STEROID-BISPORPHYRIN. A NOVEL PORPHYRIN DIMER AS ENZYME MODEL

In the present communcation a novel steroid-bisporphyrin model compound has been synthesized. The configuration of which is also presented.

Synthesis, Characterization, and Electrochemical Property of Nanometer Porphyrin Dimer

A nanometer porphyrin dimer was synthesized with fumaryl chloride as a bridge-linked reagent. The characterization was carried out with elemental analyses, ^1H NMR, UV-Vis, and IR spectrometries, and then the electrochemical properties of the porphyrins were studied. The authors found that there was moderate electronic communication between the two porphyrin rings in the nanometer porphyrin dimer.

Fluorescence Properties of Porphyrin Dimers Incorporating an Anhydride Linker

A preliminary study on a novel free base porphyrin dimer and a zinc prophyrin dimer by comparing their fluorescence properties with those of the corresponding monomers is presented. The fluorescence intensity of the free base dimer is five times higher than that of the monomer, but the fluorescence intensity of the zinc porphyrin dimer is nearly similar to that of the zinc porphyrin monomer. The emission spectra show that energy transfer occurs between the two units.

Conformation Analysis and Thermodynamics of Binding Behavior of DABCO to p/p type Dimeric Porphyrin Hosts

The binding conformations of bidentate ligand DABCO(1,4-diazobicyclo [2,2,2]octane) to a series of p'p type zinc porphyrin dimers covalently linked with flexible alkoxy chain - O(CH2)(n)O- (n=2-10) are described by H-1 NMR and UV-vis spectroscopy. DABCO can bind inside the cavities of porphyrin dimers and form a ternary sandwich complex as the alkoxy chain length is long enough. The thermodynamic parameters which control the binding behavior are investigated.

Structural Multiplicity of Monomers of an Amphiphilic Porphyrin at the Outer Surface of CTAB Micelle

A synthesized amphiphilic porphyrin, 5,10,15-tri(p-hydroxyphenyl)-20-(p-hexadecyloxyphenyl) porphyrin, can take a transfer process for the porphyrin moiety from the inner core to the outer surface laver of cetyltrimethylammonium bromide (CTAB) micelle. The increasing of FWHH of the Sorer band was attributed to the multiplicity of porphyrin monomers related with deprotonation degree, arrangement, orientation, and position of porphyrin moiety at the surface al ea rather than the aggregates associated with irregular orientation of neighboring porphyrins.

Effect of H-type Aggregation on the Photoelectric Conversion of Tetrasulfonated Phthalocyanine Adsorbed on Nanostructured TiO_2 Electrode

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The self-aggregation of chiral threonine-linked porphyrins and their zinc( II) complexes

The self-aggregation of chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes in water-alcohol system and water-alcohol-NaCI system has been studied by circular dichroism (CD), UV-Vis absorption spectra and fluorescence spectra methods. The experiment results indicate that chiral threonine-linked porphyrins and their zinc(Ⅱ) complexes have two different kinds of aggregates in water-alcohol system and water-alcohol-NaCI system. And the porphyrins may form highly organized and orientated aggregates in water-alcohol-NaCI system. The aggregates in water-alcohol-NaCI system may have helical structures.

Strong near-infrared and ultrafast femtosecond nonlinearities of a covalently-linked triply-fused porphyrin dimer-SWCNT nanohybrid

Functional materials displaying large ultrafast third-order optical nonlinearities across a wide spectral region and broad temporal domain are required for all-optical signal processing.Particularly desirable is nonlinear optical(NLO)activity at near-infrared(NIR)wavelengths with femtosecond pulses.Herein the first triply-fused porphyrin dimer(TFP)-functionalized single-walled carbon nanotube(SWCNT)nanohybrid was successfully constructed by covalently grafting TFPs onto SWCNT.The results of Z-scan techniques demonstrate that the newly obtained TFP-SWCNT nanohybrid was found with a strong NLO performance under both nanosecond and femtosecond irradiation.In the nanosecond regime,an enhancement in optical limiting(OL)of the TFP-SWCNT nanohybrid is seen at 532 nm when compared with the performance of porphyrin monomer-functionalized SWCNT nanohybrid Por-SWCNT.Under femtosecond irradiation,the TFP-SWCNT nanohybrid exhibits a particularly strong OL effect with a giant two-photon absorption(TPA)cross section value(ca.15,500 GM)at 800 nm pulses that mainly stems from intense TPA of TFP,in sharp contrast to the Por-SWCNT nanohybrid which exhibits only saturable absorption under identical irradiation.These results demonstrate that the newly-developed TFP-SWCNT nanohybrid is a very promising OL candidate for practical applications across wide spectral and temporal domains,and that covalently functionalizing carbon-based materials with triply-fused chromophores may be a useful approach to engineering adaptable photonic devices with broad-ranging NLO activity.

