Chemotherapy is a major method to treat breast cancer. However, the multidrug resistance of cancer, the low tumor accumulation of anticancer drugs, and the serious side effects result in the unsatisfactory therapeutic outcomes of chemotherapy. Collaborative therapy containing chemotherapy, hunger therapy, chemodynamic therapy and photothermal therapy could be a promising way to efficiently conduct tumor combination therapy.Chemotherapy is a major method to treat breast cancer. However, the multidrug resistance of cancer, the low tumor accumulation of anticancer drugs, and the serious side effects result in the unsatisfactory therapeutic outcomes of chemotherapy. Collaborative therapy containing chemotherapy, hunger therapy, chemodynamic therapy and photothermal therapy could be a promising way to efficiently conduct tumor combination therapy. In this study, a novel pH/redox responsive ultralarge mesoporous silica-based drug delivery system (denoted as PUGFP) was constructed to synergistically treat breast cancer. Chemotherapeutic agent paclitaxel (PTX) were loaded into the pores of ultra-large mesoporous silica. Glucose oxidase (GOD), tannic acid (TA)/Fe (III) ligand and polydopamine (PDA) were loaded onto the silica as catalyst of glucose oxidation, generator of Fenton reaction and photosensitizer, respectively. PDA absorbs near-infrared light (NIR) and converts it into thermal energy, causing local temperature rise and achieving ablation of tumor cells. The production of Fe (II) induced by glutathione improved the efficiency of the Fenton reaction resulting in significant tumor inhibition. The GOD-induced starvation therapy not only cuts off energy supply but also produces a large amount of hydrogen peroxide to kill tumor cells. The results of cell experiments demonstrated that the cell viability was 11.98

C 34 H 34 CdI 2 N 10 , monoclinic, C 2/ c (no. 15), a = 17.1805(4) Å, b = 12.8107(2) Å, c = 17.6543(4) Å, β = 113.821(3)°, Z = 4, V = 3554.59(15) Å 3 , R gt ( F ) = 0.0447, w R ref ( F 2 ) = 0.1192, T = 293(2)K.

The rational design of electrocatalytic materials based on polyoxometalates is a promising approach for the sensitive electrochemical determination of NO2-. In this study, a novel lanthanide-included arsenomolybdate, formulated as the H4(NH4)2(Him)16[Na(im)]2[Pr0.5Na0.5(H2O)3]2[AsMo10O35]4 & sdot;32H2O (1) (im = imidazole), is obtained through one-pot self-assembly synthesis method. Compound 1 features a ring-shaped framework composed of {AsMo10O35} clusters connected by {Pr0.5Na0.5(H2O)3} and {Na(im)2} units. Furthermore, compound 1 is combined with carboxylated multi-walled carbon nanotubes (CMCNT) to form a 1@CMCNT composite, which is modified onto the glassy carbon electrode (GCE) to construct the 1@CMCNT/GCE. Due to the synergistic effect between the excellent redox capacity of compound 1 and the rapid electron transfer rate of CMCNT, the 1@CMCNT/GCE exhibits outstanding performance for NO2-detection with a sensitivity of 0.5535 mu A & sdot;mu M-1, a detection limit of 0.54 mu M (S/N = 3), as well as good selectivity and stability. Moreover, the 1@CMCNT/GCE is employed to detect NO2-in tap water samples with a desired recovery of 98.30 %-100.24 %. This work provides a new method for the design of a POM-based electrochemical sensing platform for NO2-detection.

