Abstract
Glucose electrolysis offers a prospect of value-added glucaric acid synthesis and energy-saving hydrogen production from the biomass-based platform molecules. Here we report that ...nanostructured NiFe oxide (NiFeO
x
) and nitride (NiFeN
x
) catalysts, synthesized from NiFe layered double hydroxide nanosheet arrays on three-dimensional Ni foams, demonstrate a high activity and selectivity towards anodic glucose oxidation. The electrolytic cell assembled with these two catalysts can deliver 100 mA cm
−2
at 1.39 V. A faradaic efficiency of 87% and glucaric acid yield of 83% are obtained from the glucose electrolysis, which takes place via a guluronic acid pathway evidenced by in-situ infrared spectroscopy. A rigorous process model combined with a techno-economic analysis shows that the electrochemical reduction of glucose produces glucaric acid at a 54% lower cost than the current chemical approach. This work suggests that glucose electrolysis is an energy-saving and cost-effective approach for H
2
production and biomass valorization.
Adsorption technology based on ethane‐selective materials is a promising alternative to energy‐intensive cryogenic distillation for separating ethane (C2H6) and ethylene (C2H4). We employed a pore ...engineering strategy to tune the pore environment of a metal–organic framework (MOF) through organic functional groups and boosted the C2H6/C2H4 separation of the MOF. Introduction of amino (−NH2) groups into Tb‐MOF‐76 not only decreased pore sizes but also facilitated multiple guest‐host interactions in confined pores. The NH2‐functionalized Tb‐MOF‐76(NH2) has increased C2H6 and C2H4 uptakes and C2H6/C2H4 selectivity. The results of experimental and simulated transient breakthroughs reveal that Tb‐MOF‐76(NH2) has significantly improved one‐step separation performance for C2H6/C2H4 mixtures with a high C2H4 (>99.95 %) productivity of 17.66 L kg−1 compared to 7.53 L kg−1 by Tb‐MOF‐76, resulting from the suitable pore confinement and accessible −NH2 groups on pore surfaces.
By virtue of a pore engineering strategy based on isoreticular chemistry, an amino‐functionalized metal–organic framework (MOF) with suitable pore confinement and more binding sites improved the ethane/ethylene separation performance compared to the parent MOF.
One‐step C2H4 purification from ternary C2H6/C2H4/C2H2 mixtures by a single adsorbent is of great industrial significance, but few adsorbents achieve this separation. Herein, we report a robust ...metal–organic framework (MOF) that possesses methyl‐decorated nonpolar pores and shows one‐step C2H4 purification (purity >99.9 %) from binary C2H6/C2H4 mixtures and ternary C2H6/C2H4/C2H2 mixtures. The methyl groups in pores provide a suitable pore environment to simultaneously enhance the adsorption capacity for C2H2 and C2H6 compared to C2H4. Simulations revealed the multiple interactions between C2H6 or C2H2 molecules and the pore wall, while the interactions with C2H4 molecules are weak and also unfavorable due to the repulsion from methyl groups in pores. The MOF displays high C2H6 and C2H2 uptakes and benchmark C2H6/C2H4 selectivity (2.2), surpassing all of the reported MOFs for one‐step C2H4 purification from ternary C2H6/C2H4/C2H2 mixtures.
The combination of nonpolar pore environment and accessible active sites in a metal–organic framework affords benchmark C2H6/C2H4 selectivity and realizes one‐step C2H4 purification from ternary C2H6/C2H4/C2H2 mixtures.
To construct an immune-related gene prognostic index (IRGPI) for head and neck squamous cell carcinoma (HNSCC) and clarify the molecular and immune characteristics and the benefit of immune ...checkpoint inhibitor (ICI) therapy in IRGPI-defined subgroups of HNSCC.
On the basis of The Cancer Genome Atlas HNSCC immune dataset (
= 546), 22 immune-related hub genes were identified by weighted gene coexpression network analysis. Three genes were identified to construct an IRGPI by using the Cox regression method and validated with the Gene Expression Omnibus (GEO) dataset (
= 270). Afterward, the molecular and immune characteristics and the benefit of ICI therapy in IRGPI-defined subgroups were analyzed.
