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131.
A stable enzyme encapsulation technique based on the conversion of weak interactions between diazo resin/poly(styrene sulfonate) to covalent bonds was explored. Photosensitive diazoresin-based polyelectrolyte microcapsules were prepared via layer-by-layer electrostatic self-assembly of poly(styrene sulfonate) and diazoresin on MnCO(3) templates. UV-vis and zeta-potential measurements confirmed the alternate deposition of {PSS/DAR} multilayers on the micrometer-sized dissolvable templates. The DAR-based microcapsules were demonstrated to be permeable to enzymes prior to UV irradiation, while the permeability of the multilayer wall was changed substantially after photo-cross-linking. Encapsulated molecules were stably entrapped after UV irradiation, as shown by confocal microscopy and atomic force microscopy images. Activity assays revealed that encapsulated glucose oxidase possessed 52.8% of the catalytic activity exhibited by the same amount of free enzyme, proving the preservation of native conformation and accessibility of substrate. This encapsulation technique is promising for many biomedical and biotechnological applications, particularly enzyme biosensors, which require stable immobilization of functional components while allowing sufficient transport rates for substrate molecules. 相似文献
132.
Low-frequency (80-700 cm-1) Qy-excitation resonance Raman (RR) spectra are reported for thin-solid-film aggregates of several chlorophyll (Chl) a and bacteriochlorophyll (BChl) c/d pigments. The pigments include Chl a, pyrochlorophyll a (PChl a), methylpyrochloropyllide a (MPChl a), methylbacteriochloropyllide d (MBChl d), [E,M] BChl cS, [E,E] BChl cF, and [P,E] BChl cF. The BChl c/d's are the principal constituents of the chlorosomal light-harvesting apparatus of green photosynthetic bacteria. Together, the various Chl a's and BChl c/d's represent a series in which the peripheral substituent groups on the chlorin macrocycle are varied in systematic fashion. All of the Chl a and BChl c/d aggregates exhibit rich low-frequency vibrational patterns. In the case of the BChl c/d's, certain modes in the very low-frequency region (100-200 cm-1) experience exceptionally strong Raman intensity enhancements. The frequencies of these modes are qualitatively similar to those of oscillations observed in femtosecond optical experiments on chlorosomes. The RR data indicate that the low-frequency vibrations are best characterized as intramolecular out-of-plane deformations of the chlorin macrocycle rather than intermolecular modes. The coupling of the out-of-plane modes in turn implies that the Qy electronic transition(s) of the aggregate have out-of-plane character. The RR spectra of the BChl c/d's also reveal that the nature of the alkyl substituents at the 8 and 12 positions of the macrocycle plays an important role in determining the detailed features of the low-frequency vibrational patterns. The frequencies of the modes are particularly sensitive to larger substituent groups whose conformations may be more easily perturbed in the tightly packed aggregates. These factors also make aggregates of pigments containing larger substituents more susceptible to structural, electronic, and vibrational inhomgeneities. Collectively, the RR studies of the various pigments delineate the factors which influence the low-frequency vibrational characteristics of chlorosomal aggregates. 相似文献
133.
Estimation of the aqueous solubility of organic molecules by the group contribution approach 总被引:1,自引:0,他引:1
Several group contribution methods to estimate the aqueous solubility of organic molecules are proposed and evaluated for their ability to predict the water solubility of new molecules. The learning set consisted of 1168 organic compounds with experimental data taken from the literature after critical evaluation. The best method, based on a new fragment atom scheme, leads to a squared correlation coefficient of 0.95 and an average absolute calculation error of 0.50 log unit, which is superior to other group contribution methods currently available. One of the advantages of this model is that it has upper and lower limits so that the predicted solubilities cannot be unrealistily high or low. 相似文献
134.