In recent years, double dynamic bond-based hydrogels have attracted extensive attention in tumour treatment due to their multiple responses to tumour microenvironment (e.g., pH, GSH, temperature), which significantly improve treatment accuracy and efficacy. By means of dual-dynamic covalent and hydrogen-bonded networks, we designed a multi-responsive hydrogel (HDPCC) which was constructed by oxidised hyaluronic acid (HA-Cys), oxidised β-cyclodextrin including curcumin (OXβ-CD/CUR) and aldehyde functionalized silica loaded with paclitaxel (DMO-CHO/PTX) via disulfide (-S-S-) and imine (-CH=N-) bonds. Systematic characterisation of rheological properties, in vitro drug release behaviour and anti-tumour effect demonstrated that the HDPCC significantly inhibited tumour growth (3.774 ± 0.744) compared with free drugs. This was attributed to HA-Cys targeting of the CD44 receptor, glutathione response, and pH sensitivity in tumour microenvironment. GSH concentrations of 1, 5, and 10 mM have corresponding PTX release of 29.4 %, 31.0 % and 32.7 %, respectively. At 48 h, cumulative PTX release percentages were 22.1 % (pH 7.4), 25.3 % (pH 6.5), and 28.5 % (pH 5.5). DMO-CHO/PTX and OXβ-CD/CUR inclusion complex reinforced the stability of hydrogel skeleton, accompanied by anti-inflammatory CUR effect. Cell viability and animal experiments demonstrated that HDPCC had excellent biocompatibility, high biodegradability, high apoptosis rate (27.7 %), and strong cell inhibitory ability (cell viability was 30.987 ± 2.918). Our findings provide a new strategy for developing intelligent and responsive anti-tumour delivery systems.

The exploitation of photoelectrode materials with high-efficiency utilization of solar light, an outstanding separation property of photogenerated charges and a large surface area is extremely important yet significantly challenging. Herein, a three-dimensional array of reduced TiO2 nanobelts with a disordered surface and abundant oxygen vacancies was successfully constructed for PEC water splitting. As expected, the reduced 3D-TiO2 nanobelt array produced a photocurrent density of 0.96 mA cm-2 at 0.22 V vs. Ag/AgCl with a faradaic efficiency of 100%, corresponding to 2.4 times enhancement compared with that of the pristine 3D-TiO2 nanobelt array. Furthermore, IPCE was improved within both the UV and visible light regions. This enhancement originates primarily from the efficient utilization of UV-visible light as well as the promoted separation and transport of photogenerated charges induced by the cooperative effect of the disordered surface and oxygen vacancies. This research sheds new light on exploiting TiO2 nanobelts for PEC applications.

Background: A novel ultra-large mesoporous silica (ULP-MSN) was designed with the assistant of pore expanding agent potassium borohydride (KBH4). ULP-MSN was used as a drug carrier for loading paclitaxel (PTX), functionalized with glucose oxidase (GOD) and then wrapped by hydroxypropyl methyl cellulose phthalate (HPMCP). Methods: ULP-MSN was synthesized through a hydrothermal process and loaded with PTX, GOD and HPMCP by adsorption method to obtain PTX@ULP-MSN-NH2-GOD-HPMCP. ULP-MSN and PTX@ULP-MSN-NH2-GOD-HPMCP were fully characterized and examined. Results: The ULP-MSNs possessed monodispersed spherical morphology, a specific surface area of 1153.6491 m2/g and a central ultra-large mesopore size of 26 nm, with high loading ratio (40.19 %) and entrapment ratio (90.50 %). Compared with free GOD enzyme, immobilized enzymes have improved temperature stability, acid-base stability, and storage stability. After 10 repeated uses, they still retained a relatively high enzyme activity of 82 %. GOD catalyzed glucose to produce gluconic acid and hydrogen peroxide (H2O2), which expanded the abnormality of the tumor microenvironment (locally reduced pH and promoted poisonous H2O2). Increased acidity accelerated the dissolution of pH-sensitive HPMCP wrapped in the most layer, causing the spatial control of PTX release within tumor cells for chemotherapy. In vitro experiments demonstrated that the maximum cumulative release percentage reached 92 % at pH 6.5. In addition, PTX@ULP-MSN-NH2-GOD-HPMCP was found to have an excellent effect on the cytotoxicity and apoptosis. Conclusion: ULP-MSN synthesized with the assistance of KBH4 was an excellent drug carrier. KBH4 expanded the pores of silica through dissolution and growth of amorphous silica, realizing non surfactant dependent pore expansion path. ULP-MSNs were functionalized with GOD, which achieved cutting off energy supply required for normal growth of cancer cells for starvation therapy. The high drug loading ratio with combined starvation therapy and drug therapy indicated that such a novel type nanosystem provided an effective cancer treatment.