The IRGPI was constructed on the basis of
,
, and
genes. IRGPI-high patients had a better overall survival than IRGPI-low patients, consistent with the results in the GEO cohort. The comprehensive results showed that a high IRGPI score was correlated with DNA repair-related pathways; low
mutation rate; high infiltration of CD8 T cells, CD4 T cells, and M1 macrophages; active immunity and less aggressive phenotypes; and more benefit from ICI therapy. In contrast, a low IRGPI score was associated with cancer and metastasis-related pathways; high
and
mutation rate; high infiltration of B cells, M0 macrophages, and M2 macrophages; suppressive immunity and more aggressive phenotypes; and less benefit from ICI therapy.
IRGPI is a promising biomarker to distinguish the prognosis, the molecular and immune characteristics, and the immune benefit from ICI therapy in HNSCC.
Exploring the lithium resources in concentrated seawater/salt lake brine could provide necessary support for the sustainable development in future. Selective-electrodialysis (S-ED, equipped with ...monovalent selective ion-exchange membranes) is considered as an effective way to reduce the ratio of magnesium to lithium in concentrated seawater/salt lake brines. However, the effectiveness of the prefractionation of lithium chloride from brine is not clearly investigated, because both seawater and salt lake brines are complex mixtures. Nowadays, only simple systems with binary or ternary cations system have been investigated. Based on a clean production process for the utilization of concentrated seawater/salt lake brine, the prefractionation of LiCl from concentrated seawater/salt lake brines by S-ED was investigated in this work. From the concentrated seawater experiments, it is beneficial to improve the RLi (recovery ratio of Li+) at a higher voltage, but an excessively high working voltage is adverse to the preliminary separation between Li+ and Mg2+; a bigger VC/VD (initial volume ratio of concentrating and desalting solution, VD = 2.5 L in this paper) is favorable to increase RLi and reduce ESEC (specific energy consumption of Li+). At the optimal voltage of 7 V and VC/VD of 0.6, the mole ratio of LiCl: MgCl2: MgSO4 increased from 1: 2.227: 2.463 to 1: 1.461: 0.085. For the salt lake brines, the optimal voltage for the LiCl prefractionation in the selected brine system was 10 V, which had a higher RLi of 76.45% and an appropriate ESEC of 0.66 kWh/(mol Li). Finally, the parameters of RLi, ESEC and separation effect of LiCl were discussed for the salt lakes of West Taijinar, East Taijinar and Yiliping in China. It is found that the East Taijinar salt lake brine was more suitable to obtain LiCl at a lower ESEC.
Prefractionation of LiCl from concentrated seawater/salt lake brines by selective-electrodialysis (S-ED). Display omitted
•LiCl's prefractionation could be implemented by selective-electrodialysis (S-ED).•S-ED could increase LiCl: MgCl2: MgSO4 to 1: 1.461: 0.085 for concentrated seawater.•The order of LiCl extraction efficiency was East Taijinar > Yiliping > West Taijinar.•LiCl: MgCl2: MgSO4 increased to 1: 1.089: 0.199 with S-ED for East Taijinar brine.
The diverse expression pattern of CD36 reflects its multiple cellular functions. However, the roles of CD36 in colorectal cancer (CRC) remain unknown. Here, we discover that CD36 expression is ...progressively decreased from adenomas to carcinomas. CD36 loss predicts poor survival of CRC patients. In CRC cells, CD36 acts as a tumor suppressor and inhibits aerobic glycolysis in vitro and in vivo. Mechanically, CD36-Glypcian 4 (GPC4) interaction could promote the proteasome-dependent ubiquitination of GPC4, followed by inhibition of β-catenin/c-myc signaling and suppression of downstream glycolytic target genes GLUT1, HK2, PKM2 and LDHA. Moreover, disruption of CD36 in inflammation-induced CRC model as well as Apc
mice model significantly increased colorectal tumorigenesis. Our results reveal a CD36-GPC4-β-catenin-c-myc signaling axis that regulates glycolysis in CRC development and may provide an intervention strategy for CRC prevention.
