-2,3,4,6-四乙酰-Α-D-半乳糖；2,3,4,6-四乙酰氧基-α-D-吡喃糖溴化物；乙酰溴代-α-D-水解乳糖；1-溴代-2,3,4,6；四乙酰基-α-D-溴代半乳糖；乙酰溴代-Α-D-水解乳糖；溴代半乳糖苷；2,3,4,6-四-氧-乙酰基-α-D-溴代吡喃半乳糖
• 英文名称: 1-bromo-1-deoxy-2,3,4,6-tetra-O-acetyl-a-D-galactopyranoside
• 英文别名: 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide；1-bromine-2,3,4,6-tetra-O-acetyl-α-D-galactose；acetobromo-α-D-galactose；tetra-O-acetyl-α-D-galactopyranosyl bromide；(2R,3S,4S,5R,6R)-2-(acetoxymethyl)-6-bromotetrahydro-2H-pyran-3,4,5-triyl triacetate；1-bromo-2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside；2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl bromide；2,3,4,6-tetra-O-acetyl-α-galactopyranosyl bromide；2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide；acetobromogalactose；1-bromo-2,3,4,6-tetra-O-acetyl-α-D-galactopyranose；tetra-O-acetyl-α-D-galactopyranosyl-1-bromide；tetra-O-acetyl-α-D-galactosyl bromide；tetraacetyl-α-D-bromogalactose；tetra-O-acetyl-galactosyl bromide；2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl bromide；2,3,4,6-tetraacetyl-α-D-bromogalactose；2,3,4,6-tetra-O-acetyl-galactosyl bromide；α-D-galactopyranosyl bromide；α-D-acetylgalactose bromide；[(2R,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-bromooxan-2-yl]methyl acetate
• CAS: 3068-32-4
• 化学式: C₁₄H₁₉BrO₉
• mdl: MFCD00063686
• 分子量: 411.203
• InChiKey: CYAYKKUWALRRPA-HTOAHKCRSA-N

物化性质

• 熔点：
  83-85 °C
• 比旋光度：
  210 º (c=3, CHCl3)
• 沸点：
  412.0±45.0 °C(Predicted)
• 密度：
  1.7028 (rough estimate)
• 溶解度：
  氯仿（少量溶解）、乙酸乙酯（少量溶解）、甲醇（少量溶解）、水（少量溶解）
• 稳定性/保质期：
  在常温常压下保持稳定，应避免与不相容的材料接触。

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.714
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S36,S37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  29329990
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335
• 储存条件：
  密封储存于阴凉、干燥的库房中。冷藏时，请将温度控制在-20 ºC。

SDS

Name:	2 3 4 6-Tetra-O-Acetyl-alpha-D-Galactopyranosyl Bromide 95% Material Safety Data Sheet
Synonym:	Acetobromo-alpha-D-Galactose
CAS:	3068-32-4

Section 1 - Chemical Product MSDS Name:2 3 4 6-Tetra-O-Acetyl-alpha-D-Galactopyranosyl Bromide 95% Material Safety Data Sheet
Synonym:Acetobromo-alpha-D-Galactose

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
3068-32-4	2,3,4,6-Tetra-O-Acetyl-alpha-D-Galacto	95%	221-324-0

Hazard Symbols: XI
Risk Phrases: 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin.
Potential Health Effects
Eye:
Causes eye irritation. May cause chemical conjunctivitis.
Skin:
Causes skin irritation.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea.
Inhalation:
Causes respiratory tract irritation. Can produce delayed pulmonary edema.
Chronic:
Effects may be delayed.

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Section 4 - FIRST AID MEASURES
Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Do NOT use mouth-to-mouth resuscitation.
Notes to Physician:
Treat symptomatically and supportively.

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Minimize dust generation and accumulation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing.
Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation. Wash clothing before reuse.
Storage:
Store in a tightly closed container. Store in a dry area. Deep freeze (below -20C).

