Enzymatic Activation and Continuous Electrochemical Production of Methane from Dilute CO2 Sources with a Self-Healing Capsule.

Converting dilute CO2 source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption and greenhouse gas emission, but integrating electrocatalysis with CO2 capture still faced marked challenges. Herein, we show that a self-healing metal-organic macrocycle functionalized as an electrochemical catalyst to selectively produce methane from flue gas and air with the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through an enzymatic activation fashion. The capsule emulates the enzyme' pocket to abstract one in situ-formed CO2-adduct molecule with the commercial amino alcohols, forming an easy-to-reduce substrate-involving clathrate to combine the CO2 capture with electroreduction for a thorough CO2 reduction. We find that the self-healing system exhibited enzymatic kinetics for the first time with the Michaelis-Menten mechanism in the electrochemical reduction of CO2 and maintained a methane Faraday efficiency (FE) of 74.24% with a selectivity of over 99% for continuous operation over 200 h. A consecutive working lab at 50 mA·cm-2, in an eleven-for-one (10 h working and 1 h healing) electrolysis manner, gives a methane turnover number (TON) of more than 10,000 within 100 h. The integrated electrolysis with CO2 capture facilitates the thorough reduction of flue gas (ca. 13.0% of CO2) and first time of air (ca. 400 ppm of CO2 to 42.7 mL CH4 from 1.0 m3 air). The new self-healing strategy of molecular electrocatalyst with an enzymatic activation manner and anodic shifting of the applied potentials provided a departure from the existing electrochemical catalytic techniques.

Highly birefringent side-hole fiber Bragg grating for high-temperature pressure sensing.

We demonstrate a novel, to the best of our knowledge, high-temperature pressure sensor based on a highly birefringent fiber Bragg grating (Hi-Bi FBG) fabricated in a dual side-hole fiber (DSHF). The Hi-Bi FBG is generated by a femtosecond laser directly written sawtooth structure in the DSHF cladding along the fiber core through the slow axis (i.e., the direction perpendicular to the dual-hole axis). The sawtooth structure serves as an in-fiber stressor and also generates Bragg resonance due to its periodicity. The DSHF was etched by hydrofluoric acid to increase its pressure sensitivity, and the diameter of two air holes was enlarged from 38.2 to 49.6 µm. A Hi-Bi FBG with a birefringence of up to 1.8 × 10-3 was successfully created in the etched DSHF. Two distinct reflection peaks could be observed by using a commercial FBG interrogator. Moreover, pressure measurement from 0 to 3 MPa at a high temperature of 700°C was conducted by monitoring the birefringence-induced peak splits and achieved a high-pressure sensitivity of -21.2 pm/MPa. The discrimination of the temperature and pressure could be realized by simultaneously measuring the Bragg wavelength shifts and peak splits. Furthermore, a wavelength-division-multiplexed (WDM) Hi-Bi FBG array was also constructed in the DSHF and was used for quasi-distributed high-pressure sensing up to 3 MPa. As such, the proposed femtosecond laser-inscribed Hi-Bi FBG is a promising tool for high-temperature pressure sensing in harsh environments, such as aerospace vehicles, nuclear reactors, and petrochemical industries.

Nuclear receptor 5A2 regulation of Agrp underlies olanzapine-induced hyperphagia.

