Applications of Genetic Algorithm in Polymer Science and Engineering

In the last several years, genetic algorithm (GA) has gained wide acceptance as a robust optimization algorithm in almost all areas of science and engineering. Polymer science and engineering is no exception. Researchers in this field have devoted considerable attention to the optimization of polymer productionusing objective functions and constraints that lead to products having desired material properties. Multiple-objective functions have been optimized simultaneously. An example is the minimization of the reaction time in a reactor (lower costs) while simultaneously minimizing the concentration of side products (that affect the properties of the product adversely). Several end-point constraints (equality or inequality) may also be present, as, e.g., obtaining polymer of a desired molecular weight. Again, this requirement stems from producing polymer having desired strength. Solving such problems usually result in Pareto sets. A variety of adaptations of GA have been developed to obtain optimal solutions for such complex problems. These adaptations can be used to advantage in other fields too. The applications of GA in areas of polymer science and engineering other than polymerization systems are few and far between, but this field is now maturing, and it is hoped that the future will see several newer applications.     

Cholestane as a digestibility marker in the absorption of polyunsaturated fatty acid ethyl esters in Atlantic salmon

Salmonid fish require long-chain n−3 fatty acids in their diet. The digestibility of different chemical forms of fish oil fatty acids, fed as triacylglycerols, free fatty acids or ethyl esters, was examined in 300 g farmed Atlantic salmon (Salmo salar) using cholestane as an indicator of fat absorptionin lieu of the chromium oxide (Cr₂O₃) which is commonly used as a marker in digestibility studies. It was established that the two digestibility markers gave similar results. Conveniently, cholestane does not require a separate analysis if fatty acids are to be determined by appropriate gas-liquid chromatography. The long-chain polyunsaturated fatty acids were particularly well absorbed, the apparent digestibility being 90–98% when feeding triacylglycerols or free fatty acids. However, the digestibility of monounsaturated fatty acids (75–94%) was lower, and lower still for saturated fatty acids (50–80%). Ethyl esters of fatty acids were significantly less well absorbed (P<0.05) than were the corresponding fatty acids in free acid or triacylglycerol form. Irrespective of dietary fat type, only free fatty acids were identified in feces, indicating total hydrolysis of triacylglycerols and ethyl esters. Presented in part at the World Aquaculture Society meeting, June 10–14, 1990, Halifax, Canada.     

Parametric sensitivity of chain polymerization reactors exhibiting the trommsdorff effect

The recently developed mathematical technique for studying the parametric sensitivity of reactors is extended to include chain polymerization systems exhibiting the gel and glass effects, as well as physical property variations. The sensitivities of the two temperature maxima with respect to various parameters are computed. It is found that, for a sample system, poly(methyl methacrylate), all the sensitivities of the gel effect induced temperature peak attain their maxima at the same conditions—this leads to a generalized temperature sensitivity constraint applicable to reactor design or operation. This sensitivity boundary is associated with high conversions and high molecular weights. The analysis shows that the dimensionless propagation activation energy, ?_p, and the dimensionless initiation activation energy, ?_d, are the two most important parameters governing the system performance. Sensitivities of the gel effect-induced number average chain length peak with respect to various parameters are also obtained. Again, all of these chain length sensitivities show maxima at the same condition, leading to the concept of a generalized chain length sensitivity criterion of constraint. Most importantly, the temperature and chain length sensitivity boundaries are virtually identical.     

Phytol Derivatives as Drug Resistance Reversal Agents

Phytol was chemically transformed into fifteen semi‐synthetic derivatives, which were evaluated for their antibacterial and drug resistance reversal potential in combination with nalidixic acid against E. coli strains CA8000 and DH5α. The pivaloyl ( 4 ), 3,4,5‐trimethoxybenzoyl ( 9 ), 2,3‐dichlorobenzoyl ( 10 ), cinnamoyl ( 11 ), and aldehyde ( 14 ) derivatives of phytol ((2E,7R,11R)‐3,7,11,15‐tetramethyl‐2‐hexadecen‐1‐ol) were evaluated by using another antibiotic, tetracycline, against the MDREC‐KG4 clinical isolate of E. coli. Derivative 4 decreased the maximal inhibitory concentration (MIC) of the antibiotics by 16‐fold, while derivatives 9 , 10 , 11 , and 14 reduced MIC values of the antibiotics up to eightfold against the E. coli strains. Derivatives 4 , 9 , 10 , 11 , and 14 inhibited the ATP‐dependent efflux pump; this was also supported by their in silico binding affinity and down‐regulation of the efflux pump gene yojI, which encodes the multidrug ATP‐binding cassette transporter protein. This study supports the possible use of phytol derivatives in the development of cost‐effective antibacterial combinations.     

