Crystal structure of a samarium(III) nitrate chain cross-linked by a bis-carbamoyl-methyl-phosphine oxide ligand.

In the title compound poly[aqua-bis-(µ-nitrato-κ(4) O,O':O,O'')tetra-kis-(nitrato-κ(2) O,O'){µ4-tetra-ethyl [(ethane-1,2-diyl)bis(aza-nedi-yl)bis-(2-oxo-ethane-2,1-di-yl)]di-phospho-nate-κ(2) O,O'}disamarium(III)], [Sm2(NO3)6(C14H30N2O8P2)(H2O)] n , a 12-coordinate Sm(III) and a nine-coordinate Sm(III) cation are alternately linked via shared bis-bidentate nitrate anions into a corrugated chain extending parallel to the a axis. The nine-coordinate Sm(III) atom of this chain is also chelated by a bidentate, yet flexible, carbamoyl-methyl-phoshine oxide (CMPO) ligand and bears one water mol-ecule. This water mol-ecule is hydrogen bonded to nitrate groups bonded to the 12-coordinate Sm(III) cation. The CMPO ligand, which lies about an inversion center, links neighboring chains along the c axis, forming sheets parallel to the ac plane. Hydrogen bonds between the amide NH group and metal-bound nitrate anions are also present in these sheets. The sheets are packed along the b axis through only van der Waals inter-actions.

Metal-organic polymer enables efficient organic photoelectrochemical transistor biosensing.

The field of organic photoelectrochemical transistor (OPECT) is newly emerged, with increasing efforts attempting to utilize its properties in biological sensing. Advanced materials with new physicochemical properties have proven important to this end. Herein, we report a metal-organic polymers-gated OPECT biosensing exemplified by CuⅠ-arylacetylide polymers (CuAs)-modulated poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) channel. Both the photoelectrochemical properties and gating capability of CuAs are explored and optimized for high-efficacy photogating. Morever, based on its inherent structure, the specific reaction between CuAs and sulfur ions (S2-) is revealed and S2--mediated microRNA-21 detection is realized by linking with nucleic acid amplification and alkaline phosphatase catalytic chemistry. This work introduces metal-organic polymers as gating materials for OPECT biosensing.

In-situ dynamic catalysis electrode electrolyte interphase enabling Mg2+ insertion in 2D metal-organic polymer for high-capacity and long-lifespan magnesium batteries.

Rechargeable magnesium battery is regarded as the promising candidate for the next generation of high-specific-energy storage systems. Nevertheless, issues related to severe Mg-Cl dissociation at the electrolyte-electrode interface impede the insertion of Mg2+ into most materials, leading to severe polarization and low utilization of Mg-storage electrodes. In this study, a metal-organic polymer (MOP) Ni-TABQ (Ni-coordinated tetramino-benzoquinone) with superior surface catalytic activity is proposed to achieve the high-capacity Mg-MOP battery. The layered Ni-TABQ cathode, featuring a unique 2D π-d linear conjugated structure, effectively reduces the dissociation energy of MgxCly clusters at the Janus interface, thereby facilitating Mg2+ insertion. Due to the high utilization of active sites, Ni-TABQ achieves high capacities of 410 mAh/g at 200 mA g-1, attributable to a four-electron redox process involving two redox centers, benzoid carbonyls, and imines. This research highlights the importance of surface electrochemical processes in rechargeable magnesium batteries and paves the way for future development in multivalent metal-ion batteries.

Revealing the enhanced photoelectrochemical water oxidation activity of Fe-based metal-organic polymer-modified BiVO4 photoanode.

Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (ksr) and enhance the charge transfer rate constant (ktr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes.

Stretchable Sensors: Novel Human Motion Monitoring Wearables.

A human body monitoring system remains a significant focus, and to address the challenges in wearable sensors, a nanotechnology-enhanced strategy is proposed for designing stretchable metal-organic polymer nanocomposites. The nanocomposite comprises reduced graphene oxide (rGO) and in-situ generated silver nanoparticles (AgNPs) within elastic electrospun polystyrene-butadiene-polystyrene (SBS) fibers. The resulting Sandwich Structure Piezoresistive Woven Nanofabric (SSPWN) is a tactile-sensitive wearable sensor with remarkable performance. It exhibits a rapid response time (less than three milliseconds) and high reproducible stability over 5500 cycles. The nanocomposite also demonstrates exceptional thermal stability due to effective connections between rGO and AgNPs, making it suitable for wearable electronic applications. Furthermore, the SSPWN is successfully applied to human motion monitoring, including various areas of the hand and RGB sensing shoes for foot motion monitoring. This nanotechnology-enhanced strategy shows promising potential for intelligent healthcare, health monitoring, gait detection, and analysis, offering exciting prospects for future wearable electronic products.

Highly efficient and selective recovery of Au(III) by a new metal-organic polymer.