Dynamic Assemblies and Photophysical Changes of Zinc Porphyrin Dimer Regulated by N-Containing Ligands

锌卟啉更暗淡(1 ) 作为包含 N ligands 的一位新奇主人被设计了并且综合。它的主人客人建筑群的集会行为和 photophysical 变化被 1H NMR，荧光，和紫外可见的滴定评估，并且这些过程表明主人客人集会首先创造稳定的三明治建筑群，然后，轴的协作平衡出现在三明治之间复杂、免费的 ligand。汇编进程的吸收系列的变化依靠熄灭的建筑群，和荧光的稳定性取决于轴的协作平衡，它确实显示轴的 ligation/de-ligation 动力学是来自激动的状态的一条小径到为 metalloporphyrin 建筑群的扎根的状态。

Dimers as Fast Diffusing Species for the Aggregation of Oxygen in Boron-Doped Czochralski Silicon: Formation of New Thermal Donors

The thermal behaviors of oxygen-related complexes in boron doped Czochralski Silicon (Cz-Si) wafers at 450°C and 800°C were investigated using Fourier transform infrared spectroscopy (FTIR) and Hall mobility measurements. Activation of thermal donors (TDs) at 450°C leads to a decrease of both mobility and majority carrier concentration using the four point probes configuration of Van Der Pauw. It was found that annealing at 450°C would possibly affect the electronic properties of the Si wafers via the formation of interstitial dioxygen defects (IO2i), which exhibit an IR absorption band positioned at 545 cm–1. A strengthening of the IR bands peaking at around 1595 cm–1, 1667 cm–1, 1720 cm–1 and 1765 cm–1 occurs at 450°C, while they disappear at 800°C. At high temperatures, the precipitation of interstitial oxygen becomes predominant over all other oxygen-related reactions. The dynamic of oxygen-thermal donor generation-annihilation in Cz-Si involving the formation of small oxygen clusters is discussed.

An acid-triggered porphyrin-based block copolymer for enhanced photodynamic antibacterial efficacy

Bacterial infection, especially multidrug-resistant(MDR) bacterial infection has threatened public health drastically. Here, we fabricate an "acid-triggered" nanoplatform for enhanced photodynamic antibacterial activity by reducing the aggregation of photosensitizers(PSs) in bacterial acidic microenvironment. Specifically, a functional amphiphilic block copolymer was first synthesized by using a pH-sensitive monomer, 2-(diisopropylamino) ethyl methacrylate(DPA) and porphyrin-based methacrylate(TPPC6MA) with poly(oligo(ethylene glycol) methyl ether methacrylate)(POEGMA) as the macromolecular chain transfer agent, and POEGMA-b-[PDPA-co-PTPPC6MA] block copolymer was further self-assembled into spherical nanoparticles(PDPA-TPP). PDPA-TPP nanoparticles possess an effective electrostatic adherence to negatively charged bacterial cell membrane, since they could rapidly achieve positive charge in acidic bacterial media. Meanwhile, the acid-triggered dissociation of PDPA-TPP nanoparticles could reduce the aggregation caused quenching(ACQ) of the photosensitizers, leading to around 5 folds increase of the singlet oxygen(1O2) quantum yield. In vitro results demonstrated that the "acid-triggered" PDPA-TPP nanoparticles could kill most of MDR S. aureus(Gram-positive) and MDR E. coli(Gram-negative) by enhanced photodynamic therapy, and they could resist wound infection and accelerate wound healing effectively in vivo. Furthermore, PDPA-TPP nanoparticles could well disperse the biofilm and almost kill all the biofilm-containing bacteria. Thus, by making use of the bacterial acidic microenvironment, this "acid-triggered" nanoplatform in situ will open a new path to solve the aggregation of photosensitizers for combating broad-spectrum drug-resistant bacterial infection.

Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin‘tweezers’(R)-1/(S)-1 and the corresponding zinc(II)complexes(R)-2/(S)-2 were prepared as chiral host molecules,and their utility for chiral analyses(especially enantiomeric excess(ee)determinations)were evaluated.Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units.Host capabilities of the diporphyrin tweezers were investigated by titrations with(R,R)-and(S,S)-cyclohexane-1,2-diamine(CHDA).The host molecules could be used as multichannel probes of ee by using UVvis,circular dichroism(CD),fluorescence emission and 1H nuclear magnetic resonance(1 H-NMR)methods.Chiral configurations could also be differentiated using CD or 1HNMR spectroscopy.All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used(ca.10^-6 mol·L^-1).The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of(R,R)-and(S,S)-CHDA.Non-metallated(R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest.This work demonstrates the utility of 1,1’-binapthyllinked chiral hosts for chiral analysis of ditopically interacting enantiomers.

