Molecularly imprinted polymers (MIPs) with trinitrophenol (TNP) as a dummy template molecule capped with CdTe quantum dots (QDs) were prepared using 3-aminopropyltriethoxy silane (APTES) as the functional monomer and tetraethoxysilane (TEOS) as the cross linker through a seedgrowth method via a sol−gel process (i.e., DMIP@QDs) for the sensing of 2,4,6-trinitrotoluene (TNT) on the basis of electrontransfer-induced fluorescence quenching. With the presence and increase of TNT in sample solutions, a Meisenheimer complex was formed between TNT and the primary amino groups on the surface of the QDs. The energy of the QDs was transferred to the complex, resulting in the quenching of the QDs and thus decreasing the fluorescence intensity, which allowed the TNT to be sensed optically. DMIP@QDs generated a significantly reduced fluorescent intensity within less than 10 min upon binding TNT. The fluorescence-quenching fractions of the sensor presented a satisfactory linearity with TNT concentrations in the range of 0.8−30 μM, and its limit of detection could reach 0.28 μM. The sensor exhibited distinguished selectivity and a high binding affinity to TNT over its possibly competing molecules of 2,4-dinitrophenol (DNP), 4-nitrophenol (4-NP), phenol, and dinitrotoluene (DNT) because there are more nitro groups in TNT and therefore a stronger electron-withdrawing ability and because it has a high similarity in shape and volume to TNP. The sensor was successfully applied to determine the amount of TNT in soil samples, and the average recoveries of TNT at three spiking levels ranged from 90.3 to 97.8% with relative standard deviations below 5.12%. The results provided an effective way to develop sensors for the rapid recognition and determination of hazardous materials from complex matrices.
Metastasis-associated lung adenocarcinoma transcript 1 (MALAT1) is a lncRNA playing oncogenic role in several cancers, including cervical cancer. However, its role in radiosensitivity of cervical cancer is not yet well understood. This study explored the role of MALAT1 in radiosensitivity of high-risk human papillomavirus (HR-HPV)-positive cervical cancer and whether there is a ceRNA mechanism which participated in its regulation over radiosensitivity. Based on tissue samples from 50 cervical cancer cases and 25 healthy controls, we found MALAT1 expression was significantly higher in radioresistant than in radiosensitive cancer cases. In addition, MALAT1 and miR-145 expression inversely changed in response to irradiation in HR-HPV+ cervical cancer cells. By using clonogenic assay and flow cytometry analysis of cell cycle distribution and apoptosis, we found CaSki and Hela cells with knockdown of MALAT1 had significantly lower colony formation, higher ratio of G2/M phase block and higher ratio of cell apoptosis. By performing RNA-binding protein immunoprecipitation (RIP) assay and RNA pull-down assay, we confirmed that miR-145 and MALAT1 were in the same Ago2 complex and there was a reciprocal repression between them. Then, we explored the function of MALAT1-miR-145 in radiosensitivity of cervical cancers cells and demonstrated that si-MALAT1 and miR-145 had some level of synergic effect in reducing cancer cell colony formation, cell cycle regulation, and inducing apoptosis. These findings provide an important clue about microRNA-lncRNA interaction in the mechanism of radioresistance of cervical cancer.