A metal-organic polymer with high water stability was successfully developed to efficiently recover Au(III) from aqueous solutions. This material shows excellent performance for the adsorption of Au(III). Nearly 100% of Au(III) could be removed with fast adsorption rate at low concentration solutions, and the maximum adsorption capacity of 1317 mg/g could be achieved. Significantly, the material shows encouraging selectivity toward Au(III) in the presence of competitive ions such as Cu(II), Ni(II), Zn(II), and Cd(II) in both batch and flow-through experiments. Additionally, the material could be regenerated effectively by thiourea with desorption ratio of almost 100%, and exhibits excellent reutilization without significant loss of adsorption capacity. The adsorption mechanism could be attributed to reduce Au(III) to Au(0) by the material. The material still exhibits excellent adsorption performance toward Au in real electronic waste (e-waste) solutions, providing a promising adsorbent for recycle of Au(III) from e-waste.

A facile and selective approach for enrichment of l-cysteine in human plasma sample based on zinc organic polymer: Optimization by response surface methodology.

In this research, a facile and selective method was described to extract l-cysteine (l-Cys), an essential α-amino acid for anti-ageing playing an important role in human health, from human blood plasma sample. The importance of this research was the mild and time-consuming synthesis of zinc organic polymer (Zn-MOP) as an adsorbent and evaluation of its ability for efficient enrichment of l-Cys by ultrasound-assisted dispersive micro solid-phase extraction (UA-DMSPE) method. The structure of Zn-MOP was investigated by FT-IR, XRD and SEM. Analysis of variance (ANOVA) was applied for the experimental data to reach the best optimum conditions. The quantification of l-Cys was carried out by high performance liquid chromatography with UV detection set at λ=230nm. The calibration graph showed reasonable linear responses towards l-Cys concentrations in the range of 4.0-1000µg/L (r2=0.999) with low limit of detection (0.76µg/L, S/N=3) and RSD≤2.18 (n=3). The results revealed the applicability and high performance of this novel strategy in detecting trace l-Cys by Zn-MOP in complicated matrices.

Mild synthesis of a Zn(II) metal organic polymer and its hybrid with activated carbon: Application as antibacterial agent and in water treatment by using sonochemistry: Optimization, kinetic and isotherm study.

In this work, a room temperature and short method (30min) for synthesis of nanosized rod-like metal organic polymer (MOP) has been described. Reaction of 1,4-phenylenedioxy diacetic acid with zinc salt leads to the formation of [Zn(C10H8O6)(H2O)4]n and subsequently was loaded on activated carbon following sonication and structurally characterized by FTIR, SEM, EDX and XRD analysis. The combination of this new composite with sonication was applied for rapid and efficient adsorption of Bromocresol Purple (BCP). Effects of initial BCP concentration, mass of adsorbent and sonication time on response were investigated and optimized by central composite design (CCD). Analysis of variation (ANOVA) was adapted to experimental data to find best optimum conditions which was set at 15.22mgL-1, 2.41min, 0.02g and 0.009mg for initial BCP concentration, sonication time and adsorbent mass, respectively. Conduction of similar experiments at specified condition permit achievement of 98.69% removal percentage. 1,4-phenylenedioxy diacetic acid and Zn(NO3)2.4H2O which have applied for preparation of MOP are interesting antibacterial properties and accordingly MOP was screened in vitro for their antibacterial actively against Proteus vulgaris bacteria and experimental results reveal this MOP was able to inhibit growth of the tested bacteria. The experimental data were best fitted by pseudo-second order and Langmuir for kinetic model and the adsorption equilibrium isotherm, respectively.

Sonochemical synthesis and characterization of microrod to nanoparticle of new mixed-ligand zinc(II) fumarate metal-organic polymer.

Micro and nano-structures of a new mixed-ligand Zn(II) fumarate metal-organic polymer, {[Zn(tptz)(fum)].DMF}n (1), (tptz=2,4,6-tris(2-pyridyl)-s-triazine, fum=fumarate, DMF=N,N-dimethylforamide), were synthesized by sonochemical method. These new micro and nano-structures were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), IR spectroscopy and elemental analyses. Compound 1 was structurally characterized by single-crystal X-ray diffraction and consists of the primary unit of [Zn(tptz)(fum)]. Self assembly between the units of [Zn(tptz)(fum)] from Zn-O bonds results in the formation of a one-dimensional zinc(II) coordination polymer. The ZnII-ion in compound 1 has ZnO2N3 coordination sphere with a trigonal bipyramidal molecular geometry. Compound 1 was synthesized by ultrasound irradiation under different concentrations and times. The microrods structure of compound 1 with increasing of concentration and ultrasound radiation time were synthesized as nanoparticles structure successfully. So ultrasound radiation change morphology from microrods to nanoparticles.

Crystal structure of the one-dimensional metal-organic polymer catena-poly[[tris(µ-2,4,6-tri-methyl-benzoato-κ(2) O:O')dizinc]-µ-2,4,6-tri-methyl-benzoato-κ(2) O:O'].

The title complex, [Zn2(C10H11O2)4] n , has a one-dimensional polymeric structure. The asymmetric unit consists of two zinc atoms bridged by three 2,4,6-tri-methyl-benzoate anions and one bidentate bridging 2,4,6-trimethylbenzoate anion. The [Zn2(C9H11CO2)3] cluster units are inter-molecularly linked to form a one-dimensional polymer, which propagates in the direction of the crystallographic b axis. The Zn atoms adopt a tetra-hedral geometry. The Zn-O bond lengths in the intra-molecular bridges are slightly shorter than those in the inter-molecular bridges.