Al Deposition Research Articles

Abstract 12022: Predictors of Mortality in Patients With Biopsy-Proven Cardiac AL Amyloidosis

Introduction: Cardiac involvement occurs in ~50% of patients with light-chain (AL) amyloidosis and conveys a poor prognosis. This study examined the role of histopathologic and echocardiographic parameters in predicting mortality. Methods: Patients with endomyocardial biopsy-proven cardiac AL amyloidosis treated at MD Anderson Cancer Center between 6/2011 and 6/2020 were identified. Stored echocardiographic images were processed for longitudinal strain (global [GLS], apical, mid, basal) as well as radial and circumferential strain of the left ventricle (LV), right ventricle (RV) free wall, left atrium (LA), and right atrium, using the Epsilon EchoInsight Software. A detailed histomorphologic characterization of stored endomyocardial biopsy samples was performed by a cardiac pathologist and scored as < or > 5% AL deposits. Results: We identified 43 patients; 44% were women and 63% white. Median age was 65 years (IQR 59-70). Twenty-two (51%) underwent stem cell transplantation (SCT). A total of 29 patients (67%) died during follow up period (median follow up: 4.2 years (95% CI, 2.8-8.6)). Median overall survival (OS) was 18 months (95% CI, 8.1-37). Lower LA GLS and absence of SCT as a time-varying covariate were significantly and independently associated with increased risk of death in the multivariable cox regression analysis (HR 3.8, 95% CI 1.4-10.2 for LA GLS < 13.5 vs >13.5, p=0.008 and 0.20, 0.06-0.65 for SCT vs no SCT, p<0.001, respectively). Higher LV mass and lower RV TAPSE were associated with increased odds of having >5% of interstitial amyloid deposition on biopsy in the multivariable logistic regression analysis (OR 5.5, 95% CI 1.1-26.8 for >195.6g vs ≤195.6g, p=0.036 and 8.1, 1.2-54.3 for RV TAPSE<1.6cm vs ≥1.6cm, p=0.032, respectively). Conclusions: LA GLS < 13.5 was an independent predictor of mortality in our cohort, and its performance in the routine assessment of AL amyloidosis may be justified. Furthermore, SCT for cardiac AL amyloidosis was associated with improved OS. This finding needs to be confirmed by larger studies in the era of contemporary systemic therapies. Although LV mass and RV TAPSE were associated with higher interstitial amyloid deposition, histopathologic parameters did not predict mortality in this cohort.

Uniformly MXene‐Grafted Eutectic Aluminum‐Cerium Alloys as Flexible and Reversible Anode Materials for Rechargeable Aluminum‐Ion Battery

AbstractAluminum is an attractive anode material in aqueous multivalent‐metal batteries for large‐scale energy storage because of its high Earth abundance, low cost, high theoretic capacity, and safety. However, state‐of‐the‐art aqueous aluminum‐ion batteries based on aluminum anode persistently suffer from poor rechargeability and low coulombic efficiency due to irreversibility of aluminum stripping/plating and dendrite growth. Here eutectic aluminum‐cerium alloys in situ grafted with uniform ultrathin MXene (MXene/E‐Al97Ce3) as flexible, reversible, and dendrite‐free anode materials for rechargeable aqueous aluminum‐ion batteries is reported. As a result of the MXene serving as stable solid electrolyte interphase to inhibit side reactions and the lamella‐nanostructured E‐Al97Ce3 enabling directional Al stripping and deposition by making use of symbiotic α‐Al metal and intermetallic Al11Ce3 lamellas, the MXene/E‐Al97Ce3 hybrid electrodes exhibit reversible and dendrite‐free Al stripping/plating with low voltage polarization of ± 54 mV for ≥1000 h in a low‐oxygen‐concentration aqueous aluminum trifluoromethanesulfonate (Al(OTF)3) electrolyte. These superior electrochemical properties endow soft‐package aluminum‐ion batteries assembled with MXene/E‐Al97Ce3 anode and AlxMnO2 cathode to have high initial discharge capacity of ≈360 mAh g−1 at 1 A g−1, and retain ≈85% after 500 cycles, along with the coulombic efficiency of as high as 99.5%.

