丙二酸-1,3-13C2 | 99524-14-8

• 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: 丙二酸-1,3-13C2
• 英文名称: 1,3-13C₂-malonic acid
• 英文别名: Malonic acid-1,3-13C2；(1,3-13C2)propanedioic acid
• CAS: 99524-14-8
• 化学式: C₃H₄O₄
• 分子量: 106.04
• InChiKey: OFOBLEOULBTSOW-SUEIGJEOSA-N

物化性质

• 熔点：
  132-135 °C (dec.) (lit.)
• 闪点：
  172℃
• 稳定性/保质期：
  <b> <p></p> </b>

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 危险品标志：
  Xn
• WGK Germany：
  3

SDS

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SECTION 1: Identification of the substance/mixture and of the company/undertaking
Product identifiers
Product name : Malonic acid-1,3-13C2
REACH No. : A registration number is not available for this substance as the substance
or its uses are exempted from registration, the annual tonnage does not
require a registration or the registration is envisaged for a later
registration deadline.
CAS-No. : 99524-14-8
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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SECTION 2: Hazards identification
Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008
Acute toxicity, Oral (Category 4), H302
Serious eye damage (Category 1), H318
For the full text of the H-Statements mentioned in this Section, see Section 16.
Classification according to EU Directives 67/548/EEC or 1999/45/EC
Xn Harmful R22
Xi Irritant R41
For the full text of the R-phrases mentioned in this Section, see Section 16.
Label elements
Labelling according Regulation (EC) No 1272/2008
Pictogram
Signal word Danger
Hazard statement(s)
H302 Harmful if swallowed.
H318 Causes serious eye damage.
Precautionary statement(s)
P280 Wear protective gloves/ eye protection/ face protection.
P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove
contact lenses, if present and easy to do. Continue rinsing.
Supplemental Hazard none
Statements
Other hazards - none

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SECTION 3: Composition/information on ingredients
Substances
Chemical characterization : Isotopically labeled
Formula : 13C2CH4O4
Molecular Weight : 106,05 g/mol
CAS-No. : 99524-14-8
Hazardous ingredients according to Regulation (EC) No 1272/2008
Component Classification Concentration
Malonic acid-1,3-13C2
CAS-No. 99524-14-8 Acute Tox. 4; Eye Dam. 1; <= 100 %
H302, H318
Hazardous ingredients according to Directive 1999/45/EC
Component Classification Concentration
Malonic acid-1,3-13C2
CAS-No. 99524-14-8 Xn, R22 - R41 <= 100 %
For the full text of the H-Statements and R-Phrases mentioned in this Section, see Section 16

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SECTION 4: First aid measures
Description of first aid measures
General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In case of skin contact
Wash off with soap and plenty of water. Consult a physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.
Most important symptoms and effects, both acute and delayed
The most important known symptoms and effects are described in the labelling (see section 2.2) and/or in
section 11
Indication of any immediate medical attention and special treatment needed
no data available

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SECTION 5: Firefighting measures
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
no data available
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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SECTION 6: Accidental release measures
Personal precautions, protective equipment and emergency procedures
Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure
adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.
For personal protection see section 8.
Environmental precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed
containers for disposal.
Reference to other sections
For disposal see section 13.

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SECTION 7: Handling and storage
Precautions for safe handling
Avoid contact with skin and eyes. Avoid formation of dust and aerosols.
Provide appropriate exhaust ventilation at places where dust is formed.
For precautions see section 2.2.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Store under inert gas. hygroscopic
Specific end use(s)
Apart from the uses mentioned in section 1.2 no other specific uses are stipulated

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SECTION 8: Exposure controls/personal protection
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and
at the end of workday.
Personal protective equipment
Eye/face protection
Face shield and safety glasses Use equipment for eye protection tested and approved under
appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Complete suit protecting against chemicals, The type of protective equipment must be selected
according to the concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a full-face particle
respirator type N100 (US) or type P3 (EN 143) respirator cartridges as a backup to engineering
controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use
respirators and components tested and approved under appropriate government standards such
as NIOSH (US) or CEN (EU).
Control of environmental exposure
Do not let product enter drains.

