In vivo correlation between semi‐quantitative hemodynamic parameters and Ktrans derived from DCE‐MRI of brain tumors

Dynamic contrast‐enhanced (DCE) magnetic resonance imaging (MRI) has become more and more widely applied in cancer diagnosis and treatment follow‐up. Without complicated calculation, a semiquantitative parameter – modified initial area under the curve (mIAUC_c) – was proposed for better correlation with volume transfer constant (K^trans) by computer simulation. In this study, we aim to further investigate the correlation between mIAUC_c and K^trans in clinical. A total of 10 patients with brain tumors participated in this study and images were acquired by using a 3‐Tesla clinical MR scanner. The results showed that mIAUC_c was highly correlated with K^trans with the correlation coefficient of 0.913. Although the ideals of K^trans and mIAUC_c are different, mIAUC_c does the trick for brain tumors evaluations in DCE‐MRI. It reveals that mIAUC_c could be an alternative for physiological condition evaluation in DCE‐MRI. © 2012 Wiley Periodicals, Inc. Int J Imaging Syst Technol, 22, 132–136, 2012     

Core–Shell–Satellite Nanomaces as Remotely Controlled Self‐Fueling Fenton Reagents for Imaging‐Guided Triple‐Negative Breast Cancer‐Specific Therapy

Triple‐negative breast cancer (TNBC) is highly aggressive and insensitive to conventional targeted therapies, resulting in poor therapeutic outcomes. Recent studies have shown that abnormal iron metabolism is observed in TNBC, suggesting an opportunity for TNBC treatment via the iron‐dependent Fenton reaction. Nevertheless, the efficiency of current Fenton reagents is largely restricted by the lack of specificity and low intracellular H₂O₂ level of cancer cells. Herein, core–shell–satellite nanomaces (Au @ MSN@IONP) are fabricated, as near‐infrared (NIR) light‐triggered self‐fueling Fenton reagents for the amplified Fenton reaction inside TNBC cells. Specifically, the Au nanorod core can convert NIR light energy into heat to induce massive production of intracellular H₂O₂, thereby the surface‐decorated iron oxide nanoparticles (IONP) are being fueled for robust Fenton reaction. By exploiting the vulnerability of iron efflux in TNBC cells, such a self‐fueling Fenton reaction leads to highly specific anti‐TNBC efficacy with minimal cytotoxicity to normal cells. The PI3K/Akt/FoxO axis, intimately involved in the redox regulation and survival of TNBC, is demonstrated to be inhibited after the treatment. Consequently, precise in vivo orthotopic TNBC ablation is achieved under the guidance of IONP‐enhanced magnetic resonance imaging. The results demonstrate the proof‐of‐concept of NIR‐light‐triggered self‐fueling Fenton reagents against TNBC with low ferroportin levels.     

Efficient Polysulfide‐Based Nanotheranostics for Triple‐Negative Breast Cancer: Ratiometric Photoacoustics Monitored Tumor Microenvironment‐Initiated H2S Therapy

The incidence of triple‐negative breast cancer (TNBC) is difficult to predict, and TNBC has a high mortality rate among women worldwide. In this study, a theranostics approach is developed for TNBC with ratiometric photoacoustic monitored thiol‐initiated hydrogen sulfide (H₂S) therapy. The ratiometric photoacoustic (PA) probe (CY) with a thiol‐initiated H₂S donor (PSD) to form a nanosystem (CY‐PSD nanoparticles) is integrated. In this theranostics approach, H₂S generated from PSD is sensed by CY based on ratiometric PA signals, which simultaneously pinpoints the tumor region. Additionally, H₂S is cytotoxic toward TNBC cells (MDA‐MB 231), showing a tumor inhibition rate of 63%. To further verify its pharmacological mechanism, proteomics analysis is performed on tumors treated with CY‐PSD nanoparticles. Cells are killed by the significant mitochondrial dysfunction via supressed energy supply and apoptosis initiation. Besides, the observed inhibition of oxidative stress also generates the cytotoxicity. Significant Kyoto Encyclopedia of Genes Genomes pathways related to TNBC are found to be inhibited. This H₂S theranostics approach updates the current anticancer therapies which brings promise for women suffering malignant breast cancer.     