Aluminum Nanoplatelet Electrodeposition in AlCl3–1-Ethyl-3-Methylimidazolium Chloride–Urea Melts

The electrodeposition behavior of Al nanoplatelets, which are two-dimensional Al metal thin layer deposits, was investigated in five types of Lewis acidic 60–x–(40−x) [0 ≤ x ≤ 40] mol% AlCl3–1-ethyl-3-methylimidazolium chloride ([C2mim]Cl)–urea room-temperature melts. Al nanoplatelets were obtained in 60–10–30 and 60–0–40 mol% AlCl3–[C2mim]Cl–urea melts. X-ray diffraction measurements revealed that these Al nanoplatelets were oriented in the 111 direction. The formation of this anomalous Al nanoplatelets was analyzed using the operando digital microscope observation technique with our original air-tight electrochemical cell. We succeeded in video recording of the entire formation of Al nanoplatelets in the 60–0–40 mol% AlCl3–[C2mim]Cl–urea melt. Considering these results and electrode reactions involved in the Al deposition process, the electrodeposition behavior of the Al nanoplatelet formation could be attributed to the adequate quantities of free urea molecules generated during the electrode reaction and their specific adsorption onto the (111) Al crystal plane. The applied current density was an important key factor for the electrodeposition of the Al nanoplatelets in the AlCl3–[C2mim]Cl–urea melt. Al nanoplatelets were produced at low applied current densities smaller than −5.0 mA cm−2. The Al nanoplatelets became larger at lower applied current densities.

Engineering a strong and stable ultraviolet chiroptical effect in a large-area chiral plasmonic shell.

Ultraviolet chiral metamaterials (UCM) are highly desired for their strong interaction with the intrinsic resonance of molecules and ability in manipulating the polarization state of high energy photons, but rarely reported to date due to their small feature size and complex geometry. Herein, we design and fabricate a kind of novel ultraviolet chiral plasmonic shell (UCPS) by combing the stepwise Al deposition and colloid-sphere assembled techniques. The cancellation effect originated from the disorder lattices of micro-domains in the colloid monolayer has been successfully overcome by optimizing the deposition parameters, and a strong CD signal of larger than 1 deg in the UV region is demonstrated both in simulation and experiment. This strong ultraviolet chiroptical resonances mainly come from the surface chiral lattice resonance mode, the whispering gallery mode and also the interaction between neighbor shells, and can be effectively tuned by changing structural parameters, for example, the sphere diameter, or even slightly increasing the deposition temperature in experiment. To improve the stability, the fabricated UCPSs are protected by N2 in the deposition chamber and then passivated by UV-ozone immediately after each deposition step. The formed UCPS show an excellent stability when exposing in the atmospheric environment. The computer-aided geometrical model, electromagnetic modes, and the tunable chiroptical resonance modes have been systematically investigated.

Sonochemical synthesis of supersaturated Ga–Al liquid-alloy fine particles and Al3+-doped γ-Ga2O3 nanoparticles by direct oxidation at near room temperature

In this study, we investigated the fabrication of supersaturated gallium (Ga)–aluminum (Al) liquid alloy and Al3+-doped γ-Ga2O3 nanoparticles (NPs) at near room temperature (60 °C) using sonochemical and sonophysical effects. Supersaturated Ga–Al liquid alloy microparticles (Dav = 1.72 µm) were formed and stabilized at 60 °C by the thermal nonequilibrium field provided by sonochemical hot spots. Compared with liquid Ga, supersaturated Ga–Al liquid alloy was rapidly oxidized to a uniform oxide without Al2O3 or Al deposition. Thus, ultrafine Al3+-doped γ-Ga2O3 NPs were obtained after only 1 h of ultrasonic irradiation at 60 °C. The oxidation of liquid Ga was remarkably accelerated by alloying with metallic Al and ultrasonic irradiation, and the time was shortened. The average diameter and surface area of the γ-Ga2O3-based NPs were 59 nm and 181 m2/g, respectively. Compared with γ-Ga2O3, the optical bandgap of the Al3+-doped γ-Ga2O3 NPs was broadened, and the thermal stability improved, indicating Al3+-doping into the γ-Ga2O3 lattice. However, the lattice constant of γ-Ga2O3 was almost unchanged with or without Al3+-doping. Al3+ was introduced into the defect sites of Ga3+, which were massively induced in the defective spinel structure during ultrasonic processing. Therefore, sonochemical processing, which provides nonequilibrium reaction fields, is suitable for the synthesis of supersaturated and metastable materials in metals and ceramics fields.

