Total Synthesis of Phakellistatin 13 by Solution Method

Since George R. Pettit’s group isolated cycloheptapeptide phakellistatin 1 from sponge1, over ten similar cyclic peptides have been obtained2-5. Phakellistatin 134 (Figure 1) is a cycloheptapeptide isolated from the brown snubby sponge from the South Chi…     

Biotransformation of 14-Deacetoxy-13-oxo sinenxan A by Ginkgo Cell Cultures

Sinenxan A, 2a, 5a, 10b,14b-tetraacetoxy-4(20),11-taxadiene, is a taxoid isolated from the callus cultures of Taxus spp. in high yield (ca. 1~2% of dry weight)1,2. The rich resources and its taxane-skeleton vest it valuable potential for the semisynthesis of paclitaxel or other structurally related bioactive compounds, such as 搒econd -generation?taxoid anticancer agents and taxane-based multidrug resistant anticancer agents3-5. Many remarkable studies on its structural modification by chemi…     

Acceleration of carbon-13 spin-lattice relaxation times in amino acids by electrolytes

A series of amino acids and carboxylic acids were determined by C NMR spectroscopy. 13 The results showed that addition of 3M MgCl2 led to the C NMR integral area of samples being 13 well proportional to number of carbon atoms that produce the particular signal with reliability over 95%. Measurements of C spin-lattice relaxation times (T1’s) are reported for a number of amino 13 acids. T1’s of all the carbons in amino acids generally tend to decrease with the increase of the c…     

Simultaneous Determination of 13 Phenoxy Acid Herbicide Residues in Soybean by GC‐ECD

Abstract

In this study, a gas chromatography method for the multiresidue determination of 13 phenoxy acid herbicide residues (4‐CPA, 4‐CPP, phenoxy butyric acid, dicamba, MCPA, MCPP, MCPB, 2,4‐D, 3,4‐D, 2,4,5‐T, 2,4,5‐TP, 2,4‐DP, and 2,4‐DB) in soybean was developed. After the removal of fat using n‐hexane, the sample was extracted with acetonitrile‐50 mM HCl (v/v 7:3), and then followed by liquid‐liquid partition with n‐hexane (saturated by acetonitrile). The soybean extract was further cleaned up by anion exchange column. Then the residues were derived with pentafluorobenzyl bromide and the resulting pentafluorobenzyl (PFB) esters were analyzed by a gas chromatograph equipped with an electron capture detector (ECD), quantified by the external standard method. Recoveries of spiked samples at two fortified levels (0.01 and 0.1 mg/kg) are all above 70%. And the relative standard deviation was less than 20%. It shows that the limits of determination (LOD) of this method (S/N≥3) can meet the requirement of maximum residue analysis in import/export inspection for soybean.     

Hydrogen splitting by pyramidalized 13–15 donor–acceptor cryptands: A computational study

A series of new donor–acceptor cryptands, where pyramidalized donor (azaadamantane) and acceptor (bora/ala/adamantane) molecules are spatially oriented toward each other and linked via aromatic spacer, are constructed and computationally studied at M06-2X and ωB97X-D levels of theory. Kinetic stability of the perfluorinated bora- and ala-adamantane with respect to F migration to group 13 element is demonstrated. The effectiveness of the constructed cryptands, featuring pyramidalized perfluorinated acceptor moieties, in the heterolytic splitting of molecular hydrogen is predicted. Hydrogen splitting is highly exothermic and exergonic and is accompanied by small activation barriers. The most promising candidates for the experimental studies are identified. © 2019 Wiley Periodicals, Inc.     

Biotransformation of 14－Deacetoxy－13－oxo sinenxan A by Ginkgo Cell Cultures

14-Deacetoxy-13-oxo sinenxan A (1) was converted to 9α-hydroxy-13-oxo-2α, 5α,10β-triacetoxy-4(20),ll-taxadiene (2) and 10β-hydroxy-13-oxo-2α,5α,9α-triacetoxy- 4(20), ll-taxadiene (3) by Ginkgo cell suspension cultures in 45% and 15% yields, respectively.     