Room‐Temperature Solution‐Synthesized p‐Type Copper(I) Iodide Semiconductors for Transparent Thin‐Film Transistors and Complementary Electronics

Here, room‐temperature solution‐processed inorganic p‐type copper iodide (CuI) thin‐film transistors (TFTs) are reported for the first time. The spin‐coated 5 nm thick CuI film has average hole mobility (µ_FE) of 0.44 cm² V^?1 s^?1 and on/off current ratio of 5 × 10². Furthermore, µ_FE increases to 1.93 cm² V^?1 s^?1 and operating voltage significantly reduces from 60 to 5 V by using a high permittivity ZrO₂ dielectric layer replacing traditional SiO₂. Transparent complementary inverters composed of p‐type CuI and n‐type indium gallium zinc oxide TFTs are demonstrated with clear inverting characteristics and voltage gain over 4. These outcomes provide effective approaches for solution‐processed inorganic p‐type semiconductor inks and related electronics.     

Is GSH Chelated Pt Molecule Inactive in Anti‐Cancer Treatment? A Case Study of Pt6GS4

Platinum (Pt) drugs are widely used in anti‐cancer treatment although many reports advocated that tumor cells could inactivate Pt drugs via glutathione‐Pt (GSH‐Pt) adducts formation. To date, GSH chelated Pt molecules have not been assessed in cancer treatment because GSH‐Pt adducts are not capable of killing cancer cells, which is widely accepted and well followed. In this report, endogenous biothiol is utilized to precisely synthesize a GSH chelated Pt molecule (Pt₆GS₄). This Pt₆GS₄ molecule can be well taken up by aggressive triple negative breast cancer (TNBC) cells. Subsequently, its metabolites could enter nuclei to interact with DNA, finally the DNA‐Pt complex triggers TNBC cell apoptosis via the p53 pathway. Impressively, high efficacy for anti‐cancer treatment is achieved by Pt₆GS₄ both in vitro and in vivo when compared with traditional first‐line carboplatin in the same dosage. Compared with carboplatin, Pt₆GS₄ keeps tumor bearing mice alive for a longer time and is non‐toxic for the liver and kidneys. This work opens a route to explore polynuclear Pt compound with accurate architecture for enhancing therapeutic effects and reducing systemic toxicity.     

Role of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes

Owing to the capacity boost from oxygen redox activities, Li‐rich cation‐disordered rocksalts (LRCDRS) represent a new class of promising high‐energy Li‐ion battery cathode materials. Redox‐inactive transition‐metal (TM) cations, typically d⁰ TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d⁰ TM (Nb⁵⁺ and Ti⁴⁺) is systematically compared on the redox chemistry of Mn‐based model LRCDRS cathodes, namely Li_1.3Nb_0.3Mn_0.4O₂ (LNMO), Li_1.25Nb_0.15Ti_0.2Mn_0.4O₂ (LNTMO), and Li_1.2Ti_0.4Mn_0.4O₂ (LTMO). Although electrochemically inactive, d⁰ TM serves as a modulator for oxygen redox, with Nb⁵⁺ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X‐ray scattering reveal that Ti⁴⁺ is better in stabilizing the oxidized oxygen anions (O^n?, 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d⁰ TM on degradation mechanism further suggests that proper design of redox‐inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.     

Influence of the Al(Co,Ni) layer on the corrosion resistance of a cobalt based alloy (Mar‐M‐509®)

In the present work, the results of studies on the structure and corrosion resistance of Al(Co, Ni) layer are shown. The diffusion Al(Co, Ni) layer was created on the cobalt alloy Mar‐M‐509 substrate by chemical vapor deposition (CVD) method with aluminum trichloride (AlCl₃) under the hydrogen atmosphere. The scanning electron microscope (SEM) observations and microtomography measurements of layers were performed. Also an analysis of the chemical (energy‐dispersive X‐ray spectroscopy (EDS)) and phase (X‐ray diffraction (XRD)) composition was carried out. By the X‐ray diffraction method (sin² φ) also the residual stresses were calculated in the matrix of the material. The corrosion resistance was tested with impedance and potentiodynamic methods in 0.1 M Na₂SO₄, 0.1 M H₂SO₄ solutions and acidulous 0.1 M NaCl solution (pH = 4.2) at room temperature. The results indicate that the analyzed layer with a thickness of about 14 μm have a similar corrosion resistance compared to the base material – Mar‐M‐509^® cobalt alloy. Only in the strongly acidic environments, the corrosion resistance of the layer is remarkably decreased.     