ASSOCIATION BEHAVIOR OF PORPHYRIN PENDANTS IN pH-SENSITIVE WATER-SOLUBLE POLYMER

A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating water-soluble polymer PAM-TrPyP.The aggregation behavior of porphyrin pendants was investigated by UV-Visible and fluorescence spectra.The polymer displays a strong tendency of hydrophobic association even in dilute solutions.With increasing the concentration,the maximum absorption wavelength of Soret band changes from 416 nm to 407 nm,and the fluorescence corrected for the inner filter effect exhibits moderate concentration quenching.All the results indicate thatπ-πinteraction of porphyrin pendants plays a key role in association of PAM-TrPyP,and H-aggregates of porphyrins are mainly formed in the concentrated solution.On the other hand,dynamic light scattering（DLS） and transmission electron microscopy（TEM） were used to follow the changes in size and structure of the macromolecular assemblies with the concentration increase.The polymer aggregation conformation changes from loose ＂vesicle-like＂ morphology to solid globule accordingly.When pH value of solution decreases to 4.3,pyridine moieties on porphyrin pendants could be protonated and the H-aggregates formed in macromolecular matrix are destroyed by electrostatic repulsion interactions.

Effective enhancement of the emission efficiency of tetraphenylporphyrin in solid state by tetraphenylethene modification

Tetraphenylporphyrin(TPP) is a typical red-emitting luminogen showing evident aggregation caused quenching(ACQ) effect. To enhance its emission efficiency in solid state, four tetraphenylethene(TPE)units were attached to the four meso-positions of TPP core via ester group through a facile and efficient route. The derived compound(4(TPE-COO)-TPP) emits red fluorescence(peak at 655 nm) with a good quantum efficiency(F) of 7.5%, which is much higher than that of TPP(Φ～ 0.1%). In molecular aggregate formed in tetrahydrofuran(THF) and water mixtures, 4(TPE-COO)-TPP has a relative high F of 12%. The evidently subdued ACQ behavior can be ascribed to the propeller shape and bulky size of the TPE units,which prevent the close packing and strong p-p interaction of TPP cores. The loose molecular packing and weak interchromophore interactions were validated by different characterization methods including UV-visible absorption, steady state and transient fluorescence spectroscope, X-ray diffraction and scanning electronic microscope observations. It is noted that 4(TPE-COO)-TPP has an emission efficiency of 14.4% in dilute THF solution. This is due to the conjugation break between the TPP and TPE moieties, the rotational and vibrational motions of the phenyl groups cannot quench the fluorescence of 4(TPE-COO)-TPP.

HCY、FDP、D-Dimer与PLT聚集功能联合检测在AMI早期临床诊断的应用

目的探讨同型半胱氨酸(Homocysteine)、纤维蛋白原降解产物(fibrin degradation product)、D-二聚体(D-Dimer)、二磷酸腺苷(adenosine diphosphate)诱导血小板聚集功能联合检测在急性心肌梗死(a cute myocardial infarction)患者早期临床诊断中的应用价值。方法选取上海交通大学医学院附属瑞金医院2016年11月—2018年11月诊断为急性心肌梗死的患者80例(AMI组)和同期健康体检的健康人80例(对照组)作为研究对象。两组分别进行HCY、FDP、D-Dimer与ADP诱导血小板最大聚集率检测,结果进行统计学分析。结果AMI组患者的HCY、FDP、D-Dimer、A DP诱导血小板最大聚集率分别为(18.16±7.16)μmol/L、(7.54±3.86)mg/L、(1.89±0.82)mg/L、(84.08±5.27)%,对照组分别为(8.27±3.68)μmol/L、(2.32±1.71)mg/L、(0.55±0.32)mg/L、(72.85±8.37)%,AMI组各项指标水平高于健康对照组,差异具有统计学意义(P<0.05)。HCY、FDP、D-Dimer、ADP诱导血小板最大聚集率预测AMI的灵敏度分别为:83.61%、63.93%、62.30%、83.61%;特异性分别为:93.44%、91.80%、90.16%、85.25%。而四项联合检测时灵敏度和特异性为91.80%和96.72%。HCY、FDP、D-Dimer、ADP诱导血小板最大聚集率的ROC曲线下面积(AUC)分别为0.9348、0.8220、0.8117、0.8981,四项指标联合检测诊断AMI的AUC为0.9820。结论HCY、FDP、D-Dimer、ADP诱导血小板最大聚集率在AMI患者中均有升高,四者联合检测对AMI患者的早期诊断有重要价值。