Simulation of aluminium electrodeposition on complex geometry: Influence of input parameters and electrodeposition conditions

It is necessary to improve the current efficiency and thickness distribution of the electrodeposition of Al coatings on a Mg alloy from ionic liquids. To accomplish this, finite element method is presented here to help experimental processes to refine various electrodeposition conditions for improving efficiency and economy. However, the simulation of Al deposition from ionic liquids is hindered by the lack of initial parameters in existing works. In this paper, the initial kinetic parameters used in the model were obtained precisely using Tafel plots and cyclic voltammograms. The cathodic and anodic transfer coefficients were calculated to be 0.136 and 0.864 at 318.15 K. The exchange current density for Al2Cl7−/AlCl4− redox process was calculated as 4.6A/m2 at 318.15 K. Subsequently, the multiphysics model in this work combined secondary current distribution, laminar flow, and transport of diluted species. The results of the Al coating thicknesses from finite element method agree well with the experimental method. Hence, the finite element model can precisely predict the Al coating thickness, which provides a positive outlook to analyze the thickness of Al coating and promotes its utilization in industry.

(Invited) Aluminum Electrodeposition in AlCl3–1-Ethyl-3-Methylimidazolium Chloride–Urea Melts

Several non-aqueous solvents for aluminum (Al) electrodeposition have been reported so far. Currently most researches on Al electrodeposition are conducted in Lewis acidic chloroaluminate ionic liquids (ILs) and deep eutectic solvents (DESs), which contain AlCl3 over 50 mol% and have a liquid phase at room temperature. Recently these solvents have also drawn attention as electrolytes for Al metal anode anion-rechargeable batteries.1 Only a few years ago, we have reported that Al electrodeposits with unique 2D structure are obtained in a 60.0-40.0 mol% AlCl3–urea DES without any difficulty, but not in the same composition chloroaluminate IL.2 Herein, in order to understand the unique 2D structure fabrication in the AlCl3–urea, we examine Al electrodeposition in the Lewis acidic chloroaluminate ternary melts consisting of AlCl3, 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl), and urea.The preparation and purification processes for AlCl3, [C2mim]Cl, and urea, were identical with those described in previous articles.3 The molar fraction of AlCl3 used in the melts was 60 mol%. The sum of molar fraction for the [C2mim]Cl and urea was 40 mol% and these molar fraction was changed in the range of 0 ~ 40 mol%. The electrochemical measurements were conducted using a three-electrode cell. The working electrode was a Pt disk electrode. An Al plate was used for the counter electrode. The reference electrode was an Al wire immersed directly in the electrolyte. Galvanostatic electrodeposition was conducted using Cu plate electrodes. All the experiments were carried out in an Ar gas-filled glove box with O2 and H2O < 1 ppm. The resulting Al samples were characterized by SEM, EDX, and XRD. Operando digital microscope observation for the Al electrodeposition process was performed using the specially designed two-electrode airtight electrochemical cell.As described in previous article, Al deposition initiates at ca. 0 V (vs. Al(III)/Al) in both 60.0-40.0 mol% AlCl3–[C2mim]Cl IL and 60.0-40.0 mol% AlCl3–urea DES by the following commonly known electrode reaction.2,3 4 [Al2Cl7]− + 3 e− ⇌ Al + 7 [AlCl4]− Typical SEM images of the Al electrodeposits obtained in both electrolytes under the same conditions are exhibited in Fig. 1. In the 60.0-40.0 mol% AlCl3–[C2mim]Cl, dense Al crystals were uniformly electrodeposited on the Cu electrode. Interestingly, in the 60.0-40.0 mol% AlCl3–urea, 2D structured Al deposits, i.e., Al nanoplatelets, were obtained. Such unique Al deposits were yielded at the bath temperature over 313 K, if the applied current density was -5 ~ -20 mA cm-2. EDX analyses of all the electrodeposits revealed that the resultant deposits are pure Al without chloride contamination. XRD measurements strongly suggested that the Al deposits shown in Fig. 1a and 1b are polycrystalline Al and (111)-preferentially oriented Al, respectively. To the best of our knowledge, this anomalous electrodeposition behavior recognized in the 60.0-40.0 mol% AlCl3–urea has not been known in the chloroaluminate IL. Further investigation was conducted by the electrodeposition in the ternary AlCl3–[C2mim]Cl–urea melts under the same condition that can produce Al nanoplatelets in the AlCl3–urea. In the present study, we used three types of melts, 60.0-30.0-10.0 mol%, 60.0-20.0-20.0 mol%, and 60.0-10.0-30.0 mol% AlCl3–[C2mim]Cl–urea. As we expected, the increase in the urea molar faction in the melts provoked the morphology variation in the Al deposits. The 2D structure appeared in only the 60.0-10.0-30.0 mol% AlCl3–[C2mim]Cl–urea, suggesting that the urea is highly involved in the nanoplatelet formation. Because direct observation of the electrodeposition process enables to propose the plausible formation mechanism, the airtight electrochemical cell for operando digital microscope was newly designed. Further insights obtained through the operando observation will be reported in our presentation. References T. Tsuda, in Next Generation Batteries, K. Kanamura, Ed., Springer, Singapore, pp. 565-580 (2021).T. Tsuda, R. Miyakawa, A. Konda, Y. Ikeda, and S. Kuwabata, Program & Book of s (BoA) of 69th Annual ISE Meeting, p. 1512 (2018).T. Tsuda, G. R. Stafford, and C. L. Hussey, J. Electrochem. Soc., 164, H5007 (2017) and references therein. Figure 1