Antipsychotic (AP) drugs are efficacious treatments for various psychiatric disorders, but excessive weight gain and subsequent development of metabolic disease remain serious side effects of their use. Increased food intake leads to AP-induced weight gain, but the underlying molecular mechanisms remain unknown. In previous studies, we identified the neuropeptide Agrp and the transcription factor nuclear receptor subfamily 5 group A member 2 (Nr5a2) as significantly upregulated genes in the hypothalamus following AP-induced hyperphagia. While Agrp is expressed specifically in the arcuate nucleus of the hypothalamus and plays a critical role in appetite stimulation, Nr5a2 is expressed in both the CNS and periphery, but its role in food intake behaviors remains unknown. In this study, we investigated the role of hypothalamic Nr5a2 in AP-induced hyperphagia and weight gain. In hypothalamic cell lines, olanzapine treatment resulted in a dose-dependent increase in gene expression of Nr5a2 and Agrp. In mice, the pharmacological inhibition of NR5A2 decreased olanzapine-induced hyperphagia and weight gain, while the knockdown of Nr5a2 in the arcuate nucleus partially reversed olanzapine-induced hyperphagia. Chromatin-immunoprecipitation studies showed for the first time that NR5A2 directly binds to the Agrp promoter region. Lastly, the analysis of single-cell RNA seq data confirms that Nr5a2 and Agrp are co-expressed in a subset of neurons in the arcuate nucleus. In summary, we identify Nr5a2 as a key mechanistic driver of AP-induced food intake. These findings can inform future clinical development of APs that do not activate hyperphagia and weight gain.

Jag2b-Notch3/1b-mediated neuron-to-glia crosstalk controls retinal gliogenesis.

In the developing central nervous systems (CNS), neural progenitor cells generate neurons and glia in sequential order. However, the influence of neurons on glia generation remains elusive. Here, we report that photoreceptor cell-derived Jag2b is required for Notch-dependent Müller glia (MG) generation in the developing zebrafish retina. In jab2b-/- mutants, differentiating MGs are re-specified into lineage-related bipolar neuron fate at the expense of mature MG. Single-cell transcriptome analysis and knock-in animals reveal that jab2b is specifically expressed in crx+ -photoreceptor cells during MG generation. Crx promoter-driven jag2b, but not other Notch ligands, is sufficient to rescue the loss of MGs observed in jag2b-/- mutants. Furthermore, we observe a severe and moderate decrease in the number of MGs in notch3-/- and notch1b-/- mutants, respectively, and the activation of Notch3 or Notch1b rescues the MG loss in jag2b-/- mutants. Together, our findings reveal that the interaction of Jag2b and Notch3/Notch1b mediates the crosstalk between neurons and glial cells to ensure the irreversible differentiation of MG, providing novel mechanistic insights into the temporal specification of glial cell fate in a developing vertebrate CNS structure.

Engineering NH2-Cu-NH2 Triple-atom Sites in Defective MOFs for Selective Overall Photoreduction of CO2 into CH3COCH3.

Selective photoreduction of CO2 to multicarbon products, is an important but challenging task, due to high CO2 activation barriers and insufficient catalytic sites for C-C coupling. Herein, a defect engineering strategy for incorporating copper sites into the connected nodes of defective metal-organic framework UiO-66-NH2 for selective overall photo-reduction of CO2 into acetone. The Cu2+ site in well-modified CuN2O2 units served as a trapping site to capture electrons via efficient electron-hole separation, forming the active Cu+ site for CO2 reduction. Two NH2 groups in CuN2O2 unit adsorb CO2 and cooperated with copper ion to functionalize as a triple atom catalytic site, each interacting with one CO2 molecule to strengthen the binding of *CO intermediate to the catalytic site. The deoxygenated *CO attached to the Cu site interacted with *CH3 fixed at one amino group to form the key intermediate CO*-CH3, which interacted with the third reduction intermediate on another amino group to produce acetone. Our photocatalyst realizes efficient overall CO2 reduction to C3 product acetone CH3COCH3 with an evolution rate of 70.9 µmol gcat -1 h-1 and a selectivity up to 97 % without any adducts, offering a promising avenue for designing triple-atomic sites to producing C3 product from photosynthesis with water.

Unifying developmental programs for embryonic and postembryonic neurogenesis in the zebrafish retina.

The zebrafish retina grows for a lifetime. Whether embryonic and postembryonic retinogenesis conform to the same developmental program is an outstanding question that remains under debate. Using single-cell RNA sequencing of ∼20,000 cells of the developing zebrafish retina at four different stages, we identified seven distinct developmental states. Each state explicitly expresses a gene set. Disruption of individual state-specific marker genes results in various defects ranging from small eyes to the loss of distinct retinal cell types. Using a similar approach, we further characterized the developmental states of postembryonic retinal stem cells (RSCs) and their progeny in the ciliary marginal zone. Expression pattern analysis of state-specific marker genes showed that the developmental states of postembryonic RSCs largely recapitulated those of their embryonic counterparts, except for some differences in rod photoreceptor genesis. Thus, our findings reveal the unifying developmental program used by the embryonic and postembryonic retinogenesis in zebrafish.