Improvement of Low‐Temperature zT in a Mg3Sb2–Mg3Bi2 Solid Solution via Mg‐Vapor Annealing

Materials with high zT over a wide temperature range are essential for thermoelectric applications. n‐Type Mg₃Sb₂‐based compounds have been shown to achieve high zT at 700 K, but their performance at low temperatures (<500 K) is compromised due to their highly resistive grain boundaries. Syntheses and optimization processes to mitigate this grain‐boundary effect has been limited due to loss of Mg, which hinders a sample's n‐type dopability. A Mg‐vapor anneal processing step that grows a sample's grain size and preserves its n‐type carrier concentration during annealing is demonstrated. The electrical conductivity and mobility of the samples with large grain size follows a phonon‐scattering‐dominated T^?3/2 trend over a large temperature range, further supporting the conclusion that the temperature‐activated mobility in Mg₃Sb₂‐based materials is caused by resistive grain boundaries. The measured Hall mobility of electrons reaches 170 cm² V^?1 s^?1 in annealed 800 °C sintered Mg_{3 + δ}Sb_1.49Bi_0.5Te_0.01, the highest ever reported for Mg₃Sb₂‐based thermoelectric materials. In particular, a sample with grain size >30 mm has a zT 0.8 at 300 K, which is comparable to commercial thermoelectric materials used at room temperature (n‐type Bi₂Te₃) while reaching zT 1.4 at 700 K, allowing applications over a wider temperature scale.     

Interfacially Engineered High‐Speed Nonvolatile Memories Employing p‐Type Nanoribbons

A novel two‐terminal high‐speed nonvolatile memory device is demonstrated featuring the construction of a quasi‐metal‐insulator‐semiconductor (q‐MIS) architecture. The quasi‐MIS memory takes advantage of an in situ formed amorphous AlO_x interfacial layer sandwiched between p‐type ZnS nanoribbons (p‐ZnSNRs) and a Al electrode. Systematical optimization of the AlO_x interfacial layer enables the resultant memory to show excellent memory characteristics, including a fast programming speed of <100 ns, a high current ON/OFF ratio of ∼10⁸, a long retention time of 6 × 10⁴ s, and good stability over 12 months. In addition, an interface‐state‐induced mechanism is proposed to elucidate in detail the memory characteristic for the quasi‐MIS structure. This work suggests great potential of such quasi‐MIS architecture for high‐performance two‐terminal memory, and more importantly, signifies the importance of interface engineering for the construction of novel functional nano‐devices.     

Large‐Area,Uniform, Aligned Arrays of Na3(VO)2(PO4)2F on Carbon Nanofiber for Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors

Sodium–vanadium fluorophosphate (Na₃V₂O_2x(PO₄)₂F_3?2x, NVPF, 0 ≤ x ≤ 1) is considered to be a promising Na‐storage cathode material due to its high operation potentials (3.6–4 V) and minor volume variation (1.8%) during Na⁺‐intercalation. Research about NVPF is mainly focused on powder‐type samples, while its ordered array architecture is rarely reported. In this work, large‐area and uniform Na₃(VO)₂(PO₄)₂F cuboid arrays are vertically grown on carbon nanofiber (CNF) substrates for the first time. Owing to faster electron/ion transport and larger electrolyte–electrode contact area, the as‐prepared NVPF array electrode exhibits much improved Na‐storage properties compared to its powder counterpart. Importantly, a quasi‐solid‐state sodium‐ion hybrid capacitor (SIHC) is constructed based on the NVPF array as an intercalative battery cathode and porous CNF as a capacitive supercapacitor anode together with the P(VDF‐HFP)‐based polymer electrolyte. This novel hybrid system delivers an attractive energy density of ≈227 W h kg^?1 (based on total mass of two electrodes), and still remains as high as 107 Wh kg^?1 at a high specific power of 4936 W kg^?1, which pushes the energy output of sodium hybrid capacitors toward a new limit. In addition, the growth mechanism of NVPF arrays is investigated in detail.     