Development of Low Temperature Double Level TSV, Hole and Seal Process for Low Pressure Zero Level MEMS Packaging

Through Silicon Via (TSV) technology is considered one of the key methods to enable heterogeneous integration at the third dimension and realize electrical interconnection between device parts. In that context, different components (MEMS, sensors, circuits etc.) can be electrically integrated in 3D manner, increasing stack density, shrinking footprint, and reducing fabrication costs. At MEMS integration, it is important to explore the packaging method that enables the optimum performance of the active MEMS component and the TSV approach to electrically connect it with the package. Herein, we present our via-last approach to integrate a zero-level packaged MEMS wafer defined by cavity SOI (C-SOI) and CMOS readout circuitry (at thermal budget <400ºC). TSV distribution and fabrication route ensures the electrical connectivity of MEMS inertial sensor and CMOS. Furthermore, a hole is added to the layout scheme and sealed afterwards to ensure low pressure encapsulation in the MEMS cavity.In our previous work related to MEMS fabrication [1], we elaborated the superiority of C-SOI start material over conventional fabrication methods (like vapor HF). In our approach, MEMS cavity structures are realized by patterning dielectrics and the moving parts by employing deep Si etch (DSiE) method (Fig 1 a-c). To enhance the dielectric surface smoothness prior bonding, a complementary HF -based clean applied. This way, bonding requirements (Rq<1nm, Rrange<10nm) are met. CMOS wafer is fabricated with a single layer of Cu damascene process in a dielectric stack to create complementary bonding medium for MEMS wafer. Selected dielectrics at MEMS (thermal oxide) and CMOS (SiCN) can perform better at low temperature fusion bonding due to their moisture blocking capability. Next, fusion bonding at room temperature is carried out using assisted force (60kN) to enhance bonding efficiency and completed by curing the wafer pair at 350˚C.In this paper, we present further work to complete the MEMS zero-level packaging through electrical connections and vacuum seal. Fabrication sequence continues on the backside of the MEMS wafer (Fig 1d-g). First the desired top membrane (cap) thickness of MEMS wafer realized by thinning bulk Si substrate down to 50µm. After SiOx deposition, a double TSV approach is carried out aiming to create the electrical interconnections between the package components, one to reach to the sensor parts in MEMS wafer and one to reach to CMOS. TSV for enabling the connection with sensor parts (12x50μm) is realized by DSiE through the top Si membrane and buried oxide (BOX) landing at Si epi layer of C-SOI. Isolation of this TSV is obtained by conformal liner deposition using SACVD SiOx (350C). Liner opening at the TSV base is assisted by a second non-conformal dielectric deposition to protect the sidewall isolation during resistless directional liner etch back at TSV bottom. Metallization of the via is carried out by sequential PVD barrier (Ta) and seed (Cu) depositions; and the TSV is filled with electroplated Cu. MEMS top surface is then cleared either by CMP or by wet and dry etching of Cu and Ta, respectively. TSV for connecting to CMOS (20x80μm) follows the same processing route with an additional DSiE through all the C-SOI MEMS stack and landing on designated plugs on CMOS. With these two TSV schemes it is ensured to bias and measure the inertial sensor, its driving circuitry, and the zero-level package (Fig. 2a)Once the two TSVs fabrication is completed, hole for the vacuum sealing can be created. First, the top dielectric on surface of MEMS wafer is etched in circular areas of diameter 10μm to define where the venting holes will be created. This is mainly to expose Si surface and reduce possible leakage paths, as well as to increase the adhesion of the deposited metallization to close the hole under vacuum. Small hole (Ø2μm) is defined in the middle of the Si circular area by lithography and etching through the top MEMS membrane (50μm) landing on the cavity of the C-SOI (Fig 1f). Vacuum seal of the zero-level package is finalized with bond pad creation which also seals the hole under vacuum. Al deposition is carried out at high vacuum PVD system; the hole is simultaneously sealed and preserve the same vacuum as the PVD chamber. Along with the chamber vacuum level, the Al thickness and power is also very important to achieve the desired seal Fig.2b.Proposed work enables zero-level MEMS hermetic packaging with integrated CMOS and developed on 200mm wafers.[1] Development of Copper/Dielectric Hybrid Fusion Bonding with Cavity for CMOS compatible Wafer Level Hermetic Packaging, A.Malainou, J.Visker, D.Sabuncuoglu, 21st EPTC, Singapore 2019 Figure 1

