84 research outputs found
Optical sensor array of chiral MOF-based Fabry–Pérot films for enantioselective odor sensing
An optical sensor array based on photonic Fabry–Pérot films of surface-mounted metal–organic-frameworks (SURMOFs) with different homochiral structures is presented. It is used to detect and enantioselectively discriminant 3 pairs of chiral odor molecules, either pure or in binary mixtures
A MOF-based electronic nose for carbon dioxide sensing with enhanced affinity and selectivity by ionic-liquid embedment
The unequivocal detection of CO is important in many situations, like in the living environment, plant cultivation and the conservation of cultural relics and archives. Due to their large specific surface areas and highly ordered and tunable structures, metal–organic frameworks (MOFs) have the potential to improve CO sensing, however, they often suffer from low CO affinity and selectivity. Ionic liquids (ILs) have high CO affinity, but their performance in sensors is hampered by their nonporous, liquid form. Here, we present a low-cost and portable CO sensor system based on an array of gravimetric sensors made of MOF films with embedded ILs in the pores. The array is composed of MOF films of two different structures, which are HKUST-1 and UiO-66, filled with 3 different types of ILs and 2 different pore-filling levels, resulting in an array of up to 14 different sensors. We show that the different combinations of IL and MOF result in different affinities for CO and other analytes. With the help of machine learning using a neural network, the sensor array was used to quantify the CO concentration as well as to distinguish CO from other gases and vapors, like nitrogen, ethanol, methanol and water, and to distinguish certain binary mixtures. While the MOF-sensor array without IL achieves only a small accuracy for determining the CO concentration, the IL@MOF sensor array can accurately classify the gas types (98% accuracy) in mixed gas atmospheres of unknown composition and concentration as well as can determine the CO gas concentration with an average error of only 2.7%. Using only MOFs with a pronounced chemical stability (like UiO-66) in the sensor array also allows the detection and identification of CO in a humid atmosphere. Moreover, the presented sensor system has very high sensitivity with a CO limit of detection below 100 ppm, which is four times smaller than the CO concentration in air. This work shows the unprecedented performance of the sensor arrays of MOFs with embedded ILs, referred to as IL@MOF-electronic nose (IL@MOF-e-nose), for sensing the composition and concentration of CO gas mixtures
Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion
Molecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom-up layer-by-layer assembly of oriented overcrowded-alkene molecular motors forming a crystalline metal–organic framework thin film. While all stator parts of the overcrowded-alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light-induced molecular rotation. Taking advantage of the thin film\u27s transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta-)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials
Large-eddy simulation of ow and combustion dynamics in a lean partially premixed swirling combustor
A lean partially premixed swirling combustor was studied by resolving the complete flow path from the swirl vanes to the chamber outlet with large-eddy simulation (LES). The flow and combustion dynamics for non-reacting and reacting situations was analysed, where the intrinsic effects of swirl vanes and counter flows on the vortex formation, vorticity distribution for non-reacting cases were examined. A modified flame index was introduced to identify the flame regime during the partially premixed combustion. The combustion instability phenomenon was examined by applying Fourier spectra analysis. Several scalar variables were monitored to investigate the combustion dynamics at different operating conditions. The effects of swirl number, equivalence ratio and nitrogen dilution on combustion dynamics and NOx emissions were found to be significant.This work is supported by the UK EPSRC through Grant EP/K036750/1 and the National Natural Science Foundation of China through
Grant No. 51376107. The computation is supported by the Tsinghua National Laboratory for Information Science and TechnologyPeer ReviewedPostprint (author's final draft
A Colorimetric Label‐Free Sensor Array of Metal–Organic‐Framework‐Based Fabry–Pérot Films for Detecting Volatile Organic Compounds and Food Spoilage