Study of the copper(II)-Aztreonam™ system by potentiometry and spectrophotometry,and structural characterization by 13C NMR relaxation

Potentiometric and spectrophotometric results obtained for the Cu(II)-Aztreonam system give a clear indication of the cheating properties of this antibiotic toward the Cu²⁺ ion, coordinated already at pH ≌ 2. Only one single complex of 1:1 stoichiometry is formed. Measurements of ¹³C relaxation rates allow us to attribute a coordination scheme via the carboxylic and aminic groups.     

Photocycle of 13-cis-retinal in bacteriorhodopsin caused by destruction to the cooperative effect of purple membrane

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“Do it yourself” reference materials for δ 13C determinations by isotope ratio mass spectrometry

A method is described to prepare inexpensive organic reference materials for routine stable isotope work. The method blends isotope-enriched and isotope-depleted materials to match closely international measurement standards. Examples are presented showing how ¹³C-enriched and ¹³C-depleted glucose were blended to match the isotopic compositions of the international carbon isotope standards, NBS 19 and L-SVEC. Preparation of the blended standards was straightforward, and the prepared solutions proved easy to dispense into tin capsules and easy to combust in a conventional isotope analysis system. The blended materials allow a laboratory to perform a two-point calibration for isotopic composition on a daily basis, with the use of an international reference material recommended for routine quality assurance. The blending method can be applied widely to make isotope standards for other elements and compounds.     

Structural characterization of drawn (ethylene–vinyl alcohol) copolymer by high-resolution solid-state 13C NMR

High-resolution solid-state ¹³C NMR spectra of drawn (ethylene–vinyl alcohol) copolymer (EVOH) and their ¹³C spin-lattice relaxation times (T₁) were measured in order to elucidate the structure and dynamics of EVOH in the drawn state. It is found that the ¹³C chemical shift of the CH carbon for drawn EVOH moved upfield as compared with that of undrawn EVOH. Further, the mobility for the CH carbons of low molecular motion components are increased by drawing the EVOH sample. From these experimental results, the changes in the structure and dynamics of the drawn EVOH sample can be elucidated.     

Study of entangled network formation in concentrated solutions of polymer by ~(13)C NMR

Information about the exact location of topological and cohesional entanglements at molecular level has been obtained by 13C NMR relaxation analysis. The results show that about 20% of the carbon atoms in the main chain are entangled in the 25% (by weight) solution, which is independent of the content of the 1,2-segment in polybutadiene and of the kind of solvent. However, the entanglement of the carbon atone on the end group of the side chain is very weak, they behave as slipping freely at the junctions.     

Capture of CO2 from flue gas streams with zeolite 13X by vacuum-pressure swing adsorption

Vacuum swing adsorption (VSA) capture of CO₂ from flue gas streams is a promising technology for greenhouse gas mitigation. In this study we use a detailed, validated numerical model of the CO2VSA process to study the effect of a range of operating and design parameters on the system performance. The adsorbent used is 13X and a feed stream of 12% CO₂ and dry air is used to mimic flue gas. Feed pressures of 1.2 bar are used to minimize flue gas compression. A 9-step cycle with two equalisations and a 12-step cycle including product purge were both used to understand the impact of several cycle changes on performance. The ultimate vacuum level used is one of the most important parameters in dictating CO₂ purity, recovery and power consumption. For vacuum levels of 4 kPa and lower, CO₂ purities of >90% are achievable with a recovery of greater than 70%. Both purity and recovery drop quickly as the vacuum level is raised to 10 kPa. Total power consumption decreases as the vacuum pressure is raised, as expected, but the recovery decreases even quicker leading to a net increase in the specific power. The specific power appears to minimize at a vacuum pressure of approximately 4 kPa for the operating conditions used in our study. In addition to the ultimate vacuum level, vacuum time and feed time are found to impact the results for differing reasons. Longer evacuation times (to the same pressure level) imply lower flow rates and less pressure drop providing improved performance. Longer feed times led to partial breakthrough of the CO₂ front and reduced recovery but improved purity. The starting pressure of evacuation (which is not necessarily equal to the feed pressure) was also found to be important since the gas phase was enriched in CO₂ prior to removal by vacuum leading to improved CO₂ purity. A 12-step cycle including product purge was able to produce high purity CO₂ (>95%) with minimal impact on recovery. Finally, it was found that for 13X, the optimal feed temperature was around 67°C to maximize system purity. This is a consequence of the temperature dependence of the working selectivity and working capacity of 13X. In summary, our numerical model indicates that there is considerable scope for improvement and use of the VSA process for CO₂ capture from flue gas streams.     

