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1.
The molecular weight (Mw) effect of polystyrene sulphonate (PSS) on the yield stress of ZrO2 dispersion was evaluated. Three “monodispersed” samples with Mw of 1430, 9960 and 130,000, and two broad distribution samples of Mw 70,000 and 1.0 million were investigated. Adsorbed PSS gave rise to charged patch attraction that enhanced the maximum yield stress, τ y max, of dispersions at charge neutral condition [3]. As a PSS patch consists of only one molecule, the patch size should increase with increasing Mw. For PSS of Mw 1430 with just only seven repeating units the patch formed would be rectangular (linear) and small with a high charge density. For Mw of 9960 and higher, the patch would be irregular in shape with a smaller charge density. At a moderate surface coverage of ˜20%, the τ y max increases quite sharply from Mw 9960 to 130,000 and very gradually from 130,000 to 1.0 million. From Mw 9960 to 130,000, the strength of the patch attraction increases quite strongly with increasing patch size. From Mw 130,000 to 1million, the small increase in τ y max reflected a limiting patch size effect. At the limiting size, the attraction is at maximum strength. At the same coverage, PSS of Mw 1430 also displayed a strong charge patch attraction. This was attributed to a higher number of charged patch interactions at the closest point of separation and also to the high charge density of the PSS patch. The low surface coverage of 6% revealed no significant molecular weight effect on τ y max. The network structure consisted of a mixture of charge patch and bare surface interactions. Received: 4 July 2000/Accepted: 18 July 2000  相似文献   

2.
X-ray photoelectron spectroscopy (XPS) was employed to quantify adsorption of polyelectrolytes from aqueous solutions of low ionic strength onto mica, glass, and silica. Silica surfaces were conditioned in base or in acid media as last pre-treatment step (silica-base last or silica-acid last, respectively). Consistency in the determined adsorbed amount, Γ, was obtained independent of the choice of XPS mode and with the two quantification approaches used in the data evaluation. Under the same adsorption conditions, the adsorbed amount, Γ, varied as Γmica > Γsilica-base last ≈ Γglass > Γsilica-acid last. In addition, the adsorbed amount increased with decreasing polyelectrolyte charge density (100% to 1% of segments being charged) for all substrates. Large adsorbed amount was measured for low-charge density polyelectrolytes, but the number of charged segments per square nanometer was low due to steric repulsion between polyelectrolyte chains that limited the adsorption. The adsorbed amount of highly charged polyelectrolytes was controlled by electrostatic interactions and thus limited to that needed to neutralize the substrate surface charge density. For silica, the adsorbed amount depended on the cleaning method, suggesting that this process influenced surface concentration and fraction of different silanol groups. Our results demonstrate that for silica, a higher density and/or more acidic silanol groups are formed using base, rather than acid, treatment in the last step.  相似文献   

3.
Diamondoids are hydrocarbons having a carbon scaffold comprised from polymer‐like composites of adamantane cages. This article describes computed total energies and “SWB‐tension” energies (often referred to as “strain” energies) for species having n adamantane or diamantane units sharing pairwise: one carbon atom (spiro‐[n]adamantane or spiro‐[n]diamantane); one C? C bond (one‐bond‐sharing‐[n]adamantane or one‐bond‐sharing‐[n]diamantane); or one chair‐shaped hexagon of carbon atoms (1234‐helical‐cata‐[n]diamantanes). Each of the five investigated polymer‐like types is considered either as an acyclic or a cyclic chain of adamantane‐ or diamantane‐unit cages. With increasing n values, SWB‐tension energies for acyclic aggregates are found to increase linearly, while the net SWB‐tension energies of cyclic aggregates often go thru a minimum at a suitable value of . In all five cases, a limiting common energy per unit ( ) is found to be approached by both cyclic and acyclic chains as , as revealed from plots of versus 1/n for acyclic chains and of versus 1/n2 for cyclic chains. © 2015 Wiley Periodicals, Inc.  相似文献   

