Metal-Organic Framework-Assisted Construction of TiO2/Co3O4 Highly Ordered Necklace-like Heterostructures for Enhanced Ethanol Vapor Sensing Performance.

In this work, we report a metal-organic framework (MOF)-assisted strategy to synthesize necklace-like TiO2/Co3O4 nanofibers with highly ordered heterostructures via a facile approach including electrospinning and subsequent calcination. Polycrystalline TiO2 nanofibers and Co3O4 nanocages are consummately interconnected to form a highly ordered heterogeneous nanostructure, which can be of benefit for precisely accommodating the interface resistance of the p-n heterojunctions and the future realization of improved material performance. The ethanol-gas-sensing investigation showed that TiO2/Co3O4 nanofiber sensors exhibited a strong ethanol response ( Rair/ Rgas -1 = 16.7 @ 150 ppm) and a low operating temperature of 150 °C. The sensing enhancement mechanism of the TiO2/Co3O4 nanofibers is related to the formation of heterojunctions at interfaces and the high catalytic activity of MOF-derived Co3O4. Furthermore, this versatile method is a promising approach to constructing ordered heterostructures and extending the MOF-based heterogeneous materials toward wide applications.

Role of poly(ethylene oxide) in copper-containing composite used for intrauterine contraceptive devices.

Copper-containing composite is a cupric ions release system to prepare a novel copper intrauterine devices (Cu-IUDs), its biocompatibility and weight of the prepared composite Cu-IUDs are directly relevant to its such side-effects as pain and bleeding. To improve its biocompatibility and reduce its weight of such a composite Cu-IUDs, a copper-containing composite based on polymer alloy of poly(ethylene oxide) (PEO) and low-density polyethylene (LDPE) is developed. Here the role of its PEO in this novel cupric ions release system is reported. The results show that its cupric ions release rate can be adjusted easily by only changing its PEO content, and it increases remarkably with the increase of its PEO content. Our study also show that this influence is caused by the improvement of its hydrophilicity and the formation of its porous structure owing to the introduction of PEO. The improvement of its hydrophilicity make it easier for the surrounding aqueous solution to infiltrate into the composite, and the formation of its porous structure provide more routes for entry of the aqueous solution and diffusion of the released cupric ions. All these results indicate that the Cu/PEO/LDPE composite is a potential material that can be used to prepare such cupric ions release micro-devices as Cu-IUDs with slighter side-effects through its smaller weight.

An approach to give prospective life-span of the copper/low-density-polyethylene nanocomposite intrauterine device.

As a novel copper-containing intrauterine device (IUD), the prospective life-span of the copper/low-density-polyethylene (Cu/LDPE) nanocomposite IUD is very important for the future clinical use and should be given in advance. Here a novel approach, cupric ions accelerated release in diluted nitric acid solution and cupric ions concentration release in various volume of simulated uterine solution (SUS), is reported to verify the type of cupric ions release model of the cylindrical matrix-type nanocomposite IUD, and to obtain the minimal cupric ions release rate that need to ensure contraceptive efficacy and the thickness of copper particles exhausted layer of the cylindrical matrix-type nanocomposite IUD within two difficult immersion durations in experimental volume of SUS, respectively. Using these results, the prospective life-span of the cylindrical matrix-type nanocomposite IUD can be obtained. For instance, the prospective life-span of the novel γ-shape nanocomposite IUD with 25 wt% of copper nanoparticles and 2 mm of diameter and a total weight of 285 mg can be given in advance and it is about 5 years in the future clinical use.

Antifertility effectiveness of a novel polymer matrix composite and its influence on the endometrium in rhesus macaques (Macaca mulatta).