Discovery of α7-nicotinic receptor ligands by virtual screening of the chemical universe database GDB-13

The chemical universe database GDB-13 enumerates 977 million organic molecules up to 13 atoms of C, N, O, Cl, and S that are virtually possible following simple rules for chemical stability and synthetic feasibility. Analogs of nicotine were identified in GDB-13 using the city-block distance in MQN-space (CBD(MQN)) as a similarity measure, combined with a restriction eliminating problematic structural elements. The search was carried out with a Web browser available at www.gdb.unibe.ch . This virtual screening procedure selected 31?504 analogs of nicotine from GDB-13, from which 48 were known nicotinic ligands reported in Chembl. An additional 60 virtual screening hits were purchased and tested for modulation of the acetylcholine signal at the human α7 nAChR expressed in Xenopus oocytes, which led to the identification of three previously unknown inhibitors. These experiments demonstrate for the first time the use of GDB-13 for ligand discovery.     

Dynamic structure of transmembrane α-helical fragments of bacteriorhodopsin in lipid bilayer characterized by 13C chemical shift tensor and hydrogen bond distance by REDOR NMR

Dynamic structure of [1-¹³C]Ala¹⁴, [¹⁵N]Ala¹⁸-labeled transmembrane fragment A (6–42) of bacteriorhodopsin in DMPC bilayer was examined by careful analysis of ¹³C chemical shift tensors of [1-¹³C]Ala¹⁴ residue and ¹⁵N–H⋯O¹³C hydrogen bond length, as determined by its side-band patterns and rotational echo double resonance method (REDOR), respectively. It was found that rigid-body motions of this helical segment, fluctuating with a time scale of 10⁻⁴ s and dominant at a temperature above 10°C [Biopolymers 58 (2001) 78], ceased at a temperature below 0°C, to give rise to a static spectral pattern similar to that of the solid sample. No evidence was obtained for the presence of the distorted α-helix form in the DMPC bilayer, in view of the similarity between the principal components of ¹³C chemical shift tensors of the lipid bilayer and the solid. Furthermore, accurate C⋯N interatomic distance was measured between ¹⁵N and ¹³C nuclei corresponding to the hydrogen bond length, ¹⁵N–H (Ala¹⁸)⋯O¹³C (Ala¹⁴), characteristic of the α-helix form by REDOR NMR. The C⋯N distance turned out to be 4.5 Å at −30°C, which is in good agreement with that in the solid state taking the ordinary α-helix as estimated from the ¹³C chemical shifts. This finding shows that there is no anomaly in the α-helix form in the lipid bilayer. In this connection, it is emphasized that the ¹³C C_β peak of Ala residue resonating at unusually lower field is a very unique probe to be able to detect the low frequency, local anharmonic motions of the order of 10⁻² s in the lipid bilayer.     

Preparation of 13C-24-methylcholesta-5,24(28)-dien-3β-ol by cultivation of the Baikal diatom Synedra acus in NaH13CO3

A method for preparing ¹³C-24-methylcholesta-5,24(28)-dien-3gB-ol (24-methylenecholesterol) with ¹³C enrichment degree of up to 55% was proposed. The method is based on cultivation of the freshwater diatom alga Synedra acus in a medium containing sodium ¹³C-bicarbonate as the carbon source. ¹³C-24-Methylenecholesterol isolated for the first time was studied by ¹³C NMR spectroscopy and mass spectrometry.     