Remarkable improvement in microstructure and mechanical properties of cold sprayed Al deposits via impact forging post-spray treatment

A viable and novel approach was reported to significantly modify the microstructure and improve the mechanical properties of cold sprayed Al deposits. For this purpose, cold sprayed Al deposits were subjected to unidirectional impact forging in the temperature range of 250–300 °C. The evolution of microstructure and mechanical properties of the deposits were studied in detail. The results indicated that, hot-forging may significantly reduce the porosity in the deposits, and remarkably improve the Al/Al bonding due to enhanced inter-particle diffusion, dynamic recovery, and recrystallization mechanisms. Consequently, the ultimate tensile strength (UTS) and elongation in the Al deposits were remarkably enhanced from 26.2 ± 2.4–95.7 ± 1.7 MPa and 0.8 ± 0.05–36.3 ± 2.6%, respectively.

PB2155: B-CELL NON-HODGKIN’S LYMPHOMAS ASSOCIATED WITH AMYLOIDOSIS

Background: Different types of B-NHLs (MZL, LPL, B-CLL/SLL, FL, MCL, DLBCL) may show plasmacytic differentiation and may produce AL amyloid locally or as a part of systemic amyloidosis. Case reports of coincidence of B-NHL and non-AL amyloidosis were also reported, therefore correct diagnostic workflow to type amyloid deposits should include three main steps 1. special histological staining (Congo red and/or Saturn red), 2. immunoprofiling and proteomic analysis (LMD-LC/MS). Nomenclature classification distinguishes 36 amyloidogenic proteins and more are expected (ISA 2020). Aims: Analysis of amyloid deposits irrespective of origin and localization is appealing for diagnostic and experimental precising which brings new insights in pathogenesis, classification and correct therapy due to a possibility of combination or hybrid amyloid deposits, and concurrent B-NHL may be detected. Methods: Amyloid deposits were detected in variable FFPE tissues stained with Congo red and/or Saturn red with consequent immunohistochemical analysis (IHC) and proteomic analysis with the use of laser capture microdissection and liquid chromatography/tandem mass spectrometry (LMD-LC/MS/MS). Concurent B-NHLs (excl. multiple myeloma, plasmocytoma and MGUS) were diagnosed due to characteristic morphology (HE, PAS, Giemsa), immunoprofile (primary antibodies with appropriate dilution - CD3, CD5, CD10, CD20, CD21, CD23, CD30, CD138, Bcl-2, Bcl-6, MUM1/IRF4, PAX5, cyclin D1 and/or SOX11, c-Myc, Ki67) and detected clonal rearrangement of IgVH (BIOMED-2). Results: In our file with 329 amyloid positive specimens concurent B-NHLs were found in 14 specimens. 7 specimens were signed as highly suspected for B-NHL with plasmacytic differentiation and immunoglobulin light chain restriction but without evidence of IgVH clonal rearrangement. The most common B-NHL associated with localised amyloidosis was ENMZL MALT-type (10 cases, 1 case with hybrid amyloidosis AL kappa/AH IgG1), in 4 specimens LPL was detected. In all cases with IHC and/or LCM-LC/tandem MS analysis AL type of amyloid was detected including 2 cases with hybrid amyloidosis AL/AH and AL/AApoAIV, and in 1 case local AL amyloid deposition was produced after a therapy for B-NHL. Summary/Conclusion: M-protein produced by B-NHL may be low or high according to