Orthogonal single-mode helical Bragg gratings created in fiber cladding for vector bending measurement.

We demonstrate a novel, to the best of our knowledge, two-dimensional vector bending sensor based on orthogonal helical Bragg gratings inscribed in the cladding of a conventional single-mode fiber (SMF). The helical cladding fiber Bragg gratings (HCFBGs) are created by using a femtosecond laser direct writing technology and a quarter-pitch graded index fiber (GIF) is used in front of the HCFBGs to diverge the core mode into fiber cladding. In contrast to the multimode resonance observed in conventional cladding Bragg gratings inscribed by using a femtosecond laser point-by-point (PbP) or line-by-line (LbL) technology, the proposed HCFBGs exhibit stable narrowband single-mode Bragg resonance. An HCFBG with a low peak reflectivity of -50.77 dB and a narrow bandwidth of 0.66 nm was successfully fabricated by using a lateral offset of 45 µm between the HCFBG and the fiber core axis. Moreover, two orthogonal HCFBGs were fabricated in the SMF cladding and used for vector bending sensing. Strong orientation dependence could be seen in omnidirectional bending measurement, exhibiting a maximum bending sensitivity of up to 50.0 pm/m-1, which is comparable to that in a multicore FBG. In addition, both the orientation and amplitude of bending vector could be reconstructed by using the measured Bragg wavelength shifts in two orthogonal HCFBGs. As such, the proposed HCFBGs could be used in many applications, such as structural health monitoring, robotic arms, and medical instruments.

Simultaneous measurement of torsion and strain at high temperature by using a highly birefringent cladding fiber Bragg grating.

We demonstrate the fabrication of a new highly birefringent cladding fiber Bragg grating (Hi-Bi CFBG) consisting of a pair of sawtooth stressors near the fiber core by using a femtosecond laser direct writing technology. The unique sawtooth structure serves as in-fiber stressor and also generates Bragg resonance due to its periodicity. After optimization of laser pulse energy, the Hi-Bi CFBG with a high birefringence of 2.2 × 10-4 and a low peak reflectivity of ∼ -24.5 dB (corresponding to ∼ 0.3%) was successfully fabricated in a conventional single-mode fiber (SMF). And then, a wavelength-division-multiplexed Hi-Bi CFBGs array and an identical Hi-Bi CFBGs array were successfully constructed. Moreover, a simultaneous measurement of torsion and strain at high temperature of 700 °C was realized by using the fabricated Hi-Bi CFBG, in which the torsion can be deduced by monitoring the reflection difference between the two polarization peaks and strain can be detected by measuring polarization peak wavelength. A high torsion sensitivity of up to 80.02 dB/(deg/mm) and a strain sensitivity of 1.06 pm/µÉ› were achieved. As such, the proposed Hi-Bi CFBG can be used as a mechanical sensor in many areas, especially in structural health monitoring at extreme conditions.

Femtosecond laser auto-positioning direct writing of a multicore fiber Bragg grating array for shape sensing.

A multicore fiber Bragg grating (MC-FBG) array shape sensor is a powerful tool for a variety of applications. However, the efficient fabrication of high-quality MC-FBG arrays remains a problem. Here, we report for the first time, to the best of our knowledge, a new method of directly writing FBG arrays in a seven-core fiber (SCF) through the protective coating using femtosecond laser auto-positioning point-by-point technology, which is accomplished by image recognition and micro-displacement compensation. An MC-FBG array consisting of 140 individual FBGs with a grating length of 2 mm was successfully inscribed into seven cores of a 440 mm-long SCF. Each core contained 20 wavelength-division-multiplexed (WDM) FBGs with wavelengths ranging from 1522.11 nm to 1579.28 nm. In other words, the MC-FBG array consisted of 20 WDM nodes with an interval of 2 cm along the fiber, and each node contained seven identical FBGs integrated in parallel into the fiber cross-section. Moreover, the fabricated MC-FBG array exhibited a strong orientation dependence in bend sensing, with a maximum sensitivity of 55.49 pm/m-1. Subsequently, 2D and 3D shape sensing were demonstrated using the fabricated MC-FBG array, with maximum reconstruction errors per unit length of 4.51% and 10.81%, respectively. Hence, the MC-FBG arrays fabricated using the proposed method are useful in many applications, such as posture monitoring, smart robotics, and minimally invasive surgery.

