低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究

在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。     

低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究(英文)

在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。     

ESR studies op irradiated aqueous solutions of hydroxypyrimidines

The irradiated aqueous solutions of 4-hydroxypyrimidine and 2-hydroxypyrimidine hydrochloride were examined by means of the In situ radiolysis steady-etate ESR method. One and three short-lived radicals respectively were detected in alkaline solutions. The struotures and reaction mechanisms of radicals were derived. The spin density distributions were calculated by the improved McConnell's relationships and the value of coupling factor Q^H _NC was determined.     

惰性气体对HFCVD沉积金刚石气相基团的影响

发射光谱法是对等离子进行在线诊断的常用方法。在丙酮/H_2、丙酮/H_2/He和丙酮/H_2/Ar三种体系中,对热丝化学气相沉积金刚石薄膜过程中的等离子体进行了在线测量。研究了不同体积分数的惰性气体对等离子体中各活性基团强度的影响,以及CH,Hβ与C_2的相对强度的比值、电子温度的大小随惰性气体体积分数的变化关系。结果表明,各基团的强度随着惰性气体体积分数的增加呈现上升趋势,且加入同体积分数的氩气比加入氦气的影响更大;CH,Hβ与C_2的相对强度比值、电子温度随着惰性气体体积分数的增加而呈现下降趋势,且在丙酮/H_2/Ar体系中要比丙酮/H_2/He体系中小。     

Effect of intense, ultrashort laser pulses on DNA plasmids in their native state: strand breakages induced by in situ electrons and radicals

Single strand breaks are induced in DNA plasmids, pBR322 and pUC19, in aqueous media exposed to strong fields generated using ultrashort laser pulses (820 nm wavelength, 45 fs pulse duration, 1 kHz repetition rate) at intensities of 1-12 TW?cm(-2). The strong fields generate, in situ, electrons and radicals that induce transformation of supercoiled DNA into relaxed DNA, the extent of which is quantified. Introduction of electron and radical scavengers inhibits DNA damage; results indicate that OH radicals are the primary (but not sole) cause of DNA damage.     

Nitroxide-controlled free radical copolymerization of styrene and acrylonitrile monitored by electron spin resonance and fourier transform infrared technique in situ

Nitroxide-mediated homopolymerization of styrene (St) and copolymerization of styrene and acrylonitrile (An) were monitored respectively by electron spin resonance and Fourier transform infrared technique in situ, and the polymerization kinetics was investigated in detail. Homopolymerization of St was well controlled in the presence of 4-hydroxyl-2,2,6,6-tetramethyl-l-piperidinyloxy (HTEMPO, N*) at high temperature. The initiation reactions and polymerization rates were changed by varying initiators, such as benzoyl peroxide (BPO), 2,2-azobis-isobutylonitrile (AIBN) and dicyclohexyl dicarbonate peroxide (DCPO) because of the different half-period values of the initiators. For the St system containing the DCPO with longer half-period value, the reaction rate was enhanced and the final conversion was increased because the larger amount of the DCPO residual released continuously the excess radicals to increase growing radical concentration. But the polydispersity of the resulting polymer became somewhat larger. The copolymerization of St and An with AIBN as initiator in the presence of HTEMPO was also tamed in the living fashion of stable free radical polymerization in the range of the total monomer conversion below 40%. The hydrogen-abstracting effect on the penultimate unit of the primary radicals or growing radical was observed through a copolymerization process. The larger amount of St was combined into the copolymers, leading to an increase of the An contents especially in the latter period of copolymerization, due to the inhibited addition of An on the growing radicals with end An unit. The normal random copolymerization was interrupted, resulting in the different virtual reactivity ratio. The dissociation and combination equilibrium between N* and the different end St and An units on propagating radicals affected the consuming rates of St and An. A possible copolymerization mechanism containing hydrogen-abstracting reaction was suggested.     