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SECTION 9: Physical and chemical properties
Information on basic physical and chemical properties
a) Appearance Form: solid
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing Melting point/range: 132 - 135 °C - lit.
point Melting point/range: 132 - 135 °C - dec.
f) Initial boiling point and no data available
boiling range
g) Flash point 172,00 °C - closed cup
h) Evapouration rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density no data available
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Auto-ignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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SECTION 10: Stability and reactivity
Reactivity
no data available
Chemical stability
Stable under recommended storage conditions.
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Bases, Oxidizing agents, Reducing agents
Hazardous decomposition products
no data available
In the event of fire: see section 5

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SECTION 11: Toxicological information
Information on toxicological effects
Acute toxicity
LD50 Oral - rat - 1.310 mg/kg
Remarks: Behavioral:Convulsions or effect on seizure threshold. Lungs, Thorax, or Respiration:Dyspnea.
Cyanosis
LC50 Inhalation - rat - 1,00 h - > 8.989 mg/m3
Skin corrosion/irritation
Skin - rabbit
Result: Mild skin irritation - 24,00 h
Serious eye damage/eye irritation
Eyes - rabbit
Result: Severe eye irritation
Respiratory or skin sensitisation
no data available
Germ cell mutagenicity
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Additional Information
RTECS: Not available

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SECTION 12: Ecological information
Toxicity
Toxicity to fish LC50 - Lepomis macrochirus - 150 mg/l - 24,0 h
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
PBT/vPvB assessment not available as chemical safety assessment not required/not conducted
Other adverse effects
no data available

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SECTION 13: Disposal considerations
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company. Dissolve or mix the material
with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber.
Contaminated packaging
Dispose of as unused product.

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SECTION 14: Transport information
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA: no
Special precautions for user
no data available

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SECTION 15: Regulatory information
This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.
Safety, health and environmental regulations/legislation specific for the substance or mixture
no data available
Chemical Safety Assessment
For this product a chemical safety assessment was not carried out

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SECTION 16: Other information
Full text of H-Statements referred to under sections 2 and 3.
Acute Tox. Acute toxicity
Eye Dam. Serious eye damage
H302 Harmful if swallowed.
H318 Causes serious eye damage.
Full text of R-phrases referred to under sections 2 and 3
Xn Harmful
R22 Harmful if swallowed.
R41 Risk of serious damage to eyes.
Further information
Copyright 2014 Co. LLC. License granted to make unlimited paper copies for internal use
only.
The above information is believed to be correct but does not purport to be all inclusive and shall be
used only as a guide. The information in this document is based on the present state of our knowledge
and is applicable to the product with regard to appropriate safety precautions. It does not represent any
guarantee of the properties of the product. Corporation and its Affiliates shall not be held
liable for any damage resulting from handling or from contact with the above product. See
and/or the reverse side of invoice or packing slip for additional terms and conditions of sale.

反应信息

• 作为反应物：
  描述：

  丙二酸-1,3-13C2 生成 (4,6-13C2)-2,2-dimethyl-1,3-dioxan-4,6-dione
  参考文献：
  名称：

  Iminopropadienones, RN:C:C:C:O. Theory and experiment

  摘要：

  Ab initio molecular orbital calculations at the MP2/6-31G* level have been used to examine the structures and infrared spectra of a new class of compounds, the iminopropadienones, RN=C=C=C=O (R = H, CH3, and Ph). The agreement between calculated and experimental IR spectra of PhNCCCO, Ph(15)NCCCO, and PhNCC(13)CO is excellent. Inclusion of electron correlation is found to be important for the correct prediction of the relative intensities of the cumulenic stretching vibrations. All three iminopropadienones are predicted to have a slightly bent NCCCO backbone (angle CCC approximate to 176 degrees). As with carbon suboxide, these cumulenes are calculated to have an extremely flat CCC bending potential. The parent compound, HNCCCO (4a) is calculated to be thermodynamically stable toward dissociations into (i) HNCC + CO, (ii) HNC + CCO, (iii) HN + CCCO, and (iv) H. + NCCCO.. Rearrangement of 4a to the more stable cyanoketene isomer requires a sizeable barrier of 402 kJ mol(-1) [G2(MP2)]. The calculated stability of 4a is consistent with its experimental observation in neutralization-reionization mass spectrum. The adiabatic ionization energy and heat of formation of HNCCCO are predicted to be 9.51 eV and 175 kJ mol(-1), respectively.