OBJECTIVE(S): To explored the antifertility effectiveness and influence on the endometrium of a micro-copper/low-density polyethylene/methyl vinyl silicone rubber (Cu/LDPE/MVQ) composite in rhesus macaques. STUDY DESIGN: Healthy reproductive aged female rhesus macaques underwent abdominal hysterotomy for surgical placement of either the experimental Cu/LDPE/MVQ composite (Cu/LDPE/MVQ, n=5), bare copper wire (Cu, n=5), or hysterotomy only sham-operation group [(SOI, n=4), (SOII, n=6)]. Females in the Cu/LPDE/MVQ, Cu, and SOI groups were housed with fertile males for approximately three menstrual cycles. We assessed pregnancy by hysterectomy. Females in the Cu/LDPE/MVQ, Cu, and SOII groups underwent hysterectomy at about 4 months post-insertion for histologic assessment of morphologic changes of the endometrium, evaluation of materials using scanning electron microscopy (SEM), and evaluation of the inflammatory markers, including substance P receptor (SPR), associated with endometrial bleeding using enzyme linked immunosorbent assay, quantitative RT-PCR, and Western blot analyses. RESULTS: All of the SOI group females became pregnant (4/4, 100%). In contrast, no pregnancies occurred in either the Cu/LDPE/MVQ (0/5, 0%) or Cu (0/5, 0%) groups. We observed histologic features consistent with chronic endometrial inflammation in all females of the Cu group, but none of the SOII or Cu/LDPE/MVQ animals. Levels of inflammatory markers were significantly increased in the Cu group, compared with SOII or Cu/LDPE/MVQ groups (p<.05). SEM showed evidence of corrosion in the Cu wire not seen in the Cu/LDPE/MVQ group. CONCLUSION(S): Cu/LDPE/MVQ material provided a contraceptive effect similar to Cu in macaques, with a lower impact on inflammation and inflammatory markers of the endometrium. IMPLICATIONS: This study demonstrates the possibility of a Cu/LDPE/MVQ composite as an alternative to conventional copper device materials.

The forces imposed by the novel T-shape Cu/LDPE nanocomposite intrauterine devices on the simulated uterine cavity.

BACKGROUND: A simulated device was designed to study the forces, which are one of the most important factors relevant to the pain caused by the inserted intrauterine devices (IUDs), imposed by the novel T-shape copper/low-density polyethylene nanocomposite IUDs and the existing T-shape copper-containing IUDs (CuT 220C) on the uterine cavity. STUDY DESIGN: Tests were performed in a simulated uterine cavity with the same simulated uterine solution at a constant temperature of 37.0+/-0.1 degrees C. Force and deformation were measured using the Digital Push Pull Force Gauge with a gauge of displacement. RESULTS: The novel T-shape nanocomposite IUD and the existing T-shape Cu-IUD (CuT 220C) have a similar relationship between force and deformation when they are removed from the simulated uterine cavity, but they have a quite different relationship when they are pressed by axial compressive loads. CONCLUSION: It can be surmised that the novel T-shape nanocomposite IUD is superior to the existing T-shape Cu-IUD. It may alleviate the users' pain in future clinical application. Shape is a very important factor that affects the force imposed by the inserted IUDs, and it must be taken into account when a new IUD is designed.

Cupric ion release controlled by copper/low-density polyethylene nanocomposite in simulated uterine solution.

The Cu2+ release rate of novel copper/low-density polyethylene composites as an intrauterine device material in the simulated uterine solution was investigated for 280 days. The corrosion products of these composites were identified by the X-ray diffraction method. The distributions of the copper phase and the cuprous oxide phase at different corrosion depths in the composites were measured by the internal standard method. For comparison, copper particles of two sizes were embedded in a polyethylene matrix to form composites. The average copper particle diameter of the nanocomposite was 30 nm, while that of microcomposite was 52 microm. Mechanism of Cu2+ release controlled by the nanocomposite revealed that many clusters composed of copper nanoparticles, which were observed by the field emission scanning electron microscopy in the nanocomposite, led to the formation of large amounts of Cu2O and consequently facilitated the Cu2+ steady release. A scanning electron microscope with energy dispersive X-ray microanalysis mapping technique (SEM/EDX) was employed to measure the corrosion depth and to calculate the life span of the nanocomposite. The result that the nanocomposite displayed a near zero-order release after a month of incubation indicated that the Cu2+ release behavior controlled by nanocomposite was remarkably superior to that by microcomposite.

Water absorption characteristics of novel Cu/LDPE nanocomposite for use in intrauterine devices.

Intrauterine devices (IUDs), especially the copper-containing IUDs (Cu-IUDs), are one of the worldwide used forms for birth control, owing to their advantages of long-lasting and high efficacy, economy, safety, and reversibility. However, it is not perfect for the existing Cu-IUDs; some shortcomings related to its side effects have not been overcome yet. For this reason, a new Cu-IUDs material, the copper/low-density polyethylene (Cu/LDPE) nanocomposite, has been developed in our research team. The structure and water uptake characteristics of this new Cu-IUDs material have been investigated by using X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and gravimetric analysis in this paper. The results of XRD, SEM, EDS, and FT-IR show three important outcomes associated with the structure of the nanocomposite. First, the nanocomposite is hybrid of the polymer and the copper nanoparticles (nano-Cu). Second, porosities, nano-Cu aggregates, and primary alcohol (R--CH(2)--OH) are existed in the nanocomposite. Third, the nano-Cu aggregates are distributed uniformly in the polymer matrix in general. The results of Gravimetric analysis, which associated with the water uptake characteristics of the nanocomposite, exhibit that the water absorption behavior of the nanocomposite obeys the classical diffusion theory very well, the water uptake of the nanocomposite increases with the increasing of the nano-Cu loading, and that the water uptake ability of the nanocomposite with 15.0 wt % nano-Cu (50 nm in diameter) is about 150 times larger than that of the base resin and about 45 times higher than that of the Cu/LDPE microcomposite with 15.0 wt % copper microparticles (5 microm in diameter). These water uptake characteristics are mainly attributed to the structure of the Cu/LDPE composites and the size effect of the nano-Cu.