High‐Entropy Alloy (HEA)‐Coated Nanolattice Structures and Their Mechanical Properties

Nanolattice structure fabricated by two‐photon lithography (TPL) is a coupling of size‐dependent mechanical properties at micro/nano‐scale with structural geometry responses in wide applications of scalable micro/nano‐manufacturing. In this work, three‐dimensional (3D) polymeric nanolattices are initially fabricated using TPL, then conformably coated with an 80 nm thick high‐entropy alloy (HEA) thin film (CoCrFeNiAl_0.3) via physical vapor deposition (PVD). 3D atomic‐probe tomography (APT) reveals the homogeneous element distribution in the synthesized HEA film deposited on the substrate. Mechanical properties of the obtained composite architectures are investigated via in situ scanning electron microscope (SEM) compression test, as well as finite element method (FEM) at the relevant length scales. The presented HEA‐coated nanolattice encouragingly not only exhibits superior compressive specific strength of ≈0.032 MPa kg^?1 m³ with density well below 1000 kg m^?3, but also shows good compression ductility due to its composite nature. This concept of combining HEA with polymer lattice structures demonstrates the potential of fabricating novel architected metamaterials with tunable mechanical properties.

     

Next‐Generation Narrow‐Band Green‐Emitting RbLi(Li3SiO4)2:Eu2+ Phosphor for Backlight Display Application

The discovery of high efficiency narrow‐band green‐emitting phosphors is a major challenge in backlighting light‐emitting diodes (LEDs). Benefitting from highly condensed and rigid framework structure of UCr₄C₄‐type compounds, a next‐generation narrow green emitter, RbLi(Li₃SiO₄)₂:Eu²⁺ (RLSO:Eu²⁺), has emerged in the oxide‐based family with superior luminescence properties. RLSO:Eu²⁺ phosphor can be efficiently excited by GaN‐based blue LEDs, and shows green emission at 530 nm with a narrow full width at half maximum of 42 nm, and very low thermal quenching (103%@150 °C of the integrated emission intensity at 20 °C), however its chemical stability needs to be improved later. The white LED backlight using optimized RLSO:8%Eu²⁺ phosphor demonstrates a high luminous efficacy of 97.28 lm W^?1 and a wide color gamut (107% National Television System Committee standard (NTSC) in Commission Internationale de L'Eclairage (CIE) 1931 color space), suggesting its great potential for industrial applications as liquid crystal display (LCD) backlighting.     

Locally Trapping the C‐C Chemokine Receptor Type 7 by Gene Delivery Nanoparticle Inhibits Lymphatic Metastasis Prior to Tumor Resection

Triple negative breast cancer (TNBC) is the most aggressive breast cancer subtype. Currently, no targeted treatment is available for TNBC, and the most common clinical therapy is tumor resection, which often promotes metastasis risks. Strong evidence suggests that the lymphatic metastasis is mediated by the C‐C chemokine receptor type 7 (CCR7)/C‐C motif chemokine ligand 21 crosstalk between tumor cells and the lymphatic system. It is hypothesized that CCR7 is a key immune modulator in the tumor microenvironment and the local blockade of CCR7 could effectively inhibit TNBC lymphatic metastasis. Accordingly, a plasmid encoding an antagonistic CCR7 affinity protein‐CCR7 trap is delivered by tumor targeting nanoparticles in a highly metastatic 4T1 TNBC mouse model. Results show that CCR7 traps are transiently expressed, locally disrupt the signaling pathways in the tumor site, and efficiently inhibit TNBC lymphatic metastasis, without inducing immunosuppression as observed in systemic therapies using CCR7 monoclonal antibody. Significantly, upon applying CCR7 trap therapy prior to tumor resection, a 4T1 TNBC mouse model shows good prognosis without any further metastasis and relapse. In addition, CCR7 trap therapy efficiently inhibits the lymphatic metastasis in a B16F10 melanoma mouse model, indicating its great potential for various metastatic diseases treatment.     

Thiazole Imide‐Based All‐Acceptor Homopolymer: Achieving High‐Performance Unipolar Electron Transport in Organic Thin‐Film Transistors