  DOI：

  10.1021/j100055a007
• 作为产物：
  描述：

  二氧化碳-13C 生成 丙二酸-1,3-13C2
  参考文献：
  名称：

  Iminopropadienones, RN:C:C:C:O. Theory and experiment

  摘要：

  Ab initio molecular orbital calculations at the MP2/6-31G* level have been used to examine the structures and infrared spectra of a new class of compounds, the iminopropadienones, RN=C=C=C=O (R = H, CH3, and Ph). The agreement between calculated and experimental IR spectra of PhNCCCO, Ph(15)NCCCO, and PhNCC(13)CO is excellent. Inclusion of electron correlation is found to be important for the correct prediction of the relative intensities of the cumulenic stretching vibrations. All three iminopropadienones are predicted to have a slightly bent NCCCO backbone (angle CCC approximate to 176 degrees). As with carbon suboxide, these cumulenes are calculated to have an extremely flat CCC bending potential. The parent compound, HNCCCO (4a) is calculated to be thermodynamically stable toward dissociations into (i) HNCC + CO, (ii) HNC + CCO, (iii) HN + CCCO, and (iv) H. + NCCCO.. Rearrangement of 4a to the more stable cyanoketene isomer requires a sizeable barrier of 402 kJ mol(-1) [G2(MP2)]. The calculated stability of 4a is consistent with its experimental observation in neutralization-reionization mass spectrum. The adiabatic ionization energy and heat of formation of HNCCCO are predicted to be 9.51 eV and 175 kJ mol(-1), respectively.

  DOI：

  10.1021/j100055a007

文献信息

• A Novel Class of Bis- and Tris-Chelate Diam(m)inebis(dicarboxylato)platinum(IV) Complexes as Potential Anticancer Prodrugs
  作者：Hristo P. Varbanov、Simone Göschl、Petra Heffeter、Sarah Theiner、Alexander Roller、Frank Jensen、Michael A. Jakupec、Walter Berger、Mathea Sophia Galanski、Bernhard K. Keppler

  DOI：10.1021/jm500791c

  日期：2014.8.14

  A novel class of platinum(IV) complexes of the type [Pt(Am)(R(COO)2)2], where Am is a chelating diamine or two monodentate am(m)ine ligands and R(COO)2 is a chelating dicarboxylato moiety, was synthesized. For this purpose, the reaction between the corresponding tetrahydroxidoplatinum(IV) precursors and various dicarboxylic acids, such as oxalic, malonic, 3-methylmalonic, and cyclobutanedicarboxylic

  [Pt(Am)(R(COO) 2 ) 2 ]类型的新型铂 (IV) 配合物，其中 Am 是螯合二胺或两个单齿胺(m)ine 配体和 R(COO) 2是一种螯合的二羧基部分，是合成的。为此目的，利用了相应的四羟基铂（IV）前体与各种二羧酸（例如草酸、丙二酸、3-甲基丙二酸和环丁二羧酸）之间的反应。使用 1D 和 2D NMR 技术、ESI-MS、FTIR 光谱、元素分析、TGA 和 X 射线衍射对所有新化合物进行了详细表征。通过 MTT 比色法测定一组人肿瘤细胞系（CH1、SW480 和 A549）的体外细胞毒性。此外，为了更好地了解它们的药理行为，对新型复合物的亲脂性和氧化还原特性进行了评估。最有希望的候选药物，4b (Pt(DACH)(mal) 2)，对 L1210 白血病和 CT-26 结肠癌模型表现出低体内毒性但具有很强的抗癌活性。
• Gas-Phase Synthesis of Charged Copper and Silver Fischer Carbenes from Diazomalonates:  Mechanistic and Conformational Considerations in Metal-Mediated Wolff Rearrangements
  作者：Ryan R. Julian、Jeremy A. May、Brian M. Stoltz、J. L. Beauchamp

