海绵Spongia sp.化学成分的研究（I）

应用气相色谱－质谱联用技术从海绵Ｓｐｏｎｇｉａ ｓｐ．中分离鉴定出４个化学成分：１．－氯－２,２－二对氯苯基乙烯（ＤＤＭＵ,Ｉ）、１,１－二氯－２,２－二对氯苯基乙烯（ＤＤＥ,Ⅱ）、１,１－二氯－２,２－二对氯苯乙烷（ＤＤＤ,Ⅲ）和角鲨烯（Ⅳ）。前３个化合物是首次从Ｓｐｏｎｇｉａ属海绵中分离得到。     

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P₆₆₆₁₄⁺) and tetrakis(pentafluorophenyl)borate anion (TB⁻) was employed within a water|P₆₆₆₁₄TB (w|P₆₆₆₁₄TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. ¹³⁷Cs is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N,N′-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans-Uranium EXtraction processes and investigated through well established liquid|liquid electrochemistry. This study gave access to the metal ion to ligand (1:n) stoichiometry and overall complexation constant, β, of the interfacial complexation reaction which were determined to be 1:3 and 1.6 × 10¹¹ at the w|P₆₆₆₁₄TB interface while the study at w|o elicited an n equal to 1 with β equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, δ_α, with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave δ_α of 2 and 8.2 × 10⁷, respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water–organic solvent mixture into an electron spray ionization mass spectrometer.     

Dynamic contrast-enhanced MRI and MR diffusion imaging to distinguish between glandular and stromal prostatic tissues

Purpose

To compare peak enhancement (PE), determined from dynamic contrast-enhanced (DCE) magnetic resonance imaging (MRI) and the magnetic resonance (MR) directionally-averaged apparent diffusion coefficient () in glandular versus stromal prostatic tissues and, with this comparison, to infer if the hypothesis that gadolinium-DTPA (Gd-DTPA) does not enter healthy glands or ducts is plausible.

Materials and Methods

MRI, MR spectroscopic imaging, DCE MRI and MR diffusion were evaluated in 17 untreated subjects with suspected or proven prostate cancer. PE and were compared in glandular-ductal tissues [normal peripheral zone and glandular benign prostatic hyperplasia (BPH)] and stromal-low ductal tissues (central gland/mixed BPH and stromal BPH).

Results

The glandular-ductal tissues had lower PE [125±6.4 (% baseline)] and higher [1.57±0.15 (s/10⁻³ mm²)] than the stromal-low ductal tissues [PE=132±5.5 (% baseline) (P<.0008), =1.18±0.20 (s/10⁻³ mm²) (P<1×10⁻⁸)]. A statistical model based upon stepwise regression was generated and completely separated the tissue types: ductal Measure = 448+669× (s/10⁻³ mm²)−10.7×PE (1/%), R²=1.0 and P<8×10⁻¹⁰.

Conclusions

The very different MR results in the glandular-ductal versus stromal-low ductal tissues suggest that these tissues have different underlying structure. These results support the hypothesis that Gd-DTPA does not enter healthy prostatic glands or ducts. This may explain the higher PE and lower that previously have been reported in prostate cancer versus healthy tissue.     

Comparison of tumor histology to dynamic contrast enhanced magnetic resonance imaging-based physiological estimates

Purpose

The purpose of this study was to compare histologically determined cellularity and extracellular space to dynamic contrast-enhanced magnetic resonance imaging (DCE MRI)-based maps of a two-compartment model's parameters describing tumor contrast agent extravasation, specifically tumor extravascular extracellular space (EES) volume fraction (v_e), tumor plasma volume fraction (v_p) and volume-normalized contrast agent transfer rate between tumor plasma and interstitium (K_TRANS/V_T).

Materials and Methods

Obtained v_e, v_p and K_TRANS/V_T maps were estimated from gadolinium diethylenetriamine penta-acetic acid DCE T₁-weighted gradient-echo images at resolutions of 469, 938 and 2500 μm. These parameter maps were compared at each resolution to histologically determined tumor type, and the high-resolution 469-μm maps were compared with automated cell counting using Otsu's method and a color-thresholding method for estimated intracellular (V_{intracellular}) and extracellular (V_{extracellular}) space fractions.