High‐performance unipolar n‐type polymer semiconductors are critical for advancing the field of organic electronics, which relies on the design and synthesis of new electron‐deficient building blocks with good solubilizing capability, favorable geometry, and optimized electrical properties. Herein, two novel imide‐functionalized thiazoles, 5,5′‐bithiazole‐4,4′‐dicarboxyimide (BTzI) and 2,2′‐bithiazolothienyl‐4,4′,10,10′‐tetracarboxydiimide (DTzTI), are successfully synthesized. Single crystal analysis and physicochemical study reveal that DTzTI is an excellent building block for constructing all‐acceptor homopolymers, and the resulting polymer poly(2,2′‐bithiazolothienyl‐4,4′,10,10′‐tetracarboxydiimide) (PDTzTI) exhibits unipolar n‐type transport with a remarkable electron mobility (μ_e) of 1.61 cm² V^?1 s^?1, low off‐currents (I_off) of 10^?10?10^?11 A, and substantial current on/off ratios (I_on/I_off) of 10⁷?10⁸ in organic thin‐film transistors. The all‐acceptor homopolymer shows distinctive advantages over prevailing n‐type donor?acceptor copolymers, which suffer from ambipolar transport with high I_offs > 10^?8 A and small I_on/I_offs < 10⁵. The results demonstrate that the all‐acceptor approach is superior to the donor?acceptor one, which results in unipolar electron transport with more ideal transistor performance characteristics.     

A Dopant Replacement‐Driven Molten Salt Method toward the Synthesis of Sub‐5‐nm‐Sized Ultrathin Nanowires

The high‐temperature molten‐salt method is an important inorganic synthetic route to a wide variety of morphological phenotypes. However, its utility is limited by the fact that it is typically incapable of producing ultrathin (<5 nm diameter) nanowires, which have a crucial role in novel nanotechnology applications. Herein, a rapid molten salt‐based synthesis of sub‐5‐nm‐sized nanowires of hexagonal tungsten oxide (h‐WO₃) that is critically dependent on a substantial proportion of molybdenum (Mo) dopant is described. This dopant‐driven morphological transition in tungsten oxide (WO₃) may be attributable to the collapse of layered structure, followed by nanocluster aggregation, coalescence, and recrystallization to form ultrathin nanowires. Interestingly, due to the structural properties of h‐WO₃, the thus‐formed ultrathin nanowires are demonstrated to be excellent photocatalysts for the production of ammonia (NH₃) from nitrogen (N₂) and water. The ultrathin nanowires exhibit a high photocatalytic NH₃‐production activity with a rate of 370 µmol g^?1 h^?1 and an apparent quantum efficiency of 0.84% at 420 nm, which is more than twice that obtained from the best‐performing Mo‐doped W₁₈O₄₉ nanowire catalysts. It is envisaged that the dopant replacement‐driven synthetic protocol will allow for rapid access to a series of ultrathin nanostructures with intriguing properties and increase potential applications.     

High‐Performance n‐Channel Organic Transistors Using High‐Molecular‐Weight Electron‐Deficient Copolymers and Amine‐Tailed Self‐Assembled Monolayers

While high‐performance p‐type semiconducting polymers are widely reported, their n‐type counterparts are still rare in terms of quantity and quality. Here, an improved Stille polymerization protocol using chlorobenzene as the solvent and palladium(0)/copper(I) as the catalyst is developed to synthesize high‐quality n‐type polymers with number‐average molecular weight up to 10⁵ g mol^?1. Furthermore, by sp²‐nitrogen atoms (sp²‐N) substitution, three new n‐type polymers, namely, pBTTz, pPPT, and pSNT, are synthesized, and the effect of different sp²‐N substitution positions on the device performances is studied for the first time. It is found that the incorporation of sp²‐N into the acceptor units rather than the donor units results in superior crystalline microstructures and higher electron mobilities. Furthermore, an amine‐tailed self‐assembled monolayer (SAM) is smoothly formed on a Si/SiO₂ substrate by a simple spin‐coating technique, which can facilitate the accumulation of electrons and lead to more perfect unipolar n‐type transistor performances. Therefore, a remarkably high unipolar electron mobility up to 5.35 cm² V^?1 s^?1 with a low threshold voltage (≈1 V) and high on/off current ratio of ≈10⁷ is demonstrated for the pSNT‐based devices, which are among the highest values for unipolar n‐type semiconducting polymers.     

Confined Heteropoly Blues in Defected Zr‐MOF (Bottle Around Ship) for High‐Efficiency Oxidative Desulfurization