  DOI：10.1021/ja028337j

  日期：2003.4.1

  products. Silver(I) is shown to be more effective in facilitating Wolff rearrangement than copper(I), although both are more effective when compared to spectator charges such as sodium or a fixed quaternary nitrogen. Carbenes are not produced when copper(II), nickel(II), or a proton is used to form a quasi-molecular ion from the diazomalonate carbene precursor. Finally, trapping of the Fischer carbene by

  铜 (I) 和银 (I) Fischer 卡宾在气相中合成。通过电喷雾电离将各种具有附着金属离子的重氮丙二酸酯基化合物引入气相并进行碰撞活化。N(2) 的损失生成亚稳态费舍尔卡宾，随后经历沃尔夫重排和 CO 的损失。进一步激发导致另一个 CO 分子的损失和稳定的费舍尔卡宾的生成。同位素标记的化合物用于确认该过程产生的产物的归属。DFT 计算用于评估各种机械可能性并定量评估反应物和产物的能量。银（I）被证明在促进沃尔夫重排方面比铜（I）更有效，尽管与钠或固定季氮等旁观者费用相比，两者都更有效。当使用铜 (II)、镍 (II) 或质子从重氮丙二酸酯卡宾前体形成准分子离子时，不会产生卡宾。最后，研究了通过金属的开放配位位点连接的各种官能团对 Fischer 卡宾的捕获。
• Changes in the Content and Biosynthesis of Phytoalexins in Banana Fruit
  作者：Tsunashi KAMO、Nobuhiro HIRAI、Mitsuya TSUDA、Daie FUJIOKA、Hajime OHIGASHI

  DOI：10.1271/bbb.64.2089

  日期：2000.1

  Changes in the phytoalexin content in unripe fruit of banana, Musa acuminata, were analyzed after various treatments. The results show that level of hydroxyanigorufone started to increase 1-2 day after either wounding or inoculation with conidia of Colletotrichum musae. Inoculation followed by wounding induced the formation of many other phenylphenalenones. The accumulation of hydroxyanigorufone decreased, after its transient maximum, on ripening by exposure of the wounded fruit to ethylene. The level of production of hydroxyanigorufone in ripe fruit treated by wounding and/or by inoculation was much lower than that in unripe fruit. 2-Aminooxyacetic acid, an inhibitor of phenylalanine ammonia-lyase (PAL), inhibited the accumulation of hydroxyanigorufone in wounded fruit, and the PAL activity increased after wounding and ethylene treatment, respectively. Feeding experiments with [1-13C] and [2-13C]cinnamic acids, and [2-13C]malonate show that two molecules of cinnamic acid and one of malonate were incorporated into each molecule of hydroxyanigorufone. The phytoalexins isolated from fruit to which deuterated hydroxyanigorufone and irenolone had been administered revealed that 2-(4′-hydroxyphenyl)-1,8-naphthalic anhydride was biosynthesized from hydroxyanigorufone rather than from irenolone.

  分析了香蕉（Musa acuminata）未熟果实中植物毒素含量在经过各种处理后的变化。结果表明，在造成伤口或接种 Colletotrichum musae 的分生孢子后 1-2 天，羟基茴香酮的含量开始增加。接种后再造成伤口，会诱导形成许多其他苯丙烯酮。羟基苯并呋喃酮的积累量在短暂达到最大值后，在果实成熟时，通过将受伤果实暴露于乙烯中而减少。在经过伤口和/或接种处理的成熟果实中，羟基安哥氟酮的产生水平远远低于未熟果实。苯丙氨酸氨解酶（PAL）抑制剂 2-Aminooxyacetic acid 可抑制伤果中羟基安哥氟酮的积累，伤果和乙烯处理后 PAL 活性分别升高。用[1-13C]和[2-13C]肉桂酸以及[2-13C]丙二酸盐进行的喂养实验表明，每个羟基安鲁酮分子中含有两个肉桂酸分子和一个丙二酸分子。从施用了氘代羟基安哥氟酮和壬内酯的果实中分离出的植物毒素表明，2-（4′-羟基苯基）-1,8-萘酸酐是由羟基安哥氟酮而不是壬内酯生物合成的。
• FTIR studies of hydrogen bonding between α,β-unsaturated esters and alcohols
  作者：P.J. Tonge、R. Fausto、P.R. Carey