Temperature-insensitive directional transverse load sensor based on dual side-hole fiber Bragg grating.

We propose and demonstrate a temperature-insensitive directional transverse load sensor based on a fiber Bragg grating (FBG) inscribed in a section of dual side-hole fiber (DSHF). The application of transverse load results in an effective change in the refractive index and, consequently, changes in the DSHF birefringence. The directional transverse load response of the fabricated DSH-FBG was studied by monitoring the wavelength separations with transverse load applied in different direction with 15° increments. The load sensitivity exhibited two maxima and two minima in a polar coordinate system, achieving a maximum value of 699 pm/(N/mm) for transverse load applied along the slow axis and a minimum value of 285 pm/(N/mm) for transverse load applied along the fast axis. Subsequently, a finite element analysis (FEA) was conducted to simulate the resulting strain distribution of the DSHF with applied directional transverse load. The temperature response of the DSH-FBG transverse load sensor was also tested, yielding a low sensitivity of 1.5 × 10-2 pm/°C. Hence, the compact size, directional transverse load sensitivity, and temperature insensitivity of this device make it suitable for intelligent transverse load monitoring.

Femtosecond laser point-by-point inscription of an ultra-weak fiber Bragg grating array for distributed high-temperature sensing.

Ultra-weak fiber Bragg grating (UWFBG) arrays are key elements for constructing large-scale quasi-distributed sensing networks for structural health monitoring. Conventional methods for creating UWFBG arrays are based on in-line UV exposure during fiber drawing. However, the UV-induced UWFBG arrays cannot withstand a high temperature above 450 °C. Here, we report for the first time, to the best of our knowledge, a new method for fabricating high-temperature-resistant UWFBG arrays by using a femtosecond laser point-by-point (PbP) technology. UWFBGs with a low peak reflectivity of ∼ - 45 dB (corresponding to ∼ 0.0032%) were successfully fabricated in a conventional single-mode fiber (SMF) by femtosecond laser PbP inscription through fiber coating. Moreover, the influences of grating length, laser pulse energy, and grating order on the UWFBGs were studied, and a grating length of 1 mm, a pulse energy of 29.2 nJ, and a grating order of 120 were used for fabricating the UWFBGs. And then, a long-term high-temperature annealing was carried out, and the results show that the UWFBGs can withstand a high temperature of 1000 °C and have an excellent thermal repeatability with a sensitivity of 18.2 pm/°C at 1000 °C. A UWFBG array consisting of 200 identical UWFBGs was successfully fabricated along a 2 m-long conventional SMF with an interval of 10 mm, and interrogated with an optical frequency domain reflectometer (OFDR). Distributed high-temperature sensing up to 1000 °C was demonstrated by using the fabricated UWFBG array and OFDR demodulation. As such, the proposed femtosecond laser-inscribed UWFBG array is promising for distributed high-temperature sensing in hash environments, such as aerospace vehicles, nuclear plants, and smelting furnaces.

Efficient point-by-point Bragg grating inscription in sapphire fiber using femtosecond laser filaments.