红外光谱原位跟踪活性自由基聚合反应过程研究

使用新型可插入式红外光谱仪原位检测在4－羟基2，2，6，6－四甲基氧化哌啶醇（HTEMPO）存在下苯乙烯稳定自由基活性均聚合反应和苯乙烯／甲基丙烯酸羟丙酯的共聚合反应以及苯乙烯原子转移活性自由基聚合（ATRP）反应三个过程，分别考虑了它们的反应动力学，并给出了可能的聚合反应机理。研究结果表明，对于均相的苯乙烯（St)均聚合反应和苯乙烯（St)/甲基丙烯酸羟丙酯（HPMA）的自由基共聚合反应体系，聚合反应显示一定的诱导期，与反应体系中存在的HTEMPO捕捉自由基有关，而对于St／HPMA共聚合体系，诱导期更长，这是因为HPMA易和HTEMPO自由基发生氢转移反应，导致游离的HTEMPO浓度升高。最后用红外光谱实时跟踪苯乙烯非均相ATRP过程，发现苯乙烯聚合反应动力学接近于表现零级。因为单体分子在由增长自由基、卤化铜和联二吡啶形成的络合物的界面增长，与单体相内St浓度无关。     

Evaluation and comparison of three novel microbubbles: Enhancement of ultrasound-induced cell death and free radicals production

Three novel lipid-shell-type microbubbles (MBs), AS-0100, BG6356A and BG6356B, have been evaluated for their impact on ultrasound (US)-induced cell death and free radicals production. Previously studied and well-characterized US exposure conditions were employed in which human myelomonocytic lymphoma U937 cells were exposed to 1 MHz pulsed US beam (0.3 W/cm², 10% duty factor) for 1 min with or without MBs. Three different concentrations of each MB were used. Apoptosis and cell lysis were assessed by examining phosphatidylserine externalization and by counting viable cells, respectively, 6 h post-exposure. Free radicals production and scavenging activities were evaluated using electron paramagnetic resonance (EPR)-spin trapping. The results showed that only AS-0100 and BG6356A were able to enhance the US-induced apoptosis, mainly by increasing the secondary necrosis. Apoptosis and cell lysis seemed to depend more on mechanical forces exerted by oscillating MBs while free radicals played a trivial role. BG series MBs exhibited pronounced scavenging activities. Generally, despite the need for further optimization, AS-0100 and BG6356A appear to be promising as adjuncts in cases where US-induced cell death is required.     

A mathematical model of the evolution of free radical concentrations in a cell under ionizing radiation

A probabilistic mathematical model that describes the evolution of the free radical concentration in a cell under ionizing radiation is proposed. The model is of a stochastic character and allows one to describe the generation of free radicals in the process of radiolysis, as well as the interaction between the radicals of different types and between the radicals and the cell constituents (the latter is responsible for radiobiological effect). The possibility of the presence in the cell of a certain equilibrium quantity of radicals of nonradiative origin at the moment that the irradiation begins is taken into account. The results thus obtained show that under certain values of the model’s free parameters the total number of free radicals in a cell under radiation may decrease. This effect can explain the “positive” influence of small doses of ionizing radiation.     

Long-distance oxygen plasma sterilization: Effects and mechanisms

The distribution of electrons, ions and oxygen radicals in long-distance oxygen plasma and the germicidal effect (GE) of Escherichia coli on the surface of medical poly(tetrafluoroethylene) (PTFE) film were studied. The quantity of protein leakage and the production of lipid peroxide in bacterial suspension as well as the state of DNA were measured after sterilization to analyse the inactivation mechanisms. The results showed that the concentration of electrons and ions decreased rapidly with increasing the distance from the center of induction coil, which approximated to 0 at 30 cm, whereas the concentration of oxygen radicals reduced slowly, i.e. decreased 30% within 40 cm. GE value reached 3.42 in the active discharge zone (0 cm) and exceeded 3.32 within 40 cm when plasma treatment parameters were set as follows: plasma rf power at 100 W, treatment time at 60 s and oxygen flux at 40 cm³/min. Fast etching action on cell membrane by electrons, ions and attacking polyunsaturation fatty acid (PUFA) in cell membrane by oxygen radicals are primary reasons of oxygen plasma sterilization in the active discharge and the afterglow zone, respectively. The GE of UV radiation in long-distance oxygen plasma is feebleness.     

灯丝温度对原位吸收光谱和金刚石薄膜生长的影响

 报道了原位红外吸收光谱在气相合成金刚石薄膜生长过程中的应用，研究了灯丝温度对原位红外吸收光谱和金刚石薄膜生长的影响。较高的灯丝温度使甲烷分解更充分，从而产生更多诸如C₂H₂等可能对金刚石薄膜生长有利的基团，导致金刚石薄膜质量和生长速率的提高。     

High‐Performance UV Protective Waterborne Polymer Coatings Based on Hybrid Graphene/Carbon Nanotube Radicals Scavenging Filler