Stimuli-responsive molecularly imprinted polymers (SR-MIPs) have received widespread attention with the rapid development of stimuli responsive polymers and molecularly imprinted polymers, and significant progress has been achieved in recent years in the field of SR-MIPs. To date, magnetic responsive MIPs, temperature responsive MIPs, pH responsive MIPs, photo-responsive MIPs, and dual or multi stimuli responsive MIPs have been prepared, and display broad application perspectives in many fields such as drug delivery, biotechnology, separation sciences, and chemo/biosensors. In the present feature article, those SR-MIPs are summarized comprehensively, and particular attention is paid to the mechanism of SR-MIPs, their preparation methods, and the application aspects. Finally, some significant attempts to further develop SR-MIPs are also proposed. 1 Introduction Molecularly imprinted polymers (MIPs), with origins in the molecular imprinting technique proposed by Polyakov in 1931, 1 are synthesized by the copolymerization of functional monomers and cross-linkers in the presence of template molecules. Aer removal of the template molecules, recognition cavities complementary to the template molecules in shape, size and chemical functionality are formed in the highly cross-linked polymer matrix, which have a predetermined selectivity for a given analyte, or a group of structurally similar compounds. 2-4 The molecular imprinting process is represented in Scheme 1. 2 In recent years, great achievements based on MIPs have been made in many elds, such as purication and separation, 5-10 chiral recognition, 11-14 chemo/biosensing, 15-17 and catalysis and degradation, 18,19 due to the desired selectivity, physical robustness, thermal stability, as well as low cost and easy preparation of the MIPs. Stimuli responsive polymers (SRP), also known as environmental responsive polymers or smart polymers, are a class of special materials that are able to respond to specic external Shoufang Xu received her Ph.D. degree from the Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences in 2012. She received the Special Prize of Presidential Scholarship of Chinese Academy of Sciences in 2012, and the Scholarship Award for Excellent Doctoral Student granted by the Ministry of Education in 2011. She is currently a lecturer at the School of Chemistry & Chemical Engineering, Linyi University. Her research interests focus on the preparation of molecularly imprinted polymers (MIPs) and the application of MIPs in the separation and analysis of typical organic pollutants. Hongzhi Lu received his Masters degree from Shandong Normal University in 2007. He is currently a lecturer at the School of Chemistry & Chemical Engineering, Linyi University. His research interests focus on the synthesis and application of functional polymers.
Molecularly imprinted polymer coated quantum dot (MIP@QD) fluorescence sensors combined with ratiometric fluorescence techniques and mesoporous silica materials have been applied to detect TNT for the first time. The assay platform exhibited excellent selectivity and sensitivity with a detection limit as low as 15 nM.
A polymer micelle-based drug delivery system has faced many challenges due to the lack of stability especially after being diluted in blood, resulting in a premature release. Herein, we developed camptothecin (CPT)-conjugated prodrug (CPTP) micelles in which CPT was grafted to the poly(ethylene glycol)−poly(glutamic acid) block copolymer via a disulfide bond linker for a redox-triggered drug release. Then, the cisplatin (CDDP)-crosslinked CPT-prodrug micelles (CPTP/ CDDP) with a hybrid complex as a stable structure were successfully established via the CDDP (Pt)−carboxyl (COOH) chelate interaction. The resulting dual CPTP/CDDP had an average hydrodynamic radius of about 50 nm with a narrow distribution, which was conducive to the promotion of solid tumor accumulation. Importantly, CPT chemical bonding to the polymer backbone obviously stabilizes the CPT-prodrug micelles and prolongs their circulation time. Moreover, both CPT and CDDP are clinically used antitumor drugs; CDDP not only behaves as an ancillary anticarcinogen but also serves as a crosslinker to restrain the untimely burst release of CPT and to achieve synergistic antitumor efficacy. In addition, the CPTP/CDDP also exhibited a sustained reduction responsive release of CPT accompanied by the dissociation of the CDDP−COOH complex. This design ingeniously solved the contradiction between the stability and release of polymer micelle-based nanomedicines. Both in vitro and in vivo tests demonstrated an amazing antineoplastic efficacy compared with free drugs (CPT or CDDP) and just their physical mixing, indicating great promise for cancer treatment.
As a widely used photocatalyst, titania (TiO 2 ) enjoys significant advantages; however, it faces the severe challenge of poor selectivity. And interestingly, molecular imprinting gains great popularity, owing to its desired recognition specificity. Herein, by using estrone as a template molecule, we prepared molecularly imprinted TiO 2 hybridized magnetic ferroferric oxide (Fe 3 O 4 ) nanoparticles through a semicovalent approach by a liquid phase deposition method, for selective photocatalytic degradation and removal of target estrone with the irradiation of UV light. The obtained Fe 3 O 4 @SiO 2 @imprinted TiO 2 displayed high adsorption capacity, fast kinetics and high selectivity. In the presence of 10 times of coexisting nontarget compounds, the apparent rate constant, k app , for photodegradation of target estrone over the hybridized nanoparticles, was about 6 times of that over net TiO 2 . Also, excellent stability during long-time photocatalysis was exhibited. More importantly, the Fe 3 O 4 @imprinted TiO 2 provided potential application prospectives for photocatalytic removal of trace target organic pollutants in the presence of high-level pollutants.
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