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 3068-32-4: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystals
Color: white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 83-85 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Slightly soluble.
Specific Gravity/Density:
Molecular Formula: C14H19BrO9
Molecular Weight: 411.21

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions.
Conditions to Avoid:
Incompatible materials, dust generation, excess heat.
Incompatibilities with Other Materials:
Acids, aluminum, oxidizing agents, magnesium.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, hydrogen bromide.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 3068-32-4 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
2,3,4,6-Tetra-O-Acetyl-alpha-D-Galactopyranosyl Bromide - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 3068-32-4: No information available.
Canada
CAS# 3068-32-4 is listed on Canada's DSL List.
CAS# 3068-32-4 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 3068-32-4 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

2,3,4,6-四乙酰氧基-α-D-吡喃糖溴化物具有特殊的化学性质和药用活性，是许多医药、农药的中间体，应用前景非常广阔。此外，它还可用作医药及医药中间体、染发助剂、聚合物稳定剂、感光材料的抗氧化剂和抗灰雾剂等。

制备方法 第一步

将5.00克乙酸钠（61.1毫摩尔，1.1当量）溶解在70毫升乙酸酐中，形成悬浮液并加热回流。逐步加入10.0克D-半乳糖19（55.5毫摩尔，1.0当量），每次添加1至2克后立即关闭冷凝器。加完后混合物会变成清洁溶液，在回流下搅拌10分钟。随后将热溶液倒入含有400毫升冰水的1升烧杯中直至冰完全融化。向溶液中加入120毫升CH₂Cl₂，移除水层。有机相依次用冰冷的水（3次，每次400毫升）、饱和NaHCO₃水溶液（400毫升）和盐水（400毫升）洗涤，再用Na₂SO₄干燥并过滤。最后在减压下浓缩得到粗黄色油状物。通过1H NMR分析显示存在四种化合物：α,β-呋喃糖和α,β-吡喃糖。将该油溶于少量乙醚（约25毫升），加入石油醚（约50毫升）开始沉淀，再加入乙醇（约200毫升）。在24°C下保持悬浮液2至3小时，在-20°C储存16小时后过滤出白色固体并用石油醚洗涤，得到纯度≥95%的β-吡喃糖异头体。

第二步

在0℃条件下，将3.4毫升（33%，w/w）HBr在乙酸中的溶液（0.058摩尔，11.0当量）滴加到2.07克五-O-乙酰基-β-D-吡喃半乳糖20（5.31毫摩尔）在9毫升无水CH₂Cl₂的溶液中。反应混合物在0℃下搅拌30分钟后，在室温下继续搅拌，并通过薄层层析（EtOAc/己烷=2:3）监测直到原料完全消失（约3小时）。所得混合物用10毫升CH₂Cl₂稀释，分别用30毫升饱和NaHCO₃水溶液洗涤两次和20毫升H₂O洗涤一次。用Na₂SO₄干燥有机相并在真空下浓缩得到白色泡沫状的2,3,4,6-四-O-乙酰基-α-D-吡喃半乳糖基溴化物（2.16克，5.25毫摩尔，99%）。此产物在下一步中使用无需进一步纯化即可直接获得目标产物2,3,4,6-四乙酰氧基-α-D-吡喃糖溴化物。

反应信息

• 作为反应物：
  描述：

  2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物 生成 2-(三甲基硅烷基)乙基beta-吡喃半乳糖苷
  参考文献：
  名称：

  α-Neu5Ac-（2 ---- 6）-Gal结构的合成。亚锡激活未保护的D-吡喃半乳糖苷后进行6-O-唾液酸化反应。

  摘要：

  DOI：

  10.1016/0008-6215(89)85097-9
• 作为产物：
  描述：

  1',2',3',6',2,3,4,6-octa-O-acetyl-β-D-lactose 在 乙酰溴 、 三氟化硼乙醚 、 zinc dibromide 作用下， 以 二氯甲烷 为溶剂， 生成 2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物
  参考文献：
  名称：

  对甲氧基苯基糖苷转化为相应的糖基氯化物和溴化物，并转化为硫代苯基糖苷。

  摘要：

  使用硼从相应的1-O-乙酰基糖中制备对甲氧基苯基（pMP）β-D-吡喃葡萄糖苷（Glc，Gal，GlcNPhth，GalNPhth，GlcNTroc，Gal beta 4Glc，Gal alpha 4Gal），使用硼制得三氟化醚醚为助催化剂。在各种路易斯酸的存在下用酰氯或溴化物处理pMP糖苷得到相应的糖酰氯和溴化物，产率为81-98％。用硫酚和三氟化硼醚化物处理酰基保护的pMP糖苷，可以80-100％的收率和高（> 20：1）β/ alpha选择性获得相应的硫糖苷。针对一系列试剂研究了pMP糖苷的稳定性。

  DOI：

  10.1016/s0008-6215(96)90118-4

文献信息

• Synthesis and biological evaluation of a novel MUC1 glycopeptide conjugate vaccine candidate comprising a 4’-deoxy-4’-fluoro-Thomsen–Friedenreich epitope
  作者：Manuel Johannes、Maximilian Reindl、Bastian Gerlitzki、Edgar Schmitt、Anja Hoffmann-Röder