a localised or systemic AL involvement resp., localised amyloid deposition is commonly associated with ENMZL MALT-type, both localised and systemic amyloidosis may be found out in LPL. Our category of highly suspected B-NHL with plasmacytic differentiation is literary sign as “AL amyloidosis with a localized B-cell neoplasia of undetermined significance” or as “AL amyloidosis with a an associated predominant kappa or lambda light chain expressing plasma cell population without evidence for clonality”. In our file (7 cases) only kappa/lambda immunohistochemically detected monotypy was recorded without an evidence of IgVH clonal rearrangement (somatic hypermutation of IgVH may be expected). The possibility of senescence evolution in B-NHL after a therapy may also bring local AL deposits (1 case in our cohort). Coincidence or association of non-AL amyloidosis (ATTRwt, ATTRv, AA and other) with B-NHL was described mainly in single case reports and extends the differential diagnosis. In a such cases both methods (IHC and LCM-LC/tandem MS) are suitable for correct amyloid typing, although LMD-LC/tandem MS brought more promising results than IHC.

Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries.

Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition. The amorphous aluminum (a-Al) interfacial layer is triggered by an in situ lithium-ion alloying/dealloying process on a metallic Al substrate with low strength. Unveiled by experimental and theoretical investigations, the amorphous structure greatly lowers the Al nucleation energy barrier, which forces the Al deposition competitive to the electron-stealing hydrogen evolution reaction (HER). Simultaneously, the inhibited HER mitigates the passivation, promoting interfacial ion transfer kinetics and enabling steady aluminum plating/stripping for 800 h in the symmetric cell. The resultant multiple full cells using Al@a-Al anodes deliver approximately a 0.6 V increase in the discharge voltage plateau compared to that of bare Al-based cells, which far outperform all reported aqueous AMBs. In both symmetric cells and full cells, the excellent electrochemical performances are achieved in a noncorrosive, low-cost, and fluorine-free Al2(SO4)3 electrolyte, which is ecofriendly and can be easily adapted for sustainable large-scale applications. This work brings an intriguing picture of the design of metallic anodes for reversible and high-voltage AMBs.

Impact of substrate heating during Al deposition and post annealing on surface morphology, Al crystallinity, and Ge segregation in Al/Ge(111) structure

We have studied the impact of Ge substrate heating during ∼25 nm thick Al deposition and post annealing in N2 ambient on the surface flatness of an Al/Ge(111) structure, the crystallographic structure of the deposited Al layer, and formation of a Ge segregated layer. Surface segregation of Ge atoms on a flat metal surface is an effective means of growing two-dimensional Ge crystals as well as an ultrathin Ge crystalline layer. The surface morphology of the Al/Ge(111) structure becomes flat by substrate heating during Al deposition. The crystallinity of the Al layer on Ge(111) can be improved by both substrate heating and post annealing. Ge segregation on a flat Al(111) surface also occurred by post annealing.