Ultraviolet (UV) degradation is one of the most important challenges of waterborne coatings in exterior applications. One of the ways to address this issue is addition of radical scavenging species within the polymer matrix. Herein, hybrids of graphene (G) and multiwall carbon nanotubes (CNTs) in different ratios are used as radical scavenging species. Evaluated by electron paramagnetic resonance spectroscopy, it is found that the hybrid made of G/CNTs in ratio of 10:1 efficiently captures and quenches the free radicals. The waterborne polymer composites containing 1 wt% of hybrid G/CNT are synthesized by in situ miniemulsion free radical polymerization using a water soluble initiator. However, due to excellent efficiency to capture free radicals, the polymerization performed using water soluble initiators in the presence of 10:1 G/CNT filler is hindered. This is resolved by physical separation of the free radicals and the scavenging materials within different phases by use of oil soluble initiator. The resulting polymer composites, beside having excellent mechanical resistance, present exceptional stability under accelerated aging conditions during 400 h, suppressing almost completely the UV photodegradation. This is attributed to the efficient radical scavenging of the G/CNTs hybrid filler distributed within polymer matrix, resulting in high‐performance UV protective waterborne composite coatings.     

Spatiotemporal measurement using L-band ESR-CT system for water sonolysis in the presence of 1-Hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide

When using ESR to measure the radicals generated by ultrasound, it is necessary to extract a solution and place it in the ESR system. To avoid this process, we incorporated an ultrasonic reaction cell in an L-band ESR-CT system, producing a system that allows the detection of the concentration of radicals during ultrasonic irradiation. This system was used to measure the time and space dependences of OH radicals generated by ultrasonic irradiation. When a 10 ml aqueous solution of 1-hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide (HTIO) was irradiated with ultrasound, it was found that the generation of radicals was clearly shown in a CT image after a period of 10 min. It was also found that continued irradiation resulted in an increased concentration of radicals. In addition to this system, an X-band ESR system was also used to measure the concentration of OH radicals generated, and the results of both systems were then compared. Both results are very similar, showing that the proposed system, which was realized by incorporating an ultrasonic irradiation cell in the L-band ESR-CT system, operated properly. Because this system allows the measurement of sonochemical reactions in an opaque cell or an opaque solution such as blood and industrial wastewater, it is a very useful measurement system for achieving the applying of sonochemistry to the medical engineering field.     

ESR spectra and thermal diffusivity of Zn–Al layered double hydroxide

Zn–Al–NO₃–LDH was synthesized using the co-precipitation method at pH 7±0.1 and ratio Zn/Al=4. The heat treatment of LDH was studied by X-ray diffraction (XRD) and thermogravimetric analysis (TGA/DTG) to investigate the stability of the LDH structure. The in situ electron spin resonance (ESR) spectra of fresh LDH from room temperature up to 190 °C were obtained, which are due to the presence of nitrate radicals in LDH interlayer. ESR spectra of sintered LDH below 200 °C (ex situ ESR spectra) were investigated, which are also due to the nitrate radicals. However, at 200 °C and above, spectra were due to the oxygen vacancies of ZnO, which was formed during the thermal treatment of LDH. Thermal diffusivity of LDH as a function of in situ temperatures results in a nonlinear relation, which is due to the changing water content of LDH when temperature increases. However, thermal diffusivity of LDH as a function of sintered temperatures showed a linear relation and the slope of these data demonstrated the dependency between thermal diffusivity and water content of LDH below 200 °C. For temperature above 180 °C, the thermal diffusivity behavior was mainly due to the ZnO phase in LDH.     

Rotational Spectra of the Thiosulfeno Radical, HSS and DSS, between 0.3 and 0.9 THz

The rotational spectra of the HSS and DSS radicals were studied in selected regions between 331 and 883 GHz. The radicals were produced by discharging a gaseous mixture of hydrogen (or deuterium) and hydrogen sulfide in the cell. The observation of the b-type Q-branch and R-branch lines with K(a) = 2-1 and 3-2 for HSS and DSS, respectively, as well as the a-type R-branch lines allowed the improvement and the determination of the molecular constants among them (in MHz) We have reevaluated the harmonic force field of HSS and the ground state average and approximate equilibrium structural parameters. For the latter, we obtained r(HS) = 135.23 pm, r(SS) = 196.03 pm, and angle = 101.74 degrees. These results are compared with those from previous and own quantum chemical calculations as well as with results of related molecules. Copyright 2000 Academic Press.     