Corrosion behavior of copper/LDPE nanocomposites in simulated uterine solution.

We prepared copper/low-density polyethylene (LDPE) nanocomposites with various mass fractions of copper nanoparticles and investigated the Cu(2+) release rate of them for 220 days in a simulated uterine solution .The influences of copper nanoparticle mass fraction on Cu(2+) release and volume resistivity confirm that continuous network of copper nanoparticles can be obtained in composites when copper nanoparticle mass fraction ranges from 30% to 35%. Scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX) mapping technique was employed to investigate the copper distribution and corrosion depth of 30 wt% copper/LDPE composite before and after incubation. Besides, elements and phases were also analyzed by EDX and X-ray diffraction, respectively. The results suggest that copper/LDPE nanocomposites should be more efficient and feasible than conventional IUD materials.

Alterations in the endometrium of rats, rabbits, and Macaca mulatta that received an implantation of copper/low-density polyethylene nanocomposite.

A copper/low-density polyethylene nanocomposite (nano-Cu/LDPE), a potential intrauterine device component material, has been developed from our research. A logical extension of our previous work, this study was conducted to investigate the expression of plasminogen activator inhibitor 1 (PAI-1), substance P (SP), and substance P receptor (SP-R) in the endometrium of Sprague Dawley rats, New Zealand White rabbits, and Macaca mulatta implanted with nano-Cu/LDPE composite. The influence of the nano-Cu/LDPE composite on the morphology of the endometrium was also investigated. Animals were randomly divided into five groups: the sham-operated control group (SO group), bulk copper group (Cu group), LDPE group, and nano-Cu/LDPE groups I and II. An expression of PAI-1, SP, and SP-R in the endometrial tissues was examined by immunohistochemistry at day 30, 60, 90, and 180 postimplantation. The significant difference for PAI-1, SP, and SP-R between the nano-Cu/LDPE groups and the SO group (P<0.05) was identified when the observation period was terminated, and the changes of nano-Cu/LDPE on these parameters were less remarkable than those of the Cu group (P<0.05). The damage to the endometrial morphology caused by the nano-Cu/LDPE composite was much less than that caused by bulk copper. The nano-Cu/LDPE composite might be a potential substitute for conventional materials for intrauterine devices in the future because of its decreased adverse effects on the endometrial microenvironment.

Chitosan/alginate multilayer film for controlled release of IDM on Cu/LDPE composite intrauterine devices.

To reduce such side effects as pain and bleeding caused by copper-containing intrauterine device (Cu-IUD), a novel medicated intrauterine device, which is coated with an indomethacin (IDM) delivery system on the surface of copper/low-density polyethylene (Cu/LDPE) composite intrauterine device, has been proposed and developed in the present work. The IDM delivery system is a polyelectrolyte multilayer film, which is composed of IDM containing chitosan and alginate layer by layer, is prepared by using self-assembled polyelectrolyte multilayer method, and the number of the layers of this IDM containing chitosan/alginate multilayer film can be tailored by controlling the cyclic repetition of the deposition process. After the IDM containing chitosan/alginate multilayer film is obtained on the surface of Cu/LDPE composite intrauterine device, its release behavior of both IDM and cupric ion has been studied in vitro. The results show that the release duration of IDM increase with the increasing of thickness of the IDM containing chitosan/alginate multilayer film, and the initial burst release of cupric ion cannot be found in this novel medicated Cu/LDPE composite IUD. These results can be applied to guide the design of novel medicated Cu-IUD with minimal side effects for the future clinical use.

Preparation and cupric ion release behavior of Cu/LDPE porous composites with tunable pore morphology for intrauterine devices.

Copper/low-density polyethylene (Cu/LDPE) porous composites are novel materials for copper-containing intrauterine devices (Cu-IUDs). Here we report a method, i.e., by changing the mass ratio of two kinds of porogens that have different melting points through the combined techniques of injection molding and particulate leaching, to prepare the Cu/LDPE porous composites with tunable pore morphology. After these Cu/LDPE porous composites with different pore morphologies were obtained, the influences of pore morphologies on their cupric ion release behaviors were studied. The results show that the pore morphology has great influence on the cupric ion release behavior of Cu/LDPE porous composites. This phenomenon is caused by the different influences of different pore morphologies on the effective porosity and the surface hydrophilicity. And those results can be applied to guide the fabrication of Cu/LDPE porous composite Cu-IUDs with minimal weight at an appropriate cupric ion release rate.