Cu-doped TiO2 film electrodes were synthesized via sol-gel technique and physically characterized. The Cu-doped TiO2 film electrodes was sensitized by tetrakis (4-carboxyphenyl) porphyrin and applied as a photoanode of a photoelectrochemical biofuel cell (PEBFC). The Cu/TiO2-based PEBFCs showed a short-circuit current (Isc) of 75.9 μA, an open-circuit potential (Voc) of 912 mV, a maximum power density (Pmax) of 66.43 μW/cm2 and an overall energy conversion efficiency (η) of 2.16%, respectively. The PEBFCs indicated improved photoelectric performances comparing the TiO2-based PEBFC (Isc: 72.5 μA, Voc: 740 mV, Pmax: 35.34 μW/cm2, η: 1.52%). The Cu/TiO2-based PEBFCs also indicated a higher incident photon-to-collected electron conversion efficiency (IPCE), which was probably due that the doped copper reduced the band gap of a wide-gap TiO2 semiconductor as shown by ab initio band calculation. And the Cu/TiO2-based PEBFC could provide long electron lifetime and decrease electron-hole pair recombination rate, which was responsible for the better performance in the Cu/TiO2-based PEBFC than in the TiO2-based PEBFC.

Photoluminescence enhancement provides an effective way to improve the performance of quantum dots. In this study, lead(II) determination was demonstrated based on phosphorescence enhancement using 1-thioglycerol-capped Mn-doped ZnS quantum dots. Under the optimized conditions, good linear correlations were obtained for Pb2+ from 10.00 to 5000 nM and 0.05000 to 100.0 mM with correlation coefficients of 0.9997 and 0.9979 and a detection limit of 2.56 nM. The method demonstrates good linearity and selectivity, suitable sensitivity, easy operation, and the determination of Pb2+ in Chinese herbal medicine.

C 32 H 32 CdN 10 OCl 2 , monoclinic, C 2/ c (no. 15), a = 28.820(3) Å, b = 13.1075(2) Å, c = 16.7266(19) Å, β = 149.29(3)°, Z = 4, V = 3226.9(15) Å 3 , R gt ( F ) = 0.0341, wR ref ( F 2 ) = 0.0893, T = 293(2) K.

Mesoporous silica, as a drug carrier, has become the new research focus in the field of nanodrug delivery system in recent years. In this study, Mn-doped mesoporous silicas are synthesized by template and in-situ doping method and physically characterized. The drug-loading performance of silica and its impact on drug release are studied. The Mn-doped mesoporous silicas show dendritic morphology (MDMS) with a loose wrinkle structure on the surface and a large number of pores. MDMS is used as a carrier to solve the problem of low water solubility of paclitaxel. In order to avoid leakage during drug transportation, the surface of Mn-doped mesoporous silica loaded with paclitaxel is coated with N-succinyl chitosan to construct a new type of nanodrug delivery system (MDMS-PTX-NSC). Compared to MDMS, MDMS-PTX-NSC shows an increase in particle size and smooth surface. The dissolution characteristics of manganese ions and swelling behavior of N-succinyl chitosan make MDMS-PTX-NSC delivery system exhibit a good pH-responsive release. And MDMS-PTX-NSC release curve can be well fitted by Ritger-Peppas equation. The cytotoxicity test shows that the MDMS-PTX-NSC has significant biocompatibility and enhanced cytotoxicity, which reveals that the MDMS-PTX-NSC is a promising nanodrug delivery system.

Carcinoembryonic Antigen (CEA), an acidic glycoprotein with human embryonic antigen properties, is found on the surface of cancer cells that have differentiated from endodermal cells. This paper presents a label-free electrochemical immunoassay for the dual amplification detection of CEA using gold nanoparticles loaded with polypyrrole polydopamine (Au/PPy-PDA) and polymerized polycaprolactone (Ng-PCL) prepared by ringopening polymerization (ROP). First, the composite Au/PPy-PDA was adhered to the electrode surface. Then, gold nanoparticles form a Au-S bond with the sulfhydryl group in Apt1 to secure it on the electrode surface. Subsequently, the non-specific binding sites on the electrodes surface are closed by bovine serum albumin (BSA). Next, CEA is dropped onto the electrode surface, which is immobilized by antigen-antibody specific recognition, and the carboxyl-functionalized Apt2 forms a "sandwich structure" of antibody-antigen-antibody by specific recognition. Polymeric Ng-PCL is adhered to the electrode surface, leading to an increase in the electrochemical impedance signal, resulting in a complete chain of signal analysis. Finally, the response signal is detected by electrochemical impedance spectroscopy (EIS). Under optimal experimental conditions, the method has the advantages of high sensitivity and wide linear range (1 pg mL(-1)similar to 100 ng mL(-1)), and the lower limit of detection (LOD) is 0.234 pg mL(-1). And it has the same high sensitivity, selectivity and interference resistance for the real samples detection. Thus, it provides a new way of thinking about biomedical and clinical diagnosis.