Sapphire fiber Bragg gratings (SFBGs) inscribed by using femtosecond laser point-by-point (PbP) technology typically have an extremely low reflectivity due to the limited cross-sectional area of refractive index modulations (RIMs) created in sapphire fiber. Hence, we propose and experimentally demonstrate a filamentation process for fabricating PbP SFBGs. This approach provides an efficient method for producing SFBGs at various Bragg wavelengths with a higher reflectivity, since the filament tracks could enlarge the cross-sectional area of RIMs. The influences of the pulse energy and the focal depth on the generation and morphology of the filament tracks were studied, and after optimizing these parameters, high-quality filament tracks with a length of 90 µm and a width of 1.4 µm were produced into sapphire fiber with a diameter of 100 µm. These filament tracks were precisely assembled in sapphire fiber, generating an SFBG with a reflectivity of 2.3%. The total fabrication time for this SFBG only requires ${\sim}{1.1}\;{\rm s}$. Subsequently, a wavelength-division-multiplexed (WDM) SFBG array consisting of five SFBGs was efficiently constructed. Moreover, the high-temperature response of the SFBG array was investigated and the experimental results showed that the SFBG array can withstand a high temperature of 1600°C. Such a WDM SFBG array could serve as quasi-distributed high-temperature sensor which will be promising in many areas, i.e., metallurgical, chemical, and aviation industries.

Femtosecond laser line-by-line inscription of apodized fiber Bragg gratings.

The reflection spectra of conventional fiber Bragg gratings (FBGs) with uniform index modulation profiles typically have strong sidelobes, which hamper the performance of FBG-based optical filters, fiber lasers, and sensors. Here, we propose and demonstrate a femtosecond laser line-by-line (LbL) scanning technique for fabricating apodized FBGs with suppressed sidelobes. This approach can flexibly achieve various apodized modulation profiles via precise control over the length and/or transverse position of each laser-inscribed index modification track. We theoretically and experimentally studied the influences of the apodization function on the side-mode suppression ratio (SMSR) in the fabricated apodized FBG, and the results show that a maximum SMSR of 20.6 dB was achieved in a Gaussian-apodized FBG. Subsequently, we used this method to fabricate various apodized FBGs, and the SMSRs in these FBGs were reduced effectively. Specifically, a dense-wavelength-division-multiplexed Gaussian-apodized FBG array with a wavelength interval of 1.50 nm was successfully fabricated, and the SMSR in such an array is 14 dB. Moreover, a Gaussian-apodized phase-shifted FBG and chirped FBG were also demonstrated with a high SMSR of 14 and 16 dB, respectively. Therefore, such an apodization method based on a modified femtosecond laser LbL scanning technique is an effective and flexible way to fabricate various FBGs with high SMSRs, which is promising to improve the performance of optical filters, fiber lasers, and sensors.

Organophosphonate-Functionalized Telluromolybdate Containing a [TeMo10O37]10- Building Block and Its Catalytic Efficiency for Knoevenagel Condensation.

A novel organodiphosphonate-based telluromolybdate cluster, (NH4)6Na3H13[TeMo10O37(CoMo2O6L)4]·11H2O [1; L = (O3P)2C(O)(CH2)3NH2], has been successfully synthesized by a simple one-pot aqueous reaction. Intriguingly, the [TeMo10O37]10- subunit with tetrahedral geometry of TeO4 is observed in the organophosphonate-functionalized polyoxometalates for the first time. Compound 1 was prepared in a buffer solution (pH = 5.5) with alendronic acid (Ale) and (NH4)6Mo7O24·4H2O as raw materials. The polyanion [TeMo10O37(CoMo2O6L)4]22- was constructed from four {Mo2O6L} subunits encapsulating an interesting Te-Mo heterometal subunit [TeMo10O37]10- through four CoO6 octahedra and has been fully characterized by routine techniques. In addition, compound 1, as a heterogeneous catalyst, shows good conversion (92%) and high selectivity (99%) for Knoevenagel condensation reaction.

Polyoxometalate-Incorporated Framework as a Heterogeneous Catalyst for Selective Oxidation of C-H Bonds of Alkylbenzenes.