A porous Cu/LDPE composite for copper-containing intrauterine contraceptive devices.

To improve the rates of both cupric ion release and the utilization of copper in non-porous copper/low-density polyethylene (Cu/LDPE) composite, a porous Cu/LDPE composite is proposed and developed in the present work. Here 2,5-di-tert-butylhydroquinone was chosen as the porogen, ethyl acetate was chosen as the solvent for extraction, and the porous Cu/LDPE composite was obtained by using injection molding and the particulate leaching method. After any residual ethyl acetate remaining inside the porous Cu/LDPE composite had been removed by vacuum drying, the composite was characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry and absorption measurement. For comparison, a non-porous Cu/LDPE composite was also characterized in the same way. The results show that the porous structure was successfully introduced into the polymeric base of the non-porous Cu/LDPE composite, and the porous Cu/LDPE composite is a simple hybrid of copper particles and porous LDPE. The results also show that the introduction of a porous structure can improve the cupric ion release rate of the non-porous Cu/LDPE composite with a certain content of copper particles, indicating that the utilization rate of copper can be improved either the introduction of a porous structure, and that the porous Cu/LDPE composite is another promising material for copper-containing intrauterine devices.

Study on the mechanical properties of Cu/LDPE composite IUDs.

BACKGROUND: The copper/low-density polyethylene composite (Cu/LDPE composite) intrauterine devices (IUDs), which can eliminate or lessen the side effects of existing IUDs, have been developed in our laboratory. As a novel type of copper-containing IUDs, it is not clear whether the mechanical properties of the Cu/LDPE composite IUDs can meet the need of clinical use or not. Therefore, the mechanical properties of the Cu/LDPE composite IUDs have been studied in the present article. STUDY DESIGN: The influence of copper particle content and size on the mechanical properties of the Cu/LDPE composite IUDs was analyzed firstly to provide guidance for the material composition design of the Cu/LDPE composite IUDs, and then the BaSO(4)/LDPE composite, which has been applied as a framework of the existing copper-containing IUDs in clinical use for decades, has been used as reference to judge whether the mechanical properties of the Cu/LDPE composite IUDs can meet the need of clinical use or not. However, the mechanical properties of IUDs cannot be characterized directly. Therefore, the mechanical properties of both the Cu/LDPE composite IUDs and the framework of the existing copper-containing IUDs were investigated by means of tensile test using standard tensile samples, and the fracture surface morphology of the tensile samples was characterized by scanning electron microscopy (SEM). RESULTS: Both the elongation at break and the tensile strength decrease with increasing of copper particle content and increase with increasing of the copper particle size, while the elastic modulus shows an opposite tendency. The tensile strength and elastic modulus of both the Cu/LDPE microcomposite IUDs and the Cu/LDPE nanocomposite IUDs with 25 wt.% of copper particles are higher than those of existing copper-containing IUDs (TCu220C; its framework is made of the BaSO(4)/LDPE composite with 20 wt.% of BaSO(4)). CONCLUSIONS: The content and size of the copper particles have significant effect on the mechanical properties of Cu/LDPE composite IUDs. The mechanical properties of both the Cu/LDPE microcomposite IUDs and the Cu/LDPE nanocomposite IUDs with 25 wt.% of copper particles were superior to that of existing copper-containing IUDs, indicating that the novel Cu/LDPE composite IUDs can satisfy the requirement of mechanical properties in clinical application.

Will ethylene oxide sterilization influence the application of novel Cu/LDPE nanocomposite intrauterine devices?

BACKGROUND: Copper/low-density polyethylene (Cu/LDPE) nanocomposite intrauterine device (IUD) is an implanted medicinal device that must be sterilized before use. Sterilization processes act either chemically or physically, leading to a lethal change in the structure or function of organic macromolecules in microorganisms. Given the nature of their action, sterilization might also attack the macromolecules of polymers by the same mechanisms, resulting in changes in surface functional groups and in the internal structure of the polymer. If sterilization leads to changes in surface functional groups and in the internal structure of the LDPE matrix, which will influence the mechanical property and cupric ions release rate of novel Cu/LDPE nanocomposite IUDs, potential clinical application will be limited. Therefore, it is necessary to study the influence of ethylene oxide sterilization on the potential clinical application of novel Cu/LDPE nanocomposite IUDs. STUDY DESIGN: The influence of ethylene oxide sterilization on the internal structure, surface functional groups, mechanical property and cupric ions release rate of novel Cu/LDPE nanocomposite IUDs was studied using differential scanning calorimetry, attenuated total reflection Fourier transform infrared spectroscopy, tensile testing and absorbance measurement. RESULTS: Ethylene oxide sterilization did not have any influence on the internal structure, surface functional groups, mechanical property and cupric ions release rate of novel Cu/LDPE nanocomposite intrauterine devices. CONCLUSION: Ethylene oxide sterilization will not affect the potential application of novel Cu/LDPE nanocomposite IUDs.