血浆D-二聚体联合血小板聚集试验预测肿瘤患者血栓发生的应用价值

目的:分析血浆D-二聚体(D-D)联合血小板聚集试验(PAgT)预测肿瘤患者血栓发生的价值。方法:回顾性分析2019年10月-2021年9月于新余钢铁集团有限公司中心医院就诊的200例恶性肿瘤患者的临床资料,根据患者临床表现、辅助检查等,将3个月内发生静脉血栓栓塞症(VTE)的患者纳入VTE组,未发生VTE的患者纳入非VTE组。全部患者均接受血浆D-D、PAgT(血小板聚集率)检测,统计并比较两组基础资料、血浆D-D水平、血小板聚集率等,分析血浆D-D联合PAgT预测肿瘤患者血栓发生的价值。结果:200例恶性肿瘤患者中有36例发生VTE,发生率为18.00%。两组手术史、化疗史、血浆D-D水平、血小板聚集率比较,差异均有统计学意义(P<0.05)。经logistic回归分析检验,结果显示,手术史、化疗史、血浆D-D水平升高、血小板聚集率升高是肿瘤患者血栓发生的风险因子(P<0.05)。绘制ROC曲线发现,血浆D-D水平、血小板聚集率单独及联合检测预测肿瘤患者血栓发生风险的AUC均>0.80,均有一定预测价值。结论:肿瘤患者血栓发生可能与血浆D-D水平、血小板聚集率升高有关,且血浆D-D联合PAgT对肿瘤患者血栓发生风险有较高预测价值。

PAgT及血清FIB、D-D、P、β-HCG水平联合检测预测孕早期自然流产的价值

目的探讨血小板聚集率(PAgT)及血清纤维蛋白原(FIB)、D-二聚体(D-D)、孕酮、β-人绒毛膜促性腺激素(β-HCG)水平联合检测对孕早期自然流产的预测价值。方法选取该院2019年4月至2020年10月接收的有自然流产危险因素的孕妇142例纳入观察组,另选取同期健康孕妇135例纳入对照组。所有研究对象均检测PAgT及血清FIB、D-D、孕酮、β-HCG水平。比较两组上述指标和孕早期自然流产发生率;将观察组孕早期自然流产者纳入发生组,否则纳入未发生组,比较两亚组上述指标水平;绘制受试者工作特征(ROC)曲线,采用曲线下面积(AUC)评价PAgT、血清FIB、D-D、孕酮、β-HCG水平单独与联合检测对有自然流产危险因素的孕妇发生孕早期自然流产的预测效能。结果观察组PAgT、血清FIB和D-D水平均高于对照组,血清孕酮和β-HCG水平均低于对照组,差异有统计学意义(P<0.05)。观察组孕早期自然流产发生率为32.39%(46/142),高于对照组的2.22%(3/135),差异有统计学意义(P<0.05)。发生组PAgT、血清FIB和D-D水平均高于未发生组,血清孕酮和β-HCG水平均低于未发生组,差异有统计学意义(P<0.05)。PAgT及血清FIB、D-D、孕酮、β-HCG水平联合检测预测孕早期自然流产的灵敏度和AUC分别为97.83%和0.988,均高于各项指标单独检测(P<0.05),特异度与各项指标单独检测比较,差异均无统计学意义(P>0.05)。结论相较于健康孕妇,有孕早期自然流产风险的孕妇PAgT、血清FIB和D-D水平偏高,而血清孕酮和β-HCG水平偏低,上述指标联合检测可提高对有自然流产危险因素的孕妇孕早期自然流产的预测效能。

新型桥连双卟啉化合物的合成及结构表征

通过将 4,4′-二羧基 -2 ,2′-联吡啶、 2 ,6-二溴甲基吡啶、 2 ,6-二羟甲基吡啶和 1 ,8-二氨基萘分别与 5 -( 4 -羟基苯基 ) -1 0 ,1 5 ,2 0 -三苯基卟啉 ( 1 a)、 5 -( 4 -甲酰苯基 ) -1 0 ,1 5 ,2 0 -三苯基卟啉 ( 1 b)和 5 -[4-( 4′-溴代丁氧基 )苯基 ]-1 0 ,1 5 ,2 0 -三苯基卟啉 ( 1 c)反应 ,合成了 3类新型的双卟啉化合物 2 a— 2 e,经 IR,1 H NMR,MS。

氨基酸桥联新型手性锌双卟啉配合物的合成与表征

生命系统中的金属卟啉生物大分子在卟啉的Ｓｏｒｅｔ带均表现出诱导圆二色性（ＩｎｄｕｃｅｄＦｉｇ．１Ｓｔｒｕｃｔｕｒｅｏｆａｍｉｎｏａｃｉｄｂｒｉｄｇｅｄｚｉｎｃｐｏｒ┐ｐｈｙｒｉｎｄｉｍｅｒＯ，Ｏ┐Ｃ２┐ＡＡ┐Ｃ２┐（ＴＰＰ）２Ｚｎ２Ｒ＝Ｂｎ，ＡＡ＝Ｐ...