4.
A binary catalytic system, RuCl2(N‐heterocyclic carbene)(p‐cymene)/alkyne, was developed for improved molecular weight control in ring‐opening metathesis polymerization (ROMP) reactions of norbornene derivatives in organic and aqueous media. Monometallic ruthenium arene compounds were activated using aryl and aliphatic terminal alkynes to form highly active metathesis species. The effects of alkyne structure and concentration on the overall catalytic activity were systematically investigated. The catalytic activity of the metathesis active species can be tuned by varying alkyne substituents. Also, the initiation rate of the ROMP reaction can be tuned by increasing the alkyne‐to‐Ru ratio. ROMP polymers with a wide range of molecular weights (91–832 kDa) were isolated in organic media, whereas polymers with a molecular weight range of 110–280 kDa with average particle sizes of 150–250 nm were isolated in aqueous media. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

5.
Highly homogenous α zein protein was isolated from maize kernels in an environment‐friendly process using 95% ethanol as solvent. Due to the polyploidy and genetic polymorphism of the plant source, the application of high resolution separation methods in conjunction with precise analytical methods, such as MALDI‐TOF‐MS, is required to accurately estimate homogeneity of products that contain natural zein protein. The α zein protein product revealed two main bands in SDS‐PAGE analysis, one at 25 kDa and other at 20 kDa apparent molecular mass. Yet, high resolution 2DE revealed approximately five protein spot groups in each row, the first at ca. 25 kDa and the second at ca. 20 kDa. Peptide mass fingerprinting data of the proteins in the two dominant SDS‐PAGE bands matched to 30 amino acid sequence entries out of 102 non‐redundant data base entries. MALDI‐TOF‐MS peptide mapping of the proteins from all spots indicated the presence of only α zein proteins. The most prominent ion signals in the MALDI mass spectra of the protein mixture of the 25 kDa SDS gel band after in‐gel digestion were found at m/z 1272.6 and m/z 2009.1, and the most prominent ion signals of the protein mixture of the 20 kDa band after in‐gel digestion were recorded at m/z 1083.5 and m/z 1691.8. These ion signals have been found typical for α zein proteins and may serve as marker ion signals which upon chymotryptic digestion reliably indicate the presence of α zein protein in two hybrid corn products.  相似文献   

6.
Potential metal chelators containing one or several acyltetronic acid moieties were prepared from cyclic or acyclic amines and polyamines, and from bis(phenols) by reaction with 1–4 equiv of 3-bromoacetyltetronic acid in the presence of potassium carbonate. The affinity constants of the chelating agents for toxic metallic cations Cd2+, Cs+, and Pb2+ and for dimethylarsinic acid were measured, at pH 7.5 and 9.3. Compound 4, an acyclic triamine containing four acyltetronic moieties, was found to complex efficiently all the tested species.  相似文献   

7.
Purification and characterization of halotolerant, thermostable alkaline l-glutaminase from a Bacillus sp. LKG-01 (MTCC 10401), isolated from Gangotri region of Uttarakhand Himalaya, is being reported in this paper. Enzyme has been purified 49-fold from cell-free extract with 25% recovery (specific activity 584.2 U/mg protein) by (NH4)2SO4 precipitation followed by anion exchange chromatography and gel filtration. Enzyme has a molecular weight of 66 kDa. l-Glutaminase is most active at pH 11.0 and stable in the pH range 8.0–11.0. Temperature optimum is 70 °C and is completely stable after 3 h pre-incubation at 50 °C. Enzyme reflects more enhanced activity with 1–20% (w/v) NaCl, which is further reduced to 80% when NaCl concentration was increased up to 25%. l-Glutaminase is almost active with K+, Zn2+, and Ni2+ ions and K m and V max values of 240 μM and 277.77 ± 1.1 U/mg proteins, respectively. Higher specific activity, purification fold, better halo-tolerance, and thermostability would make this enzyme more attractive for food fermentation with respect to other soil microbe derived l-glutaminase reported so far.  相似文献   