IDM release behavior and surface characteristics of the novel Cu/IDM/LDPE nanocomposite for intrauterine device.

Copper/indomethacin/low-density polyethylene (Cu/IDM/LDPE) nanocomposite was prepared as a novel material for intra-uterine device (IUD). IDM release profile of the nanocomposite was investigated by using spectrophotometer. The results show that IDM release rate of Cu/IDM/LDPE nanocomposite is higher in simulated uterine solution than that in methanol, confirming that the release process of IDM is dominated mainly by pore diffusion. The decrease in copper particle size and the increase in copper mass content all accelerate IDM release, indicating that IDM release rate can be adjusted by changing copper loading or copper particle size. The surface of the incubated nanocomposite was characterized by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray microanalysis. A few deposits composed of P, Cl, Ca, Cu and O were observed on the nanocomposite surface, which may be related to the presence of IDM particles with large particle size.

Zn(2+) release behavior and surface characteristics of Zn/LDPE nanocomposites and ZnO/LDPE nanocomposites in simulated uterine solution.

To decrease the side effects of the existing copper-bearing intrauterine devices, the zinc/low-density polyethylene (Zn/LDPE) nanocomposite and zinc-oxide/low-density polyethylene (ZnO/LDPE) nanocomposite have been developed in our research for intrauterine devices (IUDs). In this study, the influences of preparation methods of nanocomposites and particle sizes of zinc and zinc oxide on Zn(2+) release from composites incubated in simulated uterine solution were investigated. All release profiles are biphasic: an initial rapid release phase is followed by a near zero-order release period. Zn(2+) release rates of nanocomposites prepared by compressing moulding are higher than those of the nanocomposites prepared by hot-melt extrusing. Compared with Zn(2+) release from the microcomposites, the release profiles of the nanocomposites exhibit a sharp decrease in Zn(2+) release rate in the first 18 days, an early onset of the zero-order release period and a high release rate of Zn(2+) at the later stage. The microstructure of the Zn/LDPE sample and the ZnO/LDPE sample after being incubated for 200 days was characterized by SEM, XRD and EDX techniques. The results show that the dissolution depth of ZnO/LDPE nanocomposite is about 60 mum. Lots of pores were formed on the surface of the Zn/LDPE sample and ZnO/LDPE sample, indicating that these pores can provide channels for the dissolution of nanoparticles in the matrix. The undesirable deposits that are composed of ZnO are only detected on the surface of Zn/LDPE nanocomposite, which may increase the risk of side effects associated with IUDs. It can be expected that ZnO/LDPE nanocomposite is more suitable for IUDs than Zn/LDPE nanocomposite.

Effect of implanted Cu/low-density polyethylene nanocomposite on the morphology of endometrium in the mouse.

OBJECTIVE: To investigate the damage of endometrium caused by the implanted Cu/low-density polyethylene (LDPE) nanocomposite and the contraceptive effect of this novel copper-containing intrauterine device material. DESIGN: Experimental animal study. SETTING: TongJi Medical College of Huazhong University of Science and Technology. PATIENT(S): Sixty healthy female mice. INTERVENTION(S): Twenty mice received no implants, 20 mice received the Cu/LDPE nanocomposite, and 20 mice received bulk copper. MAIN OUTCOME MEASURE(S): Morphologic features of the endometrium, contraceptive effect, and surface condition of the implanted implants. RESULT(S): The contraceptive effect of both the Cu/LDPE nanocomposite and bulk copper is 100%, the damage of the endometrium caused by the Cu/LDPE nanocomposite is much less than that caused by bulk copper, and the surface of the implanted Cu/LDPE nanocomposite is much smoother and much softer than that of the implanted bulk copper. CONCLUSION(S): The contraceptive effect of the Cu/LDPE nanocomposite is comparable with that of bulk copper, and the damage of the endometrium caused by the Cu/LDPE nanocomposite is much less than that caused by bulk copper. The endometrium injury is related to the surface condition of the implanted intrauterine device material.