Results

The top five K_TRANS/V_T values obtained from each tumor at 469 and 938 μm resolutions are significantly different from those obtained at 2500 μm (P<.0001) and from one another (P=.0014). Using these top five K_TRANS/V_T values and the corresponding tumor EES volume fractions v_e, we can statistically differentiate invasive ductal carcinomas from noninvasive papillary carcinomas for the 469- and 938-μm resolutions (P=.0017 and P=.0047, respectively), but not for the 2500-μm resolution (P=.9008). The color-thresholding method demonstrated that v_e measured by DCE MRI is statistically similar to histologically determined EES. The V_{extracellular} obtained from the color-thresholding method was statistically similar to the v_e measured with DCE MRI for the top 10 K_TRANS/V_T values (P>.05). DCE MRI-based K_TRANS/V_T estimates are not statistically correlated with histologically determined cellularity.

Conclusion

DCE MRI estimates of tumor physiology are a limited representation of tumor histological features. Extracellular spaces measured by both DCE MRI and microscopic analysis are statistically similar. Tumor typing by DCE MRI is spatial resolution dependent, as lower resolutions average out contributions to voxel-based estimates of K_TRANS/V_T. Thus, an appropriate resolution window is essential for DCE MRI tumor diagnosis. Within this resolution window, the top K_TRANS/V_T values with corresponding v_e are diagnostic for the tumor types analyzed in this study.     

A feasible high spatiotemporal resolution breast DCE-MRI protocol for clinical settings

Three dimensional bilateral imaging is the standard for most clinical breast dynamic contrast-enhanced (DCE) MRI protocols. Because of high spatial resolution (sRes) requirement, the typical 1–2 min temporal resolution (tRes) afforded by a conventional full-k-space-sampling gradient echo (GRE) sequence precludes meaningful and accurate pharmacokinetic analysis of DCE time-course data. The commercially available, GRE-based, k-space undersampling and data sharing TWIST (time-resolved angiography with stochastic trajectories) sequence was used in this study to perform DCE-MRI exams on thirty one patients (with 36 suspicious breast lesions) before their biopsies. The TWIST DCE-MRI was immediately followed by a single-frame conventional GRE acquisition. Blinded from each other, three radiologist readers assessed agreements in multiple lesion morphology categories between the last set of TWIST DCE images and the conventional GRE images. Fleiss’ κ test was used to evaluate inter-reader agreement. The TWIST DCE time-course data were subjected to quantitative pharmacokinetic analyses. With a four-channel phased-array breast coil, the TWIST sequence produced DCE images with 20 s or less tRes and ~ 1.0×1.0×1.4 mm³ sRes. There were no significant differences in signal-to-noise (P=.45) and contrast-to-noise (P=.51) ratios between the TWIST and conventional GRE images. The agreements in morphology evaluations between the two image sets were excellent with the intra-reader agreement ranging from 79% for mass margin to 100% for mammographic density and the inter-reader κ value ranging from 0.54 (P<.0001) for lesion size to 1.00 (P<.0001) for background parenchymal enhancement. Quantitative analyses of the DCE time-course data provided higher breast cancer diagnostic accuracy (91% specificity at 100% sensitivity) than the current clinical practice of morphology and qualitative kinetics assessments. The TWIST sequence may be used in clinical settings to acquire high spatiotemporal resolution breast DCE-MRI images for both precise lesion morphology characterization and accurate pharmacokinetic analysis.     

Reductive dechlorination of tetrachloroethylene (PCE) catalyzed by cyanocobalamin

A biomimetic system has been developed for the reductive dechlorination of tetrachloroethylene (PCE). PCE was dechlorinated to trichloroethylene (TCE) and 1,2-dichloroethylene (DCE) in the presence of dithiothreitol or Ti (III) citrate and catalytic amounts of cyanocobalamin in both homogeneous reaction mixtures and packed bed reactor systems. In packed bed reactors with Ti (III) citrate as the reductant, PCE (0.18 mM) conversion averaged 55% at residence times of 1.75 and 3.5 h. The product distribution was 94% TCE and 6% DCE at the lower residence time. DCE formation increased to 45% at the higher residence time. No reduction of PCE was observed in the absence of cyanocobalamin. This system may be useful as a means of pretreatment of halogenated aliphatic hydrocarbons in advance of biological treatment.