Developing new catalysts for highly efficient and selective oxidation of saturated C-H bonds is significant due to their thermodynamic strength. Via incorporation of PW12O403-, pyridine-2,5-dicarboxylic acids (pydc), and Fe(III) ions into one framework, a new polyoxometalate-based metal-organic framework, [HFe4O2(H2O)4(pydc)3PW12O40]·10.5H2O (FeW-PYDC), was successfully prepared by a hydrothermal method. Interestingly, FeW-PYDC features a three-dimensional porous structure with {Fe4O2} interconnecting with PW12O403- units. FeW-PYDC displayed excellent performance in the selective oxidation of C-H bonds of alkylbenzenes with high conversion (95.7%) and selectivity (96.6%). As an effective heterogeneous catalyst, FeW-PYDC demonstrates good reusability and structural stability.

A Copper-Containing Polyoxometalate-Based Metal-Organic Framework as an Efficient Catalyst for Selective Catalytic Oxidation of Alkylbenzenes.

A copper-containing polyoxometalate-based metal-organic framework (POMOF), CuI12Cl2(trz)8[HPW12O40] (HENU-7, HENU = Henan University; trz = 1,2,4-triazole), has been successfully synthesized and well-characterized. In addition, the excellent catalytic ability of HENU-7 has been proved by the selective oxidation of diphenylmethane. Under the optimal conditions, the diphenylmethane conversion obtained over HENU-7 is 96%, while the selectivity to benzophenone is 99%, which outperforms most noble-metal-free POM-based catalysts. Moreover, HENU-7 is stable to reuse for five runs without an obvious loss in activity and also can catalyze the oxidation of different benzylic C-H with satisfactory conversions and selectivities, which implied the significant catalytic activity and recyclability.

Intensity-modulated bend sensor by using a twin core fiber: theoretical and experimental studies.

A new optical fiber bend sensor is proposed and demonstrated based on a sandwich structure created by splicing a segment of twin core fiber (TCF) between two segments of single mode fibers (SMFs). One core of the TCF is aligned with the cores of two segments of SMFs. An incident beam is directed into the TCF by the lead-in SMF. Light couples back and forth between two cores. The bend sensing performance of the sensor is investigated by intensity-modulated method. The intensity of the operation wavelength is modulated by the change of refractive index and geometrical deformation in the bent TCF. Experimental results show such a bend sensor achieves sensitivity of +0.671 /m-1 and resolution of 0.003 m-1 in the range of 0 to 1.25 m-1. In addition, the sensitivity and bend measurement range can be flexibly adjusted through selection of the length of TCF and sensing configuration. As such, the proposed sensor can be further developed for large or small bend ranges measurement.

36-Nuclearity Organophosphonate-Functionalized Polyoxomolybdates: Synthesis, Characterization and Selective Catalytic Oxidation of Sulfides.

The crown-shaped 36-molybdate cluster organophosphonate-functionalized polyoxomolybdates with the highest nuclearity in organophosphonate-based polyoxometalate chemistry, (NH4 )19 Na7 H10 [Cu(H2 O)TeMo6 O21 {N(CH2 PO3 )3 }]6 ⋅31 H2 O, has been reported for the first time. The synthesized 36-molybdate cluster was characterized by routine techniques and tested as a heterogeneous catalyst for selective oxidation of sulfides with impressive catalytic and selective performances after heat treatment. High efficiency (TON=15333) was achieved in the selective oxidation of sulfides to sulfoxides, caused by the synergic effect between copper and polyoxomolybdates and the generation of the cuprous species during the heat treatment.

Synthesis and Characterization of a Crown-Shaped 36-Molybdate Cluster and Application in Catalyzing Knoevenagel Condensation.

A novel crown-shaped 36-molybdate cluster with organophosphonate-functionalized polyoxomolybdates, (NH4)17Na7H12[Co(H2O)TeMo6O21{N(CH2PO3)3}]6·42H2O, has been successfully synthesized and well-characterized. It owns the highest nuclearity in the family of organophosphonate-based polyoxometalates reported so far. Furthermore, for the first time in the field, we illustrated that polyoxomolybdate could work as an effective heterogeneous catalyst for the Knoevenagel condensation reaction with high TOF (7714 h-1) and good recyclability. Impressively, the catalytic performance of 1 was also tested successfully in a large scale (∼10 g) reaction, where 89% of reaction yield and 3216 of TON were afforded.