8.
Commercially available lithium hydroxide monohydrate (LiOH·H2O) was found to be a novel ‘dual activation’ catalyst for tandem cross-aldol condensation between cyclic/acyclic ketones and aromatic/heteroaromatic/styryl/alkyl aldehydes leading to an efficient and easy synthesis of α,α′-bis(aryl/alkylmethylidene)ketones at r.t. in short times. The reaction of aryl, heteroaryl, styryl and alkyl aldehydes with acyclic and five/six-membered cyclic ketones afforded excellent yields after 2 min to 1.25 h. The reaction conditions were compatible with various electron withdrawing and electron donating substituents, e.g. Cl, F, NO2, OMe and NMe2. The rate of the cross-aldol condensation was influenced by the nature of the ketone and electronic and steric factors associated with the aldehyde. The reaction took place at a faster rate for acyclic ketone (e.g., acetone) than that for cyclic ketone (e.g., cyclohexanone). In case of cycloalkanones, the rate of the reaction was dependent on the size of the ring of the cycloalkanone. The cross-aldol condensation of cyclopentanone was faster than that of cyclohexanone for a common aldehyde. In case of reactions involving aliphatic aldehyde having α-hydrogen atom no self-aldol condensation of the aldehyde took place.  相似文献   

9.
The effects of alkyl, amino, phosphino, oxy, and thio moieties on the stability, multiplicity and reactivity of α-cyclopropylsilylenes with acyclic, cyclic, and unsaturated cyclic structures are compared and contrasted at B3LYP/AUG-cc-pVTZ//B3LYP/6-31G∗ level. The simultaneous stabilizing effects of heteroatom and cyclopropyl α-substituents on the above silylenes create the following trend of singlet-triplet energy gaps (?ES-T): amino ≈ oxy > thio > alkyl > phosphino. The ΔES-T values for all the above silylenes increase through cyclization, because cyclization stabilizes singlet states of all our α-heteroatom substitued silylenes while destabilizes their corresponding triplet states. The ΔES-T values for all the heteroatom substituted cyclic silylenes decrease upon unsaturation, due to the higher stabilization of triplet compared to the singlet state. Interestingly, isodesmic reactions showed the phosphino substituents stabilize the triplet more than the corresponding singlet states, not only in the unsaturated form but also in the acyclic and cyclic structures. This is in contrast to cyclopropyl which stabilizes singlet considerably more than the corresponding triplet states. The reactivity of the above silylenes is discussed in terms of nucleophilicity, and electrophilicity; showing phosphino- and aminocyclopropylsilylenes more nucleophilic than oxy- and thiocyclopropylsilylenes.  相似文献   

10.
A chiral bidentate phosphoramidite (5a) was synthesized from Shibasaki’s linked-(R)-BINOL and P(NMe2)3 as a new ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds. The effects of 5a and Feringa’s monodentate phosphoramidite (4, R1, R2 = Et) on the yields and enantioselectivities were fully investigated. The reaction was significantly accelerated in the presence of a base such as KOH and Et3N, allowing the reaction to be completed at the lower temperatures than 50 °C. The addition to cyclic enones such as 2-cyclopentenone, 2-cyclohexenone and 2-cycloheptenone at 50 °C in the presence of an [Rh(coe)2Cl]2-4 (R1, R2 = Et) complex resulted in enantioselectivities up to 98%, though it was less effective for acyclic enones (0–70% ee). On the other hand, a complex between [Rh(nbd)2]BF4 and 5a completed the addition to cyclic enones within 2 h at room temperature in the presence of Et3N with 86–99% yields and 96–99.8% ee. This catalyst was also effective for acyclic enones, resulting in 62–98% yields and 66–94% ee. The 1,4-additions of arylboronic acids to unsaturated lactones and acyclic esters with rhodium(I)-phosphoramidites complexes were also investigated.  相似文献   