  DOI：10.1016/0022-2860(95)09117-3

  日期：1996.6

  function of temperature and applying the van't Hoff equation. The decrease in νCO of the ester carbonyl group upon hydrogen bond formation ΔνCO has also been measured and correlated with the enthalpy of hydrogen bond formation. A linear correlation is observed between the enthalpy of hydrogen bond formation −ΔH and ΔνCO, with −ΔH = 1.36ΔνCO − 16.1, where ΔH is measured in kJ mol−1 and Δν in cm−1. Comparison

  摘要 测量了两种 α,β-不饱和酯噻吩基丙烯酰基 (TAOMe) 和 5-甲基噻吩基丙烯酰基 (5MeTAOMe) 甲酯的酯羰基与氢键供体乙醇、苯酚和CCl4 中的 3,5-二氯苯酚。对于酯类，氢键强度是通过定量结合和未结合供体的量、使用 OH 拉伸区域作为温度的函数并应用范特霍夫方程来测量的。还测量了形成氢键时酯羰基的 νCO 的减少 ΔνCO，并将其与氢键形成的焓相关联。观察到氢键形成焓-ΔH和ΔνCO之间存在线性相关性，其中-ΔH = 1.36ΔνCO - 16.1，其中 ΔH 以 kJ mol-1 为单位，Δν 以 cm-1 为单位。与其他羰基受体化合物的数据比较表明，上述 α,β-不饱和酯的羰基比饱和酯或酮的羰基更容易极化。此处导出的−ΔH 和ΔνCO 之间的定量关系已被用于确定一系列酰基丝氨酸蛋白酶中底物和酶组之间氢键形成焓的变化。
• Ring Current Effects in the Active Site of Medium-Chain Acyl-CoA Dehydrogenase Revealed by NMR Spectroscopy
  作者：Jiaquan Wu、Alasdair F. Bell、Andrew A. Jaye、Peter J. Tonge

  DOI：10.1021/ja050083p

  日期：2005.6.1

  Medium-chain acyl-CoA dehydrogenase (MCAD) catalyzes the flavin-dependent oxidation of fatty acyl-CoAs to the corresponding trans-2-enoyl-CoAs. The interaction of hexadienoyl-CoA (HD-CoA), a product analogue, with recombinant pig MCAD (pMCAD) has been studied using C-13 NMR and H-1-C-13 HSQC spectroscopy. Upon binding to oxidized pMCAD, the chemical shifts of the C1, C2, and C3 HID carbons are shifted upfield by 12.8, 2.1, and 13.8 ppm, respectively. In addition, the H-1 chemical shift of the C3-H is also shifted upfield by 1.31 ppm while the chemical shift of the C4 HD-CoA carbon is unchanged upon binding. These changes in chemical shift are unexpected given the results of previous Raman studies which revealed that the C3=C2-C1=0 HD enone fragment is polarized upon binding to MCAD such that the electron density at the C3 and C1 carbons is reduced, not increased (Pellet et al. Biochemistry 2000, 39, 13982-13992). To investigate the apparent discrepancy between the NMR and Raman data for HD-CoA bound to MCAD, C-13 NMR spectra have been obtained for HD-CoA bound to enoyl-CoA hydratase, an enzyme system that has also previously been studied using Raman spectroscopy. Significantly, binding to enoyl-CoA hydratase causes the chemical shifts of the C1 and C3 HID carbons to move downfield by 4.8 and 5.6 ppm, respectively, while the C2 resonance moves upfield by 2.2 ppm, in close agreement with the alterations in electron density at these carbons predicted from Raman spectroscopy (Bell, A. F.; Wu, J.; Feng, Y.; Tonge, P. J. Biochemistry 2001, 40, 1725-33). The large increase in shielding experienced by the C1 and C3 HD carbons in the HD-CoA/MCAD complex is proposed to arise from the ring current field from the isoalloxazine portion of the flavin cofactor. The flavin ring current, which is only present when the enzyme is placed in an external magnetic field, also explains the differences in C-13 NMR chemical shifts for acetoacetyl-CoA when bound as an enolate to MCAD and enoyl-CoA hydratase and is used to rationalize the observation that the line widths of the C1 and C3 resonances are narrower when the ligands are bound to MCAD than when they are free in the protein solution.