The Keggin‐type polyoxometalates (POMs) are effective catalysts for oxidative desulfurization (ODS) and confining these POMs in metal–organic frameworks (MOFs) is a promising strategy to improve their performances. Herein, postsynthetic modification of POMs confined in MOFs by adding thiourea creates more unsaturated metal sites as defects, promoting ODS catalytic activity. Additional modification by confining 1‐butyl‐3‐methyl imidazolium POMs in MOFs is performed to obtain higher ODS activity, owing to the affinity between electron‐rich thiophene‐based compounds and electrophilic imidazolium compounds. The ODS catalytic activities of four Zr‐MOF‐based composites (bottle around ship) including phosphomolybdate acid (PMA)/UiO‐66, [Bmim]₃PMo₁₂O₄₀/UiO‐66, PMA/Thiourea/UiO‐66, and [Bmim]₃PMo₁₂O₄₀/Thiourea/UiO‐66 are therefore investigated in detail. In order to explore the catalytic mechanism of these MOF composites, their microstructures and electronic structures are probed by various techniques such as X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared, Raman, scanning electron microscope, transmission electron microscope, BET, X‐ray photoelectron spectroscopy, EPR, UV–vis, NMR spectra, and H₂‐temperature‐programmed reduction. The results reveal that phosphomolybdate blues and imidazolium phosphomolybdate blues with different Mo⁵⁺/Mo⁶⁺ ratios with the Keggin structure are confined in defected UiO‐66 for all four composites. This approach can be applied to design and synthesize other POMs/MOFs composites as efficient catalysts.     

Zn‐Ion Hybrid Micro‐Supercapacitors with Ultrahigh Areal Energy Density and Long‐Term Durability

On‐chip micro‐supercapacitors (MSCs), as promising power candidates for microdevices, typically exhibit high power density, large charge/discharge rates, and long cycling lifetimes. However, as for most reported MSCs, the unsatisfactory areal energy density (<10 µWh cm^?2) still hinders their practical applications. Herein, a new‐type Zn‐ion hybrid MSC with ultrahigh areal energy density and long‐term durability is demonstrated. Benefiting from fast ion adsorption/desorption on the capacitor‐type activated‐carbon cathode and reversible Zn stripping/plating on the battery‐type electrodeposited Zn‐nanosheet anode, the fabricated Zn‐ion hybrid MSCs exhibit remarkable areal capacitance of 1297 mF cm^?2 at 0.16 mA cm^?2 (259.4 F g^?1 at a current density of 0.05 A g^?1), landmark areal energy density (115.4 µWh cm^?2 at 0.16 mW cm^?2), and a superb cycling stability without noticeable decay after 10 000 cycles. This work will inspire the fabrication and development of new high‐performance microenergy devices based on novel device design.     

Twinned Growth of Metal‐Free,Triazine‐Based Photocatalyst Films as Mixed‐Dimensional (2D/3D) van der Waals Heterostructures

Design and synthesis of ordered, metal‐free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed‐dimensional (2D/3D) metal‐free van der Waals (vdW) heterostructures based on triazine (C₃N₃) linkers grow as large area, transparent yellow‐orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E _g,opt = 1.91 eV, E _g,elec = 1.84 eV) and are moderately porous (124 m² g^?1). The material consists of a crystalline 2D phase that is fully sp² hybridized and provides structural stability, and an amorphous, porous phase with mixed sp²–sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one‐pot reaction mixture: unprecedented for metal‐free frameworks and a direct consequence of on‐catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal‐free, light‐induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h^?1 g^?1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of “wet” chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.     

Teilkohärente Ausscheidungen in einer Eisen‐Chrom‐Kohlenstoff‐Legierung

Semicoherent precipitates in a Fe‐Cr‐C alloy Precipitation processes in ferromagnetic materials can be recorded very well by measuring the sensitive coercive field strength. It should be tested, whether also semicoherent precipitates have a sufficient clear interaction with Bloch‐walls. For this purpose the mild‐magnetic alloy X1FeCr25 served. To carry out the evidence sensitively, a method based on differences between H_C^t (heat‐treated state at T = 600…︁700°C) – H_C⁰ (quenched state from high temperature) = Δ H_C was used. A quantitative record of the amount of precipitates (as particle size) is possible by a decomposition parameter Δ H_C/Δ t. Plate‐like β′‐precipitates with planes {100}∥{100} in the α‐Fe solid solution have been proved by transmission electron microscopic investigations; this is the preparation state for the transition into the stable fcc phase M₂₃C₆. As a result, the quantitative electron microscopic proof of the β′‐phase can be supported by magnetic measurements, qualitatively and quantitatively. The estimated values of the activation energy for the process in the 1st maximum of precipitation in X1FeCr25 are higher than for the stable phases as the orthorhombic M₃C or the cubic complex M₆C in other steels and give a hint to the difficult processes related to nucleation as to the transition into M₂₃C₆.