  DOI：10.3762/bjoc.11.15

  日期：——

  The development of selective anticancer vaccines that provide enhanced protection against tumor recurrence and metastasis has been the subject of intense research in the scientific community. The tumor-associated glycoprotein MUC1 represents a well-established target for cancer immunotherapy and has been used for the construction of various synthetic vaccine candidates. However, many of these vaccine prototypes suffer from an inherent low immunogenicity and are susceptible to rapid in vivo degradation. To overcome these drawbacks, novel fluorinated MUC1 glycopeptide-BSA/TTox conjugate vaccines have been prepared. Immunization of mice with the 4’F-TF-MUC1-TTox conjugate resulted in strong immune responses overriding the natural tolerance against MUC1 and producing selective IgG antibodies that are cross-reactive with native MUC1 epitopes on MCF-7 human cancer cells.

  选择性抗癌疫苗的开发，提供增强对肿瘤复发和转移的保护，一直是科学界研究的焦点。与肿瘤相关的糖蛋白MUC1代表了癌症免疫疗法的一个成熟靶点，并已被用于构建各种合成疫苗候选物。然而，许多这些疫苗原型存在固有的低免疫原性，并容易在体内迅速降解。为了克服这些缺点，已制备了新型氟化MUC1糖肽-BSA/TTox结合疫苗。用4’F-TF-MUC1-TTox结合物免疫小鼠导致强烈的免疫反应，覆盖了对MUC1的自然耐受性，并产生了选择性的IgG抗体，与MCF-7人类癌细胞上的原生MUC1表位发生交叉反应。
• Synthesis, chemical characterization and antimicrobial activity of new acylhydrazones derived from carbohydrates
  作者：Fernanda Dias Guilherme、Julia Évelin Simonetti、Lais Regina Santos Folquitto、Adriana Cotta Cardoso Reis、Josidel Conceição Oliver、Amanda Latércia Tranches Dias、Danielle Ferreira Dias、Diogo Teixeira Carvalho、Geraldo Célio Brandão、Thiago Belarmino de Souza

  DOI：10.1016/j.molstruc.2019.02.045

  日期：2019.5

  formula using this technique. All of the synthesized compounds were screened for their antibacterial, antifungal and antiviral activities. Five compounds (12, 13, 14, 16 and 19) exerted a modest antifungal activity against the strains evaluated. Derivative 14 showed fungicidal activity against Candida glabrata at 173.8 μM and saccharide unit contributed to the increase of the antifungal potential against

  摘要 合成了一系列新的糖基化酰腙，所有化学结构均通过高分辨率质谱 (HRMS)、1H 和 13C 核磁共振 (1H-NMR; 13C-NMR) 和傅里叶变换红外 (FTIR) 光谱方法确认。在 HRMS 分析中观察到的计算值和实测值之间的质量准确度接近或低于 5 ppm，这对于使用该技术提出分子式是可以接受的。筛选所有合成的化合物的抗菌、抗真菌和抗病毒活性。五种化合物（12、13、14、16 和 19）对所评估的菌株具有适度的抗真菌活性。衍生物 14 在 173.8 μM 时显示出对光滑念珠菌的杀真菌活性，并且糖单位有助于增加对该菌株的抗真菌潜力。
• INTRACELLULAR SUBSTANCE TRANSPORT SYSTEM AND USE THEREOF
  申请人：National University Corporation Hokkaido University

  公开号：US20200138973A1

  公开（公告）日：2020-05-07

  The present invention pertains to a complex including nanoparticles and, carried on the surface of the nanoparticles, a lysosomal enzyme inhibitor or kinase inhibitor shown by general formula (A) and a phospholipid mimetic substance shown by general formula (B). In general formula (A), n1 is an integer of 2-30, n2 is an integer of 2-30, the -S- terminal is a nanoparticle-carrying site, and R10 is a suicide substrate site or a kinase inhibition site. In general formula (B), n3 is an integer in the range of 2-30, and the -S- terminal is a nanoparticle-carrying site. The present invention provides a versatile system capable of efficiently delivering a drug to endolysosomes and allowing the drug to function at a low concentration on lysosomal enzymes, and an anticancer agent in which this system is used.