Studies of Molecular Motions of Ocotillol-Type Saponins in Solution by ~(13)C Nuclear Magnetic Relaxation

In this paper, the fully anisotropicoverall tumbling motions and side groups internal rotation of ocotillol-type saponins separated from the leaves of Panax Quidquefolium L. are investigated by ~(13)C nuclear magnetic relaxation. The fully anisotropic overall tumbling motion model with methyl conformation jumps internal rotation among three equivalent sites is presented, and the spectral density function of this model is derived. The rotation rates for overall tumbling motions to ocotillol-type saponins (OTS) are computed by Woessner's fully anisotropic overall tumbling motion model, and the internal rotation rate and barrier for side groups in OTS are calculated using free diffusion internal rotation model, restriction diffusion internal rotation model and conformation jumps internal rotation model, respectively.     

Study of phase transitions in 4-n-alkoxybenzilidene-4′-n-alkylanilines by one and two dimensional 13C NMR

Abstract

The phase transition of a series of homologous liquid-crystalline compounds, nO.m (4-n-alkoxybenzilidene-4′-n-alkylanilines), from the nematic phase to the smectic A phase has been studied by ¹³C NMR. The order parameters, determined by a two dimensional technique called separated local field spectroscopy combined with off-magic angle spinning, of different molecular segments of these compounds are related linearly to the ¹³C chemical shifts. Changes in the order parameters of the phenyl rings as well as those of the chains during the S_A–N transition depend on the nature of the phase transition. These changes are quantitatively related to the McMillan ratio, which is defined as the ratio between the S_A–N transition temperature (T _SAN) and the nematic to isotropic transition temperature (T _NI), i.e. M = T _SAN/T _NI. The S_A–N transition is first order for M > M _TCP, and second order for M < M _TCP, where TCP is the tricritical point. The value of M _TCP was found to be 0·958 ± 0·004, in excellent agreement with that obtained from spin probe studies (0·959 ± 0·005) reported by Freed and co-workers [1].     

Capture of CO2 from high humidity flue gas by vacuum swing adsorption with zeolite 13X

Capture of CO₂ from flue gas streams using adsorption processes must deal with the prospect of high humidity streams containing bulk CO₂ as well as other impurities such as SO _x , NO _x , etc. Most studies to date have ignored this aspect of CO₂ capture. In this study, we have experimentally examined the capture of CO₂ from a 12% synthetic flue gas stream at a relative humidity of 95% at 30 °C. A 13X adsorbent was used and the migration of the water and its subsequent impact on capture performance was evaluated. Binary breakthrough of CO₂/water vapor was performed and indicated a significant effect of water on CO₂ adsorption capacity, as expected. Cyclic experiments indicate that the water zone migrates a quarter of the way into the column and stabilizes its position so that CO₂ capture is still possible although decreased. The formation of a water zone creates a “cold spot” which has implications for the system performance. The recovery of CO₂ dropped from 78.5% to 60% when moving from dry to wet flue gas while the productivity dropped by 22%. Although the concentration of water leaving the bed under vacuum was 27%(vol), the low vacuum pressure prevented condensation of water in this stream. However, the vacuum pump acted as a condenser and separator to remove bulk water. An important consequence of the presence of a water zone was to elevate the vacuum level thereby reducing CO₂ working capacity. Thus although there is a detrimental effect of water on CO₂ capture, long term recovery of CO₂ is still possible in a single VSA process. Pre-drying of the flue gas steam is not required. However, careful consideration of the impact of water and accommodation thereof must be made particularly when the feed stream temperature increases resulting in higher feed water concentration.     

Hyperpolarized 13C Magnetic Resonance Imaging of Fumarate Metabolism by Parahydrogen-induced Polarization: A Proof-of-Concept in vivo Study

Hyperpolarized [1-¹³C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-¹³C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-¹³C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-¹³C]fumarate at sufficient ¹³C polarization for ex vivo detection of hyperpolarized ¹³C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo ¹³C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis.     

De Vries smectic A phase formed by a liquid crystal side chain copolymer? A 13C NMR study

We study the orientation and order parameter of a liquid crystalline random side chain copolymer by ¹³C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A–smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X‐ray and elastic characterizations of structurally similar materials.