High‐efficiency electromagnetic (EM) functional materials are the core building block of high‐performance EM absorbers and devices, and they are indispensable in various fields ranging from ...industrial manufacture to daily life, or even from national defense security to space exploration. Searching for high‐efficiency EM functional materials and realizing high‐performance EM devices remain great challenges. Herein, a simple solution‐process is developed to rapidly grow gram‐scale organic–inorganic (MAPbX3, X = Cl, Br, I) perovskite microcrystals. They exhibit excellent EM response in multi bands covering microwaves, visible light, and X‐rays. Among them, outstanding microwave absorption performance with multiple absorption bands can be achieved, and their intrinsic EM properties can be tuned by adjusting polar group. An ultra‐wideband bandpass filter with high suppression level of −71.8 dB in the stopband in the GHz band, self‐powered photodetectors with tunable broadband or narrowband photoresponse in the visible‐light band, and a self‐powered X‐ray detector with high sensitivity of 3560 µC Gyair−1 cm−2 in the X‐ray band are designed and realized by precisely regulating the physical features of perovskite and designing a novel planar device structure. These findings open a door toward developing high‐efficiency EM functional materials for realizing high‐performance EM absorbers and devices.
A facile one‐step solution processing method is developed to rapidly prepare gram‐scale MAPbX3 microcrystals. Utilizing its intrinsic electromagnetic (EM) properties, a series of EM devices is designed and fabricated, which can be applied in the fields of ultra‐wideband bandpass filters and multi‐band photodetection covering X‐rays, UV, visible light, and microwaves.
Chronoamperometry was used to study the dynamics of Pt nanoparticle (NP) collision with an inert ultramicroelectrode via electrocatalytic amplification (ECA) in the hydrogen evolution reaction. ECA ...and dynamic light scattering (DLS) results reveal that the NP colloid remains stable only at low proton concentrations (1.0 mm) under a helium (He) atmosphere, ensuring that the collision events occur at genuinely single NP level. Amperometry of single NP collisions under a He atmosphere shows that each discrete current profile of the collision event evolves from spike to staircase at more negative potentials, while a staircase response is observed at all of the applied potentials under hydrogen‐containing atmospheres. The particle size distribution estimated from the diffusion‐controlled current in He agrees well with electron microscopy and DLS observations. These results shed light on the interfacial dynamics of the single nanoparticle collision electrochemistry.
Evolution or stability? Under a helium atmosphere, the electrochemical catalytic current profile of the hydrogen evolution reaction on a single platinum nanoparticle (Pt NP) evolves from a spike to a staircase at more negative potentials on the underlying inert ultramicroelectrode (UME). Under a hydrogen atmosphere, the current profile stabilizes as a staircase at all polarized potentials but at least 5 times lower than that in helium.
Tunable terahertz (THz) functional devices have exhibited superior performances due to the use of active materials, such as liquid crystals, graphene, and semiconductors. However, the tunable range ...of constitutive parameters of materials is still limited, which leads to the low modulation depth of THz devices. Here, we demonstrate a broadband tunable THz absorber based on hybrid vanadium dioxide (VO
) metamaterials. Unlike other phase change materials, VO
exhibits an insulator-to-metal transition characteristic and the conductivity can be increased by 4-5 orders of magnitude under external stimulus including electric fields, optical, and thermal pumps. Based on the unique transition character of VO
, the maximum tunable range of the proposed absorber can be realized from 5% to 100% by an external thermal excitation. Meanwhile, an absorption greater than 80% in a continuous range with a bandwidth about 2.0 THz can be obtained when VO
is in its metal phase at high temperature. Furthermore, the absorber is insensitive to the incident angle up to 50° and such a broadband THz absorber can be used in applications including imaging, modulating, cloaking, and so on.
The basic principle of quantum mechanics1 guarantees the unconditional security of quantum key distribution (QKD)2–6 at the cost of forbidding the amplification of a quantum state. As a result, and ...despite remarkable progress in worldwide metropolitan QKD networks7,8 over the past decades, a long-haul fibre QKD network without a trusted relay has not yet been achieved. Here, through the sending-or-not-sending protocol9, we achieve twin-field QKD10 and distribute secure keys without any trusted repeater over a 511 km long-haul fibre trunk that links two distant metropolitan areas. The fibre trunk contains 12 fibres in the cable, three of which are used for the quantum channel, optical synchronization and frequency locking, respectively. The remaining nine are used for classical fibre communication. Our secure key rate is around three orders of magnitude greater than that expected if the previous QKD field-test system was applied over the same length. Efficient quantum-state transmission and stable single-photon interference over such a long-haul deployed fibre pave the way to large-scale fibre quantum networks.A field test of twin-field quantum key distribution was implemented through a 511 km optical fibre. To this end, precise wavelength control of remote independent laser sources and fast time- and phase-compensation systems are developed.
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