On theC p toC v conversion of solid linear macromolecules II

A modification is proposed for the Nernst-Lindemann equation that is used to convert calculated heat capacities at constant pressure (C _p ) to heat capacities at constant volume (C _v ) for solid, linear macromolecules. the constant A₀ per mole of repeating unit in this equation is derived by taking into account the variable number of vibrators excited at different temperatures. With the new equation it is possible to calculateC _p for solid polymers over a wider temperature range. The constant is calculated for solid polymers from experimental thermal expansivity, isothermal compressibility and heat capacity data obtained from the literature. An average value of (3.9±2.4)×10^–3(K mol)/J was obtained for A₀ (new) from data on 22 solid polymers. This average value may be used as a universal constant in case no experimental data on compressibility and expansivity are available for computation ofA ₀. The remaining variation of A₀ (new) with temperature is discussed and example calculations are shown for polyethylene. Effects of premelting and possibly large-amplitude motion are discovered for polyethylene in the temperature range 290 to 410 K.

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Zusammenfassung Es wurde eine Abänderung der Nernst-Lindemann Gleichung vorgeschlagen, mit deren Hilfe für feste, lineare Makromoleküle errechnete Wärmekapazitäten bei konstantem Druck (C _p ) in Wärmekapazitäten bei konstantem Volumen (C _p ) umgerechnet werden können. Zur Ableitung der molaren Konstanten A₀ in dem sich wiederholenden Teil der Gleichung wurde die variable Anzahl der erregten Schwinger bei verschiedenen Temperaturen berücksichtigt. Mit der neuen Gleichung wird es möglich, dieC _p fester Polymere für einen breiten Temperaturbereich zu errechnen. Die Konstante wurde für die festen Polymere auf Grund des ermittelten thermischen Ausdehnungsvermögens und der isothermen Kompressibilität sowie der der Literatur entnommenen Wärmekapazitätsangaben berechnet. Aus Angaben von 22 festen Polymeren wurde für A₀(neu) ein Durchschnittswert von (3,9±2,4)×10^–3 (K mol)/J erhalten. Verfügt man zur Berechnung von A₀ über keine experimentellen Werte für Kompressibilität und Ausdehnungsvermögen, so kann dieser durchscnittswert als universale Konstante angewendet werden. Die verbleibende Temperaturabhängigkeit von A₀(neu) wird besprochen und Beispielrechnungen für Polyäthylen gegeben. Für Polyäthylen wurden im Temperaturbereich 290 bis 410 K Effekte durch Vorschmelzen und Bewegungen mit großer Amplitude festgestellt.

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-, (C _p ) (C _v ) , . A ₀ , . C _p . A ₀ , , . 22 , A ₀ () (3,9±2,4)· 10^–3 ·/. A ₀ . A ₀ , . 290–410 .

     

Bilirubin protects grafts against nonspecific inflammation-induced injury in syngeneic intraportal islet transplantation

Nonspecific inflammatory response is the major cause for failure of islet grafts at the early phase of intraportal islet transplantation (IPIT). Bilirubin, a natural product of heme catabolism, has displayed anti-oxidative and anti-inflammatory activities. The present study has demonstrated that bilirubin protected islet grafts by inhibiting nonspecific inflammatory response in a syngeneic rat model of IPIT. The inflammation-induced cell injury was mimicked by exposing cultured rat insulinoma INS-1 cells to cytokines (IL-1β, TNF-α and IFN-γ) in in vitro assays. At appropriate lower concentrations, bilirubin significantly attenuated the reduced cell viability and enhanced cell apoptosis induced by cytokines, and protected the insulin secretory function of INS-1 cells. Diabetic inbred male Lewis rats induced by streptozotocin underwent IPIT at different islet equivalents (IEQs) (optimal dose of 1000, and suboptimal doses of 750 or 500), and bilirubin was administered to the recipients every 12 h, starting from one day before transplantation until 5 days after transplantation. Administration of bilirubin improved glucose control and enhanced glucose tolerance in diabetic recipients, and reduced the serum levels of inflammatory mediators including IL-1β, TNF-α, soluble intercellular adhesion molecule 1, monocyte chemoattractant protein-1 and NO, and inhibited the infiltration of Kupffer cells into the islet grafts, and restored insulin-producing ability of transplanted islets.     

Regulation of redox balance using a biocompatible nanoplatform enhances phototherapy efficacy and suppresses tumor metastasis

Many cancer treatments including photodynamic therapy (PDT) utilize reactive oxygen species (ROS) to kill tumor cells. However, elevated antioxidant defense systems in cancer cells result in resistance to the therapy involving ROS. Here we describe a highly effective phototherapy through regulation of redox homeostasis with a biocompatible and versatile nanotherapeutic to inhibit tumor growth and metastasis. We systematically explore and exploit methylene blue adsorbed polydopamine nanoparticles as a targeted and precise nanocarrier, oxidative stress amplifier, photodynamic/photothermal agent, and multimodal probe for fluorescence, photothermal and photoacoustic imaging to enhance anti-tumor efficacy. Remarkably, following the glutathione-stimulated photosensitizer release to generate exogenous ROS, polydopamine eliminates the endogenous ROS scavenging system through depleting the primary antioxidant, thus amplifying the phototherapy and effectively suppressing tumor growth in vitro and in vivo. Furthermore, this approach enables a robust inhibition against breast cancer metastasis, as oxidative stress is a vital impediment to distant metastasis in tumor cells. Innovative, safe and effective nanotherapeutics via regulation of redox balance may provide a clinically relevant approach for cancer treatment.

Amplified oxidative stress achieved by modulating redox homeostasis with PDA–MB for highly effective synergistic phototherapy to inhibit primary tumors and metastases.     