[reaction: see text] A catalyst for enolate formation was designed that incorporates an amine base along with a thiourea to bind to the oxygen atom of the substrate and enolate through hydrogen bonding. A computational model of the transition state was developed in which the thiourea (modeled initially as a urea) and amine were separate molecules. This model and models incorporating one or two methanol molecules in place of the urea showed an out-of-plane hydrogen bond, apparently to the carbonyl pi-bond, in addition to an in-plane hydrogen bond to an unshared electron pair. In contrast, optimized complexes of the ketone and the fully formed enolate showed only in-plane hydrogen bonding. The transition state model with the urea and amine was used to define a database search with the computer program CAVEAT to identify structures suitable for linking the amine and urea/thiourea moieties in the transition state. On the basis of a group of structures identified from this search, a flexible but conformationally biased linker was designed to connect the two catalytic moieties. The molecule having the amine and thiourea moieties connected by this linker was synthesized and was shown to catalyze proton exchange between methanol and deuterated acetone. The catalyst was about 5-fold more efficient than the amine and thiourea as separate molecules and relative to a similar but less conformationally biased catalyst. 相似文献
135.
Annals of the Institute of Statistical Mathematics - The research is about a systematic investigation on the following issues. First, we construct different outcome regression-based estimators for... 相似文献
136.
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138.
Artuso M Gao M Goldberg M He D Horwitz N Moneti GC Mountain R Muheim F Mukhin Y Playfer S Rozen Y Stone S Xing X Zhu G Bartelt J Csorna SE Egyed Z Jain V Gibaut D Kinoshita K Pomianowski P Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Würthwein F Asner DM Athanas M Bliss DW Brower WS Masek G Paar HP Gronberg J Korte CM Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Roberts D Ryd A Tajima H Witherell MS Balest R Cho K 《Physical review letters》1995,75(5):785-789
139.
Battle M Ernst J Kwon Y Roberts S Thorndike EH Wang CH Dominick J Lambrecht M Sanghera S Shelkov V Skwarnicki T Stroynowski R Volobouev I Wei G Zadorozhny P Artuso M Goldberg M He D Horwitz N Kennett R Mountain R Moneti GC Muheim F Mukhin Y Playfer S Rozen Y Stone S Thulasidas M Vasseur G Zhu G Bartelt J Csorna SE Egyed Z Jain V Kinoshita K Edwards KW Ogg M Britton DI Hyatt ER MacFarlane DB Patel PM Akerib DS Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ 《Physical review letters》1994,73(8):1079-1083
140.
Ting Wu Tianqun Lang Chao Zheng Wenlu Yan Yu Li Runqi Zhu Xin Huang Huae Xu Yaping Li Qi Yin 《Advanced functional materials》2023,33(7):2212109
The red blood cell membrane (RBCm) provides tight protection, lowers the immunogenicity, and prolongs the circulation time of drugs in vivo when acting as the coating of drug delivery systems. However, the cellular uptake and release of drugs are hindered by RBCm. Docetaxel (DTX) is the first-line medicine for treating triple-negative breast cancer (TNBC), but it induces tumor metastasis. To solve these dilemmas, in this study, the photosensitizer 1,1-dioctadecyl-3,3,3,3-tetramethylindotricarbocyanine iodide (DiR)-modified RBCm (DM) is prepared, which is coated onto a hybrid micelle consisting of the prodrugs of DTX and the anti-metastasis agent calcitriol (CTL), obtaining a nanoparticle, named HDC-DM. In a 4T1 tumor-bearing mouse model, after injecting HDC-DM, the intratumoral DTX and CTL concentrations are increased by 1.7 and 2.5 times compared with the free drug groups. After irradiating tumors with near-infrared laser, DiR elicits the photothermal effect, triggering the rupture of RBCm and drug release, promoting drug penetration in tumors, and inducing immunogenic cell death. The tumor growth inhibition rate is 77%, and the formation of lung metastases is reduced by 82%, with good biocompatibility. It is suggested that the combination of phototherapy, chemotherapy, and anti-metastatic therapy using HDC-DM is expected to be a powerful strategy for treating TNBC. 相似文献