C11H12CdN6Cl2, triclinic, P1‾ $P\overline{1}$ (no. 2), a = 6.8644(8) Å, b = 10.4577(8) Å, c = 10.6304(12) Å, α = 112.218(9)°, β = 94.638(9)°, γ = 93.289(8)°, Z = 2, V = 700.93(13) Å3, R gt(F) = 0.0427, wR ref(F 2) = 0.1137, T = 293(2) K.

The catalytic ability of nanozymes has become an enzymology hotspot in the field of application. Most nanozymes were characterized to simultaneously have oxidase-like and peroxidase-like activities, but the practical application often focuses on certain activity; other complex activities may cause interference. The peroxidase-like activity (POD-like activity) of nanozymes have been widely used in the colorimetric detection of H2O2 or substances producing H2O2 as an intermediate, such as the detection of small biological molecules with the oxidative reaction of a chromogenic reagent in the presence of POD-like nanozymes. In this work, we used polydopamine (PDA) as the surface coating of Cu-CeO2 nanosheets (PDA@ Cu-CeO2), which enhanced peroxidase-like activity while inhibiting their oxidase-like activity, providing a feasible method for the sensitive determination of cholesterol by integrating visual colorimetric detection and a smartphone application as a readout. The absorbance intensity and RGB values displayed a linear range on cholesterol from 0.05 to 1.2 mM with the LOD (limit of detection) of 42.7 and 99.4 μM. In addition, the method is expected to apply in detecting cholesterol in human serum with acceptable accuracy.

C13H15CdN5Cl2, monoclinic, P21/c (no. 14), a = 11.5514(4) Å, b = 16.7843(5) Å, c = 8.9691(3) Å, β = 101.927(3)∘, Z = 4, V = 1701.41(10) Å3, Rgt(F) = 0.0379, wRref(F2) = 0.1020, T = 293(2) K.

C9H8AgN7O3, monoclinic, P21/c (no. 14), a = 8.3179(3) Å, b = 16.6800(5) Å, c = 9.0138(3) Å, β = 103.839(4)°, Z = 4, V = 1214.30(7) Å3, R gt(F) = 0.0423, wR ref(F 2) = 0.1065, T = 293(2) K.

This work describes the preparation of manganese-doped mesoporous silica nanospheres via an in situ doping method. The results of scanning electron microscopy and N 2 adsorption demonstrate that mesoporous silica possesses a spherical shape, a highly porous structure, a large specific surface area of 922.21 m 2 g −1 , and a pore volume of 0.257 cm 3 g −1 . The mesoporous silica nanocarrier is loaded with doxorubicin, and carboxymethyl chitosan encapsulation is performed to prevent doxorubicin leakage. The easy release characteristics of manganese under acidic conditions and the swelling properties of carboxymethyl chitosan endow the drug-loading system with an excellent pH/responsive release property. A cytotoxicity test shows that mesoporous silica nanospheres–doxorubicin–carboxymethyl chitosan had significant biocompatibility and enhanced cytotoxicity, thus revealing mesoporous silica nanospheres–doxorubicin–carboxymethyl chitosan as a promising delivery system.