The unambiguous detection and classification of volatile organic compounds (VOCs) are crucial in many fields. For using VOC-sensing to explore the alteration and spoilage of food, very inexpensive sensors are desired. Simple colorimetric sensors seem highly attractive for these applications. Here, a label-free, colorimetric sensor array made of metal-organic-framework-based (MOF-based) Fabry-Pérot (FP) films is presented where the signal read-out is performed either by their optical spectra or by pictures taken with a smartphone camera. Exposing the FP-MOF-films to various VOCs causes a reversible shift of the photonic pattern, where the magnitude of the shift depends on the VOC type, its concentration, and the MOF structure. The application of machine- learning- algorithms on the sensor data allows to identify the VOCs with a high classification accuracy (92% at 100 ppm). It is shown that the sensor array read-out can also be performed with a common smartphone camera, also precisely classifying the VOC analytes. Moreover, fresh and spoiled food, like milk and meat, is distinguished by its head space. Thus, the study presents a very inexpensive platform of small colorimetric sensors that allow determining the quality, alteration, and spoilage of food, and it may contribute to realizing smart labels and intelligent packaging
On–off conduction photoswitching in modelled spiropyran-based metal-organic frameworks
Materials with photoswitchable electronic properties and conductance values that can be reversibly changed over many orders of magnitude are highly desirable. Metal-organic framework (MOF) films functionalized with photoresponsive spiropyran molecules demonstrated the general possibility to switch the conduction by light with potentially large on-off-ratios. However, the fabrication of MOF materials in a trial-and-error approach is cumbersome and would benefit significantly from in silico molecular design. Based on the previous proof-of-principle investigation, here, we design photoswitchable MOFs which incorporate spiropyran photoswitches at controlled positions with defined intermolecular distances and orientations. Using multiscale modelling and automated workflow protocols, four MOF candidates are characterized and their potential for photoswitching the conductivity is explored. Using ab initio calculations of the electronic coupling between the molecules in the MOF, we show that lattice distances and vibrational flexibility tremendously modulate the possible conduction photoswitching between spiropyran- and merocyanine-based MOFs upon light absorption, resulting in average on-off ratios higher than 530 and 4200 for p- and n-conduction switching, respectively. Further functionalization of the photoswitches with electron-donating/-withdrawing groups is demonstrated to shift the energy levels of the frontier orbitals, permitting a guided design of new spiropyran-based photoswitches towards controlled modification between electron and hole conduction in a MOF
Substrate‐Bound Diarylethene‐Based Anisotropic Metal–Organic Framework Films as Photoactuators with a Directed Response
Molecular machines and responsive materials open a plethora of new opportunities in nanotechnology. We present an oriented crystalline array of diarylethene (DAE)-based photoactuators, arranged in a way to yield an anisotropic response. The DAE units are assembled, together with a secondary linker, into a monolithic surface-mounted metal–organic framework (SURMOF) film. By Infrared (IR) and UV/Vis spectroscopy as well as by synchrotron X-ray diffraction, we show that the light-induced extension changes of the molecular DAE linkers multiply to yield mesoscopic and anisotropic length changes. Due to the special architecture and substrate-bonding of the SURMOF, these length changes are transferred to the macroscopic scale, leading to the bending of a cantilever and performing work. This research shows the potential of assembling light-powered molecules into SURMOFs to yield photoactuators with a directed response, presenting a path to advanced actuators
Promoting Sino-UK Collaboration on Developing Low Carbon and Sustainable Methodologies for Brownfields and Marginal Land Re-use in China
The authors are grateful to all partners of the SPF project which include a wide team of
collaborators and advisors across China and UK for their useful discussions and contribution during the project. Ming Liu and Chris He (Department of Science, Technology & Innovation, British Consulate-General Guangzhou), Rongxia Liu and Xia Yang (Administrative Centre for China’s Agenda21), Kate Canning (Arup) and David Middleton (Department for Environment and Rural Affairs, UK) helped discussion and revision of the report.
We acknowledge the financial support from the Foreign Common Office’s Prosperity Fund programme. We also are grateful to the contribution of the University of Brighton and the Land Trust who supported the PSRP case study development project and shared its findings with this project.
This report is one of the outputs of the China Prosperity Strategic Programme Fund (SPF) on “Promoting Sino-UK collaboration on developing low carbon and sustainable methodologies for Brownfields and marginal land re-use in China” (project 16AG15)Rapid urbanisation and changes in land use resulting from industrial change has left a legacy of
vast polluted industrial and commercial areas (also called brownfields) and marginal land areas.