11.
In this study, an effective method was developed for the isolation and enrichment of Ginkgo biloba extract by continuous chromatography system. The adsorption and desorption ratio of flavonoids as main index, the best macroporous resin was screened out from six resins by static adsorption and desorption tests. At the same time the adsorption and desorption parameters were optimized by dynamic adsorption and desorption tests. Under optimal parameters, five operations consisting of loading, washing, desorbing, regenerating, and balancing were integrated across the continuous chromatography system for the purpose of refining 66 L of crude extract solution. The results were as follows, 198.22 g of Ginkgo biloba extracts was produced, which contained 65.83 g of flavonoids and 15.44 g of lactones. The content of flavonoids and lactones increased from 2.76 and 0.72% in the crude extract to 33.21 and 7.79%, with a recovery yield of 91.26 and 81.21%. Methodology validation showed that the proposed method had high stability and reproducibility. Compared with the traditional macroporous resin method, the proposed method had a short processing time and low solvent consumption. Our studies indicated that the newly developed method is an effective procedure for the isolation and enrichment of Ginkgo biloba extract.  相似文献   

12.
This work discusses the results appearing in Wu et al.’s (2014) article dealing with three aliphatic-aromatic polyesters based on terephthalic acid and their spectral identification. Using an instrument equipped with a switch that allows ions with masses below 5 kDa to be discarded (ion deflector), the authors report the MALDI spectrum of a commercial poly(ethylene terephthalate) with signals up to 80 kDa. I plot the spectral intensities and fit them with a Gaussian curve. The result is carefully examined. Thereafter, attention is moved to the MALDI spectra obtained when the ion deflector is turned off. A computation that gives the number-average and the weight-average molar mass (Mn and Mw) was performed, but the result was Mn = 1362 g/mol and Mw = 1416 g/mol. These values are much too low and they cannot be used. In order to explain this failure, I modified a model developed for poly(pentylene adipate). This hypothesis is discarded and the correct explanation is found. I also discuss other types of instrumentation, for instance, Py-GC/MS combined with library-search and also NMR spectroscopy, with specific reference to the chemical shifts of the -CH2- protons in aliphatic-aromatic polyesters.  相似文献   

13.
Reaction of cyclic carbonates or sulfites of acyclic alkynyl diols with organocopper reagents proceeded in SN2′ fashion and afforded α-allenic alcohols of high enantiomeric purity. The stereochemistry of this transformation was shown to be highly anti-diastereoselective.  相似文献   

14.
Cobalt-containing complexes capable of catalyzing reactions of trialkyl- and alkylhaloalanes (R n AlCl3–n ) with olefins, allenes, and acetylenes were synthesized. The reactions afford cyclic and acyclic organoaluminum compounds.  相似文献   

15.
Two regioselective, high-yielding one-pot routes to oxygen-bridged cyclic diaryliodonium salts and ortho-aryloxy-substituted acyclic diaryliodonium salts are presented. Starting from easily available ortho-iodo diaryl ethers, complete selectivity in formation of either the cyclic or acyclic product could be achieved by varying the reaction conditions. The complimentary reactivities of these novel ortho-oxygenated iodonium salts were demonstrated through a series of chemoselective arylations under metal-catalyzed and metal-free conditions, to deliver a range of novel, ortho-functionalized diaryl ether derivatives.  相似文献   

16.
The state of tetra(3-nitro-5-tert-butyl)phthalocyanine in DMSO medium was studied. Sufficiently high stability of the obtained proton transfer complex is established, and its structure is suggested. It is shown that this complex is kinetically unstable in the highly basic media. Effect of the nature of cyclic and acyclic nitrogen-containing bases on the rate and activation parameters of destruction of the proton transfer complex of tetra(3-nitro-5-tert-butyl)phthalocyanine was found  相似文献   