Two new coordination polymers (CPs) [Cd(mbmb)I-2](n) (1) and {[Cd-2(mbmb)(3)I-2 (SCN)(2)]center dot 0.25(H2O)}(n) (2) have been synthesized with 1-[(2-methyl-1H-benzoimidazol-1-yl)methyl]-1H-benzotriazole (mbmb), and structurally characterized by X-ray single crystal diffraction analysis, elemental analysis, 1H -NMR spectra and IR spectra. The X-ray analysis reveals that both polymers 1-2 crystallize in the triclinic space group P-1. Polymer 1 displays 1D chain structure and further connected through two different intermolecular pi...pi stacking interactions to form a 2D network. Polymer 2 possesses a 2D layer network, which is further extended into more stable 3D architecture. Moreover, polymers 1-2 were examined for photo-catalytic degradation activities, and the result shows that they both present outstanding photocatalytic activities for the degradation of MB and RhB with remarkable efficiencies. For MB, the degradation effi-ciencies are 96.12% (1) and 95.59% (2); for RhB, the degradation efficiencies are 97.14% (1) and 94.51% (2). Polymer 1 shows higher photocatalytic performance in the degradation of MB and RhB. (C) 2022 Elsevier B.V. All rights reserved.

The biodegradability of inorganic nanocarriers is one of the most critical issues in their further clinical translations. In this work, a manganese-doped approach was developed to endow inorganic mesoporous silica (SiO2) nanospheres with pH-sensitive biodegradation. Manganese-doped mesoporous silica nanospheres (MMS) were prepared by in-situ doping method, with a particle diameter of 160–175 nm and pore diameter of 3–5[Formula: see text]nm by characterization of N2 adsorption method, powder X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectrum, field emission scanning electron microscope and transmission electron microscope techniques. Quercetin was used as the model drug to load, and MMS loaded with quercetin (MMS–QUE) was surface-modified using a carboxymethyl chitosan (MMS–QUE–CMCS) to prevent quercetin leakage. Based on the dissolution characteristics of manganese ions and the swelling behavior of carboxymethyl chitosan, the MMS–QUE–CMCS could be degraded in response to acid. The MMS–QUE–CMCS delivery system exhibited a good pH-responsive release. The cytotoxicity test showed that the MMS–QUE–CMCS had a significant biocompatibility and an enhanced cytotoxicity, thus revealing that the MMS–QUE–CMCS was a promising delivery system.

The rational design of crystalline materials coupled with polyoxometalate as electrocatalyst is an effective strategy for the sensitive electrochemical detection of H2O2. Here, a novel organic-inorganic hybrid complex [NH4](4)[Cu(pic)(2)](3)[Mo8O26] (1) (Hpic = 2-picolinic acid) was synthesized via in situ self -assembly synthesis method and fully characterized. Structural analysis reveals that compound 1 adopts a two-dimensional (2D) layered structure based on the 1D {Mo8O26Cu(pic)(2) }n chains linked with the {Cu-2(pic)(4 )}n polymers via Cu-O bridge. The morphology of 1 features a columnar construct, smooth sur-face and sharp fringes with an average size of < 50 mu m. Electrochemical studies reveal that compound 1 exhibits the multi-electron redox processes ascribed to MoVI centers, and has good electrocatalytic activity for H2O2 reduction. By utilizing compound 1 as electrode material, the designed electrode shows excellent electrochemical performance for H2O2 detection, including a wide linear range (20-220 mu M), high sensitivity of 0.027 mu A.mu M-1 and a low detection limit of 3.34 mu M, as well as good stability and reproducibility. (C) 2022 Elsevier B.V. All rights reserved.

This work describes the preparation of manganese-doped mesoporous silica nanospheres via an in situ doping method. The results of scanning electron microscopy and N 2 adsorption demonstrate that mesoporous silica possesses a spherical shape, a highly porous structure, a large specific surface area of 922.21 m 2 g −1 , and a pore volume of 0.257 cm 3 g −1 . The mesoporous silica nanocarrier is loaded with doxorubicin, and carboxymethyl chitosan encapsulation is performed to prevent doxorubicin leakage. The easy release characteristics of manganese under acidic conditions and the swelling properties of carboxymethyl chitosan endow the drug-loading system with an excellent pH/responsive release property. A cytotoxicity test shows that mesoporous silica nanospheres–doxorubicin–carboxymethyl chitosan had significant biocompatibility and enhanced cytotoxicity, thus revealing mesoporous silica nanospheres–doxorubicin–carboxymethyl chitosan as a promising delivery system. Keywords carboxymethyl chitosan , doxorubicin , drug-loading system , mesoporous silica , nanosphere