指数升温脱附研究

本文采用分子筛吸附苯或正已烷, 进行指数程序升温脱附。结果表明, 活化能与脱附最大速率所对应的温度(T_m)有线性关系, 即E_d=KT_m。对指数升温条件下得到的脱附图谱与各个脱附动力学参量之间的关系进行了数学分析, 并将分析结果与线性升温所得的结果相比较。各对应的动力学参数的数值基本相同。我们推导得到的指数升温基本方程与目前通用的线性升温基本方程~[2]相比较, 如果温度的测量精度相同则指数升温计算方法的精度比线性升温高(2T+△T)倍。实验还说明, 指数升温的曲线比线性升温容易控制。     

Interlaboratory trial validation of an event-specific qualitative polymerase chain reaction-based detection method for genetically modified RT73 rapeseed

The qualitative event-specific polymerase chain reaction detection method of genetically modified (GM) RT73 rapeseed was developed based on the cloned 3' end flanking sequence of RT73 rapeseed integration. The specificity of the method for GM RT73 rapeseed was validated using several different GM rapeseed lines, GM maize lines, GM soybean line, non-GM rapeseed, and other non-GM crops. In this study, the developed method was validated through an interlaboratory study by 12 laboratories from 6 countries. The sensitivity of this method was evaluated using several mixed rapeseed meals with different GM RT73 rapeseed contents from 5.0 to 0.01% prepared by our laboratory. The evaluated results showed that all of the rapeseed endogenous reference high mobility group protein gene (HMG I/Y), figwort mosaic virus 35S (FMV 35S) promoter, and RT73 event-specific fragment could be detected from rapeseed samples at 0.1% (w/w) with a confidence level of more than 95%. All results from the 12 laboratories indicated that the developed method could be considered fit for the detection and identification of GM RT73 rapeseed.     

Sequential electrochemical oxidation and site-selective growth of nanoparticles onto AFM probes

In this work, we reported an approach for the site-selective growth of nanoparticle onto the tip apex of an atomic force microscopy (AFM) probe. The silicon AFM probe was first coated with a self-assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) through a chemical vapor deposition (CVD) method. Subsequently, COOH groups were selectively generated at the tip apex of silicon AFM probes by applying an appropriate bias voltage between the tip and a flat gold electrode. The transformation of methyl to carboxylic groups at the tip apex of the AFM probe was investigated through measuring the capillary force before and after electrochemical oxidation. To prepare the nanoparticle terminated AFM probe, the oxidized AFM probe was then immersed in an aqueous solution containing positive metal ions, for example, Ag+, to bind positive metal ions to the oxidized area (COOH terminated area), followed by chemical reduction with aqueous NaBH 4 and further development (if desired) to give a metal nanoparticle-modified AFM probe. The formation of a metal nanoparticle at the tip apex of the AFM probe was confirmed by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA).     

Palladium-catalyzed cascade reactions of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide

Reaction of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide 1 in the presence of a palladium catalyst afforded dihydropyrroles 3 in moderate to excellent yields. It is proposed that the cyclic products were formed via a palladium-catalyzed cascade cyclization-coupling process.     

Syntheses and characterizations of poly[2‐(dimethylamino)ethyl methacrylate]–poly(propylene oxide)–poly[2‐(dimethylamino)ethyl methacrylate] ABA triblock copolymers

A novel, near‐monodisperse, well‐defined ABA triblock copolymer, poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(propylene oxide)‐b‐poly[2‐(dimethylamino)ethyl methacrylate], was synthesized via oxyanion‐initiated polymerization. The initiator was a telechelic‐type potassium alcoholate prepared from poly(propylene glycol) and KH in dry tetrahydrofuran. The copolymers produced were characterized by Fourier transform infrared, ¹H NMR, and gel permeation chromatography (GPC). GPC and ¹H NMR analyses showed that the products obtained were the desired copolymers, with narrow molecular weight distributions (ca. 1.09–1.11) very close to that of the original poly(propylene glycol). ¹H NMR, surface tension measurements, and dynamic light scattering all indicated that the triblock copolymer led to interesting aqueous solution behaviors, including temperature‐induced micellization and very high surface activity. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 624–631, 2002; DOI 10.1002/pola.10144     

Synergistic antibacterial and antibiotic effects of bisbenzylisoquinoline alkaloids on clinical isolates of methicillin-resistant Staphylococcus aureus (MRSA)

The antibacterial activity of two bisbenzylisoquinoline alkaloids, tetrandrine (Tet) and demethyltetrandrine (d-Tet), alone and in combination with the antibiotics ampicillin (AMP), azithromycin (AZM), cefazolin (CFZ) and levofloxacin (LEV) against 10 clinical isolates of staphylococcal chromosomal cassette mec (SCCmec) III type methicillin-resistant Staphylococcus aureus (MRSA) was studied. Susceptibility to each agent alone was tested using a broth microdilution method. The chequerboard and time-kill tests were used for the combined evaluations. The minimal inhibitory concentrations/minimal bactericidal concentrations (MICs/MBCs, μg/mL) ranges alone were 64-128/256-1,024 for both Tet and d-Tet. Significant synergies against 90% of the isolates were observed for the Tet/CFZ combination, with their MICs being reduced by 75-94% [fractional inhibitory concentration indices (FICIs) ranged from 0.188 to 0.625], respectively. An additive bactericidal result was also observed for the Tet (d-Tet)/CFZ combination in the time-kill experiments. These results demonstrated that Tet and d-Tet enhanced the in vitro inhibitory efficacy of CFZ. Their potential for combinatory therapy of patients infected with MRSA warrants further pharmacological investigation.