17.
Size-fractions from a soil humic acid were separated by preparative size-exclusion chromatography (SEC), desalted, and concentrated by ultrafiltration and vacuum centrifugation without being subjected to any freeze-drying process. After having assessed the lack of formation of any multiple-charged ions by high-resolution Fourier transform ion cyclotron resonance electrospray ionization (ESI) mass spectrometry (MS), the size-fractions were used by direct infusion to compare the molecular ion distribution by both atmospheric pressure chemical ionization (APCI)- and ESI-MS in negative mode. The weight- (Mw) and number-averaged (Mn) molecular weight obtained by ESI-MS were invariably larger than by APCI-MS for all size-fractions, thereby indicating that ESI is more efficient than APCI to evaluate the molecular mass distribution of humic samples. No substantial difference was observed when concentration and pH of unfreeze-dried humic size-fractions were varied. The negative mode was applied to assess the effect of cone voltage from −20 to −60 V on ESI of the humic size-fractions further separated through an on-line SEC column. The resulting mass spectra and Mw and Mn values suggested that the variation of cone voltage in ESI-MS affects the ionization potential of associated humic molecules more in solution rather than their fragmentation. These findings agree with previous observations which indicated a limitation of ESI in providing consistent mass detection for a complex mixture of heterogeneous humic molecules, especially when they are aggregated by a freeze-drying process.  相似文献   

18.
Recently, planar-chiral phosphine-olefin ligands based on (η6-arene)chromium(0) and (η5-cyclopentadienyl)manganese(I), which are known as first- and second-generation, respectively, have been developed. These ligands were employed for Rh-catalyzed asymmetric 1,4-addition to enones. First-generation ligands involve high enantioselectivity for cyclic enones (>98% ee). Second-generation ligands involve high enantioselectivity for not only cyclic enones but also for acyclic enones (>98% ee). In this study, we have performed DFT calculations to investigate the origin of enantioselectivity. The theoretical values of enantioselectivities were found to be in good agreement with the experimental values obtained for a cyclic enone, 2-cyclopenten-1-one, using both the first- and second-generation ligands. Regarding an acyclic enone, 3-penten-2-one, it was found that the s-cis type decreases the enantioselectivity because the transition states in the s-cis type have a large steric repulsion. Energy decomposition analysis (EDA) and natural bond orbital (NBO) analysis indicate that it is important to study the orbital interactions in the transition states of the insertion step for the acyclic enone attacked from si-face with the second-generation ligand. © 2018 Wiley Periodicals, Inc.  相似文献   

19.
Three‐ and four‐arm star shaped polymers, as well as diblock copolymers, are synthesized via acyclic diene metathesis (ADMET) polymerization. This is accomplished by using an asymmetric α,ω‐diene containing a terminal double bond and an acrylate, which is polymerized in the presence of multifunctional acrylates as selective and irreversible chain transfer agents using Hoveyda‐Grubbs second generation catalyst. High cross‐metathesis selectivities are achieved at low temperatures enabling good control over molecular weights. Furthermore, additional polyethyleneglycol (PEG) blocks are attached to these polymers via Heck coupling of the acrylate end‐groups of these polymers with aryl iodide functionalized PEG, obtaining three‐ and four‐arm star shaped di‐ and triblock copolymers with molecular weights up to 31 kDa.

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20.
The cellulosic part of rice straw was modified to develop N-halamine derivatives for disinfection. The process involved cross-linking of the cellulosic material with amino/amide/imide containing compounds; cyclic and acyclic. The structures of the prepared materials were identified using FTIR and solid state 13CNMR. The modified materials were halogenated to form N-halamines and the antimicrobial activity of each evaluated against examples of Gram-positive (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli) using a variety of methods; agar plate, blended agar, stirred flask and in columns. One of the N-halamines achieved a 9 log reduction against both E. coli and S. aureus in 4 h. In addition, no S. aureus growth was recorded on agar plates blended with 0.5 g of this same material.  相似文献   

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