  本发明涉及一种包括纳米粒子的复合物，所述纳米粒子表面携带有一种由通用式（A）显示的溶酶体酶抑制剂或激酶抑制剂以及一种由通用式（B）显示的磷脂类拟物物质。 在通用式（A）中，n1是2-30的整数，n2是2-30的整数，-S-端是纳米粒子携带位点，R10是自杀底物位点或激酶抑制位点。在通用式（B）中，n3是2-30范围内的整数，-S-端是纳米粒子携带位点。本发明提供了一种多功能系统，能够有效地将药物传递至内溶酶体，并使药物在低浓度下对溶酶体酶起作用，以及使用该系统的抗癌剂。
• Synthetic Studies on Glycopeptides Concerned with Defense Response of Plants. I. Syntheses of Supprescins A and B.
  作者：Takuya KANEMITSU、Yukio OGIHARA、Tadahiro TAKEDA

  DOI：10.1248/cpb.45.643

  日期：——

  Two glycopeptides, supprescins A and B, that suppress the production of pisatin, a phytoalexin of pea, were synthesized. In the synthesis of supprescin A, condensation of 3, 4, 6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl trichloroacetimidate or its glycosidic β isomer with N-(carbobenzoxy)-L-seryl-O-benzyl-L-seryl-glycine methyl ester was carried out in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) to give the monoglycosyl tripeptide derivatives. For the synthesis of supprescin B, glycosylation of 2, 3, 4, 6-tetra-O-acetyl-α-D-galactopyranosyl bromide and 1, 2, 3, 6-tetra-O-benzoyl-α-D-galactopyranose was promoted by silver trifluoromethanesulfonate (AgOTf) to provide a disaccharide derivative. The coupling of diglycosyl imidate, 2, 3, 4, 6-tetra-O-acetyl-β-D-galactopyranosyl-(1→4)-3, 6-di-O-benzoyl-2-azido-2-deoxy-D-galactopyranosyl trichloroacetimidate, and N-(carbobenzoxy)-L-seryl-O-benzyl-L-seryl-glycyl-4-benzyl-L-aspartyl-5-benzyl-L-glutamyl-O-benzyl-L-threonine methyl ester in the presence of TMSOTf afforded the diglycosyl hexapeptide derivatives. Reduction, followed by N-acetylation, and then removal of the remaining protecting groups afforded the desired supprescin B.

  两种糖肽，抑制蛋白A和B，能够抑制豌豆中一种植物抗毒素——豌豆素的合成，它们已被制备出来。在制备抑制蛋白A的过程中，三甲基硅基三氟甲磺酸酯(TMSOTf)的存在下，将3,4,6-三-O-乙酰基-2-叠氮-2-脱氧-α-D-半乳糖吡喃糖基三氯乙酰亚胺酯或其糖苷β异构体与N-(羧基苄氧羰基)-L-丝氨酸-O-苄基-L-丝氨酰甘氨酸甲酯进行缩合反应，得到单糖基三肽衍生物。在制备抑制蛋白B的过程中，2,3,4,6-四-O-乙酰基-α-D-半乳糖吡喃糖基溴和1,2,3,6-四-O-苯甲酰基-α-D-半乳糖吡喃糖在三氟甲磺酸银(AgOTf)的促进下进行糖基化反应，生成二糖衍生物。在TMSOTf的存在下，将二糖基亚胺酯，2,3,4,6-四-O-乙酰基-β-D-半乳糖吡喃糖基-(1→4)-3,6-二-O-苯甲酰基-2-叠氮-2-脱氧-D-半乳糖吡喃糖基三氯乙酰亚胺酯与N-(羧基苄氧羰基)-L-丝氨酸-O-苄基-L-丝氨酰甘氨酰-4-苄基-L-天冬氨酰-5-苄基-L-谷氨酰-O-苄基-L-苏氨酸甲酯进行偶联反应，得到二糖基六肽衍生物。随后进行还原、N-乙酰化和剩余保护基团的去除，最终得到了所需的抑制蛋白B。
• [EN] HYDROLASE ENZYME SUBSTRATES AND USES THEREOF<br/>[FR] SUBSTRATS D'ENZYME HYDROLASE ET LEURS UTILISATIONS
  申请人：GEN ATOMICS

  公开号：WO2012099904A1

  公开（公告）日：2012-07-26

  The present invention provides novel methods for determining the presence or amount of a hydrolytic enzyme in a sample, based on novel substrates for the enzymes, and also provides compositions and methods that provide highly sensitive assay methods for such hydrolytic enzymes.

  本发明提供了一种新颖的方法，用于基于酶的新型底物确定样品中水解酶的存在或数量，并且提供了提供对这种水解酶进行高灵敏度测定的组合物和方法。