Free radical scavenging activities of white and red wines: An EPR spin trapping study

Free radical scavenging activities of wine samples were investigated by means of electron paramagnetic resonance (EPR) spin trapping. 1,1-Diphenyl-2-picrylhydrazyl served as a source of free radicals, OH radicals were produced by the Fenton system, and in situ thermally generated SO₄⁻ radicals from K₂S₂O₈ and carbon-centered radicals from azo-compounds were also used. 5,5-Dimethylpyrroline-N-oxide (DMPO) was used as a spin trapping agent. Three white and four red wine samples from the Slovak wine regions, along with 12% (v/v) aqueous ethanol solution as a reference sample, were compared. In general, the lowest scavenger activity was found in the reference sample, a higher one in the white, and a considerably higher one in the red wines, except when the Fenton system was used as the radical source. Here, unexpectedly, unlike in the other radical sources, the wine samples increased the yield of DMPO-adducts by about 5 times, compared to the reference sample. This is probably due to an additional activation of the Fenton system by wine components. Higher concentrations of Mn²⁺ ions as determined by EPR spectroscopy corresponded to an increased scavenging activity of wines.     

Sonodynamic therapy--a review of the synergistic effects of drugs and ultrasound

Sonodynamic therapy, the ultrasound dependent enhancement of cytotoxic activities of certain compounds (sonosensitizers) in studies with cells in vitro and in tumor bearing animals, is reviewed. The attractive features of this modality for cancer treatment emerges from the ability to focus the ultrasound energy on malignancy sites buried deep in tissues and to locally activate a preloaded sonosensitizer. Possible mechanisms of sonodynamic therapy include generation of sonosensitizer derived radicals which initiate chain peroxidation of membrane lipids via peroxyl and/or alkoxyl radicals, the physical destabilization of the cell membrane by the sonosensitizer thereby rendering the cell more susceptible to shear forces or ultrasound enhanced drug transport across the cell membrane (sonoporation). Evidence against the role of singlet oxygen in sonodynamic therapy is discussed. The mechanism of sonodynamic therapy is probably not governed by a universal mechanism, but may be influenced by multiple factors including the nature of the biological model, the sonosensitizer and the ultrasound parameters. The current review emphasizes the effect of ultrasound induced free radicals in sonodynamic therapy.     

Phase space manipulation of cold free radical OH molecules

We report bunching, slowing, and acceleration of a supersonically cooled beam of diatomic hydroxyl radicals (OH). In situ observation of laser-induced fluorescence along the beam propagation path allows for detailed characterization of longitudinal phase-space manipulation of OH molecules through the Stark effect by precisely sequenced inhomogeneous electric fields.     

The design of 2/8-type high-pressure cell applied to in situ neutron diffraction

The DIA-type Kawai cell possesses a larger volume and a quasi-hydrostatic pressure environment and has been widely used in materials' synthesis and x-ray diffraction experiments.However, few high-pressure in situ neutron diffraction experiments were performed in the DIA-type Kawai cell because there is no wide window for neutron diffraction and the second-stage anvils and guild block material attenuates the neutron signal significantly.In this work, we tentatively modified the normal DIA-type Kawai cell(MA 2-6-8) into a MA 2-8 mode by removing the six first-stage tungsten carbide anvils.As a consequence, the eight tungsten carbide anvils(Kawai cell) are directly driven by the guide blocks.The results of ex situ and in situ pressure calibration show that the cell pressure can reach 5 GPa with small truncation edge lengths(TEL) of 3 mm even at the load of 300 kN.It suggests that this MA 2-8 cell may open a new way for high-pressure and high-temperature in situ neutron diffraction.     

ESR Study on Scavenging Effect of Squalene on Free Radicals in Mainstream Cigarette Smoke

Radicals in mainstream cigarette smoke (MCS) have been proposed to contribute to the harm caused by cigarette smoking. In the present study, we used natural antioxidant, squalene, to treat cigarette filters and tobacco for scavenging gas- and particulate-phase free radicals in MCS. The scavenging activities of cigarette filter and tobacco containing squalene against gas and particulate-phase free radicals were detected and quantified using spin-trapping or directly electron spin resonance spectroscopy method. The results revealed that squalene could significantly scavenge gas- and particulate-phase free radicals in MCS in a dose-dependent manner. The radical-scavenging activity of cigarette filter treatment was higher than that of tobacco treatment, irrespective of either gas-phase free radicals, or particulate-phase free radicals in MCS. Among them, 3 mg squalene/filter treatment showed that the highest scavenging effects against gas- and particulate-phase free radicals were 35.9 and 35.4%, respectively. The use of squalene as potential scavenger for reducing free radicals in cigarette smoke is discussed.