The thickness of dendronized polymers can be tuned by varying their generation g and the dendron functionality X. Systematic studies of this effect require (i) synthetic ability to produce large samples of high quality polymers with systematic variation of g, X and of the backbone polymerization degree N, (ii) a theoretical model relating the solvent swollen polymer diameter, r, and persistence length, lambda, to g and X. This article presents an optimized synthetic method and a simple theoretical model. Our theory approach, based on the Boris-Rubinstein model of dendrimers predicts r approximately n(1/4)g(1/2) and lambda approximately n(2) where n = [(X - 1)(g) - 1]/(X - 2) is the number of monomers in a dendron. The average monomer concentration in the branched side chains of a dendronized polymer increases with g in qualitative contrast to bottle brushes whose side chains are linear. The stepwise, attach-to, synthesis of X = 3 dendronized polymers yielded gram amounts of g = 1-4 polymers with N approximately = 1000 and N approximately = 7000 as compared to earlier maxima of 0.1 g amounts and of N approximately = 1000. The method can be modified to dendrons of different X. The conversion fraction at each attach-to step, as quantified by converting unreacted groups with UV labels, was 99.3% to 99.8%. Atomic force microscopy on mixed polymer samples allows to distinguish between chains of different g and suggests an apparent height difference of 0.85 nm per generation as well as an increase of persistence length with g. We suggest synthetic directions to allow confrontation with theory.
Synthesis of novel zwitterionic block copolypeptides, poly(N-isopropylacrylamide)-block-poly(L-glutamic acid-co-L-lysine) [PNiPAM(n)(PLG(x)-co-PLLys(y))m , where n is the number-average degree of polymerization (DP(n)) of PNiPAM block, x and y are the mole fraction of glutamic acid and lysine residues, respectively, and m is the total DP(n) of the peptide block], and their stimuli-responsiveness to temperature and pH variation in aqueous solutions are described. Initiated with the amino-terminated poly(N-isopropylacrylamide) (PNiPAM(n)-NH2), ring-opening polymerization (ROP) of a mixture of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA), and Boc-L-lysine N-carboxyanhydride (BLLys-NCA) afforded the block copolypeptides PNiPAM(n)(PBLG(x)-co-PBLLys(y))m, with a poly(N-isopropylacrylamide) block together with a random copolypeptide block, which was then deprotected with HBr/trifluoroacetic acid into the double hydrophilic block copolypeptides, PNiPAM(n)(PLG(x)-co-PLLys(y))m. Their block ratios and lengths, as well as the amino acid residue ratios in the random copolypeptide block are varied (n = 360, x = 0.4-0.5, y = 0.4-0.6, and m = 220-252). The secondary structures of the copolypeptides in aqueous solution at different pH conditions were examined. Phase transitions in aqueous solutions induced by both pH and temperature variation were investigated by (1)H NMR spectroscopy. The transitions induced by temperature were also explored by turbidity measurements using UV/vis spectroscopy for their lower critical aggregation temperature (LCAT) determination. Furthermore, these aggregation processes were followed by dynamic light scattering measurements.
This paper presents a Model Predictive Control (MPC)-based coordinated voltage control scheme for distribution networks with high penetration of distributed generation (DG) and energy storage. In this scheme, the DG units, energy storage devices and on-load tap changer (OLTC) are optimally coordinated to maintain all bus voltages in the network within a permissable range. To better coordinate the economical operation and voltage regulation, two control modes are designed according to the operating conditions. In the preventive mode, the DG units operate in the maximum power point tracking (MPPT) mode. State-of-charge (SoC) of energy storage system (ESS) units and power outputs of DG and ESS units are optimized while maintaining the voltages within the feasible range. In the corrective mode, active power curtailment of DG units is also used as a necessary method to correct the severe voltage deviations. The voltage sensitivity coefficients with respect to the power injections and tap changes are updated in real time using an analytical sensitivity calculation method to improve the computation efficiency. A test system consisting of two 20kV feeders fed from the same substation based on a real distribution network was used to validate the proposed coordinated voltage control scheme under both normal and large-disturbance conditions.
Viscosities of dilute solutions were measured for four generations of peripherically charged dendronized poly(methyl methacrylate)s (CDPs) of two different chain lengths in water (no salt added) and of their uncharged analogues (UCPs) in chloroform. In all cases it was possible to describe ln(ηsolution/ηsolvent) as a function of polymer concentration by two adjustable parameters: a hydrodynamic interaction parameter B and [η], the intrinsic viscosity of the polymer. The [η] values for the first generation of polyelectrolytes are markedly lower (given number of monomeric units) than that of aqueous solutions of Na-polystyrene sulfonate reported earlier, despite the fact that each monomeric unit is much larger and bears two charges instead of one; as the number of generation rises, [η] falls markedly for the CDPs as well as for the UCPs, where the effect is considerably more pronounced for the polyelectrolyte. The increase in molar mass M associated with the addition of dendrons leads to a maximum in the molar hydrodynamic volume [η]M for the second generation of the CDP; in case of the UCPs this volume increases steadily. The interaction parameter B is normally positive but may for the higher generations become negative, corresponding to a more than exponential augmentation of η with polymer concentration. A consistent description of the findings is presented in terms of intra- and intermolecular interactions between the -NH and -O- groups of the dendrons and the distances of the charges from the polymer backbone.
Organic mercurial compounds are the most specific and sensitive reagents for reaction with the sulfhydryl groups (OSHs) in peptides and proteins because of the strong mercury-sulfur affinity. Using the monofunctional organic mercury ion RHg ϩ as a mass spectrometry (MS)-tag has the advantages of reacting with one sulfhydryl group, offering definite mass shift, and especially stable and characteristic nonradioactive isotopic distribution. Mass spectrometric analysis of derivatized sulfhydryls in peptides/proteins is thus an alternative for precisely counting the number of sulfhydryl groups and disulfide bonds (OSOSO). Here the tags used include monomethylmercury chloride, monoethylmercury chloride, and 4-(hydroxymercuri) benzoic acid. The feasibility of this strategy is demonstrated using HPLC/ESI-MS to count OSHs and OSOSO in model peptides/proteins, i.e., glutathione, phytochelatins, lysozyme and -lactoglobulin, which contain increasing OSHs and various OSOSO linkages. (J Am
Members of the interleukin 12 (IL-12) family have been known to be inflammatory factors since their discovery. The IL-12 family consists of IL-12, IL-23, IL-27, IL-35, and a new member, IL-39, which has recently been identified and has not yet been studied extensively. Current literature has described the mechanisms of immunity of these cytokines and potential uses for therapy and medical cures. IL-12 was found first and is effective in combatting a wide range of naturally occurring viral infections through the upregulation of various cytokines to clear the infected cells. IL-23 has an essential function in immune networks, can induce IL-17 production, and can antagonize inhibition from IL-12 in the presence of T helper (Th) 17 cells, resulting in type II IFN (IFN-γ) regulation. IL-27 has a competitive relationship to IL-35 because they both include the same subunit, the Epstein–Barr virus-induced gene3 (EBi3). This review provides a simple introduction to the IL-12 family and focuses on their functions relevant to their actions to counteract viral infections.
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