Recent evidence from the UK, EU and USA indicate that these land areas may have considerable
potential for renewables production, for example from solar, wind or biomass. In parallel there
are opportunities for carbon storage in rehabilitated soil, as well as substitution by the
production of renewables. The UK is also leading the understanding in the wider parallel
benefits that can be achieved from ecosystem services and public health benefits from
improved provision of green space. These multiple services can be provided together, in synergy,
from soft re-uses of post-industrial sites, and in this way the post-industrial regeneration areas
in China should be seen as a major opportunity for new enterprise, society and the wider
environment. The improving bankability of renewable energy projects, and the possibility of
creating a voluntary carbon offset business, means that revenue streams may be sufficient to
pay for ongoing land management over time as a profit generating activity. In terms of fastest
benefit to UK PLC and China, the likelihood is that combination of renewable energies with “dual
use” for habitat will provide both more readily commercial brownfield re-use opportunities for
cities in China in the short term, and also create better carbon management opportunities, as
well as a variety of wider sustainability benefits. Thus this type of re-uses will create a platform
for rapid commercial exchange and development between Chinese and UK companies.
Considering that China is preparing an action plan for managing soil pollution and remediation
across the country estimated to be RMB 7tn which is equivalent to one-third of the national
exchange reserves, this report on developing low carbon and sustainable methodologies for
brownfields and marginal land re-use in China provides timely information that will support the
decision making for sustainable remediation opportunities in China.
The report is intended to serve as a tool and resource guide to stakeholders involved in land
remediation willing to engage in sustainable remediation implementation for renewable energy
and carbon management applications. It is intended to inform remediation stakeholders
unfamiliar with sustainable remediation about the concept, practices, and available resources.
The report capitalises on UK leadership positions on the sustainable rehabilitation of
brownfields land (SURF-UK), the soft re-use of brownfields (e.g. for energy or amenity rather
than buildings); effective end-use directed risk management for contaminated land, and
sustainable remediation.Foreign Common Office’s Prosperity Fund programme SPF project 16AG1
Zinc finger and SCAN domain containing 1, ZSCAN1, is a novel stemness-related tumor suppressor and transcriptional repressor in breast cancer targeting TAZ
IntroductionCancer stem cells (CSCs) targeted therapy holds the potential for improving cancer management; identification of stemness-related genes in CSCs is necessary for its development.MethodsThe Cancer Genome Atlas (TCGA) and the Molecular Taxonomy of Breast Cancer International Consortium (METABRIC) datasets were used for survival analysis. ZSCAN1 correlated genes was identified by Spearman correlation analysis. Breast cancer stem-like cells (BCSLCs) were isolated by sorting CD44+CD24- cells from suspension cultured breast cancer (BC) spheroids. The sphere-forming capacity and sphere- and tumor-initiating capacities were determined by sphere formation and limiting dilution assays. The relative gene expression was determined by qRT-PCR, western blot. Lentivirus system was used for gene manipulation. Nuclear run-on assay was employed to examine the levels of nascent mRNAs. DNA pull-down and Chromatin immunoprecipitation (ChIP) assays were used for determining the interaction between protein and target DNA fragments. Luciferase reporter assay was used for evaluating the activity of the promoter.Results and discussionZSCAN1 is aberrantly suppressed in BC, and this suppression indicates a bad prognosis. Ectopic expression of ZSCAN1 inhibited the proliferation, clonogenicity, and tumorigenicity of BC cells. ZSCAN1-overexpressing BCSLCs exhibited weakened stemness properties. Normal human mammary epithelial (HMLE) cells with ZSCAN1 depletion exhibited enhanced stemness properties. Mechanistic studies showed that ZSCAN1 directly binds to -951 ~ -925bp region of WWTR1 (encodes TAZ) promoter, inhibits WWTR1 transcription, thereby inhibiting the stemness of BCSCs. Our work thus revealed ZSCAN1 as a novel stemness-related tumor suppressor and transcriptional repressor in BC
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