Radiolabeled Polymeric Nanoconstructs Loaded with Docetaxel and Curcumin for Cancer Combinatorial Therapy and Nuclear Imaging

Growing evidence suggests that multifaceted diseases as cancer can be effectively tackled by hitting simultaneously different biological targets and monitoring patient‐specific responses. Combinatorial therapies, relying on the administration of two or more molecules with different cytotoxic mechanisms, are rapidly progressing in the clinic. Here, 100 nm spherical polymeric nanoconstructs (SPNs) are proposed for the combinatorial treatment of tumors by codelivering a potent antimitotic drug—docetaxel (DTXL)—and a broad spectrum anti‐inflammatory molecule—curcumin (CURC). In vitro, SPNs loaded with DTXL and CURC induce a threefold decrease in IC₅₀ as compared to DTXL‐loaded SPNs. This synergic antitumor effect is also significant in mouse models of glioblastoma multiforme, where, after 22 d of treatment, the combinatorial approach leads to complete disease regression. At 90 d post‐treatment initiation, mice injected with DTXL + CURC SPNs have a 100% survival, whereas only 50% of the DTXL SPN treated mice survive. SPNs are also labeled with radioactive ⁶⁴Cu(DOTA) molecules to document, via PET imaging, the progressive tumor mass shrinkage. Sensitization of DTXL by CURC is associated with NF‐κB downregulation and increased apoptosis. These theranostic nanoconstructs could be used for combinatorial treatment and assessment of therapeutic efficacy in other malignancies.     

Hierarchically Structured Magnetic Nanoconstructs with Enhanced Relaxivity and Cooperative Tumor Accumulation

Iron oxide nanoparticles are formidable multifunctional systems capable of contrast enhancement in magnetic resonance imaging, guidance under remote fields, heat generation, and biodegradation. Yet, this potential is underutilized in that each function manifests at different nanoparticle sizes. Here, sub‐micrometer discoidal magnetic nanoconstructs are realized by confining 5 nm ultra‐small super‐paramagnetic iron oxide nanoparticles (USPIOs) within two different mesoporous structures, made out of silicon and polymers. These nanoconstructs exhibit transversal relaxivities up to ≈10 times (r ₂ ≈ 835 mm ^?1 s^?1) higher than conventional USPIOs and, under external magnetic fields, collectively cooperate to amplify tumor accumulation. The boost in r ₂ relaxivity arises from the formation of mesoscopic USPIO clusters within the porous matrix, inducing a local reduction in water molecule mobility as demonstrated via molecular dynamics simulations. The cooperative accumulation under static magnetic field derives from the large amount of iron that can be loaded per nanoconstuct (up to ≈65 fg) and the consequential generation of significant inter‐particle magnetic dipole interactions. In tumor bearing mice, the silicon‐based nanoconstructs provide MRI contrast enhancement at much smaller doses of iron (≈0.5 mg of Fe kg^?1 animal) as compared to current practice.     

Poly(4‐methyl‐1‐pentene)/clay nanocomposites: effect of organically modified layered silicates

The preparation and properties of poly(4‐methyl‐1‐pentene) (PMP)/clay nanocomposites are reported. Melt intercalation of PMP is carried out with organoclays of different cation/charge exchange capacities and modifiers to facilitate intercalation of the polymer into the silicate layers. The effect of modifiers on the structure and properties of PMP/clay nanocomposites is explored. XRD patterns confirm the intercalation of polymer in the layered silicates as evidenced by the increase in the inter‐layer spacing which is dependent on the type of modifier used. Dynamic mechanical analysis shows increments in the storage modulus over the temperature range studied for all of the three clays, but the extent depends on the type of clay modifier used. The coefficient of thermal expansion is lower for all of the nanocomposites, as compared to the pristine polymer, indicating improved dimensional stability Copyright © 2003 Society of Chemical Industry     

A study of protean systems—Redundancy optimization in consecutive-k-out-of-n:F systems

A Protean system is a system that is subject to changes from time to time. A consecutive-k-out-of-n:F system that has a fluctuation of demand on the system performance, may be classed under Protean systems. The changing demand may be handled by improving the system performance using some extra resources. In this paper, the extra resources considered are in the form of i.i.d. components. These components are allocated with the objective of maximising the system reliability. There are three methods developed in this paper. The first method is developed by formulating the problem mathematically. The second method involves enumeration of all possible allocations of a given number of i.i.d. components. The third method is a heuristic, based on component reliability importance. The accuracy of the heuristic is established by comparing it with the second method. These two methods are compared using computer programs developed by one of the authors.     

Effect of intramolecular reactions in multifunctional step growth polymerizations in cascades of continuous-flow,stirred-tank reactors

A simple kinetic model describing intramolecular reactions in multifunctional step growth polymerizations of RA_j monomers is presented. The model is far simpler than more detailed kinetic or Monte Carlo models which pose severe numerical difficulties close to gelation. The formulation presented is quite general, but it requires a relationship for the ensemble-cum-time average number of rings, r _n, per molecule having n RA_j units. A very simple yet intuitively correct equation has been chosen for r _n, which involves an empirical parameter ?? Results on cascades of homogeneous continuous-flow stirred-tank reactors (HCSTRs) show trends which are physically expected. The present formulation could possibly be used for scale-up of HCSTRs, with ?? obtained experimentally. It is hoped that future studies using rigorous models would lead to more fundamental and improved relationships for r _n.     

替换机械式开关的单IC基电子电路

简单廉价电路使用一个低成本按键开关就可以触发电源的开关.该电路可替换更高价格及外形较大的按键式机械开关.按键开关触发一个单稳电路.