Boron contributes to excessive aluminum tolerance in trifoliate orange (Poncirus trifoliata (L.) Raf.) by inhibiting cell wall deposition and promoting vacuole compartmentation

Boron (B) is an indispensable micronutrient for plant growth that can also alleviate aluminum (Al) toxicity. However, limited data are available on the underlying mechanisms behind this phenomenon. Here, we found that a certain range of B application could alleviate the inhibitory effects of Al toxicity on citrus. Transcriptome analysis revealed that several Al stress-responsive genes and pathways were differentially affected and enriched, such as coding for the secretion of organic acid and the distribution of Al in subcellular components after B addition. Specifically, B application enhanced rhizosphere pH and induced malate exudation by expressing PtALMT4 and PtALMT9 genes occurred in Al-treated root, which ultimately reduced the absorption of Al and coincided with down-regulated the expression of PtNrat1. Moreover, B supply suppressed the pectin methyl-esterase (PME) activity and displayed a lower level of PtPME2 expression, while enhanced the PtSTAR1 expression, which is responsible for reducing cell wall (CW) Al deposition. Boron addition enhanced the PtALS1 and PtALS3 expression, accompanied by a higher proportion of vacuolar Al compartmentation during Al exposure. Collectively, the protective effects of B on root injury induced by Al is mainly by subsiding the Al uptake in the root apoplast and compartmentalizing Al into vacuole.

Monoclonal gammopathy of (un)known significance

Monoclonal gammopathies are a frequently diagnosed entity. However, the diagnosis is not always clinically relevant. The diagnosis of a monoclonal gammopathy requires serum electrophoresis, immunofixation and free light chain measurement. Sometimes, monoclonal gammopathies occur in the course of transient or autoimmune inflammation. Further diagnostics should only be performed after risk assessment according to Mayo criteria. In non-low risk patients, a symptomatic myeloma has to be ruled out via SLiM-CRAB criteria. The diagnostic work-up should include whole-body MRI and a bone marrow puncture as well as a 24 h urine sample. If it does not imply myeloma, the diagnosis of MGUS is confirmed and a follow-up after 6 months is recommended. After that, low-risk patients only need SLiM-CRAB screening at clinical signs of progression. All other patients should receive serologic follow-ups once a year. Importantly, MGUS patients show higher morbidity. Amongst a higher prevalence of osteoporosis and immunodeficiency, a wide array of MGUS-associated diseases such as AL amyloidosis, deposition diseases and Fc binding-dependent effects can occur. This article gives an overview over the work-up, observation and caveats of monoclonal gammopathy of (un)known significance.

Solid-Solution-Based Metal Coating Enables Highly Reversible, Dendrite-Free Aluminum Anode

Aluminum-ion batteries have attracted great interest in the grid-scale energy storage field due to their good safety, low cost and the high abundance of Al. However, Al anodes suffer from severe dendrite growth, especially at high deposition rates. Here, we report a simple strategy for constructing a highly reversible, dendrite-free, Al-based anode through directly introducing a solid-solution-based metal coating to a Zn foil substrate. Compared with Cu foil substrates and bare Al, a Zn foil substrate shows a lower nucleation barrier of Al deposition due to the intrinsic, definite solubility between Al and Zn. During Al deposition, a thin, solid-solution alloy phase is first formed on the surface of the Zn foil substrate and then guides the parallel growth of flake-like Al on Zn substrate. The well-designed, Zn-coated Al (Zn@Al) anode can effectively inhibit dendrite growth and alleviate the corrosion of the Al anode. The fabricated Zn@Al–graphite battery exhibits a high specific capacity of 80 mAh·g−1 and an ultra-long lifespan over 10,000 cycles at a high current density of 20 A·g−1 in low-cost molten salt electrolyte. This work opens a new avenue for the development of stable Al anodes and can provide insights for other metal anode protection.

Bi-functional poly(vinylidene difluoride) coated Al anodes for highly rechargeable aqueous Al-ion batteries

Aqueous rechargeable aluminum (Al) ion batteries have attracted much attention due to the high abundance of Al metal and high volumetric energy density (8040 mAh cm−3). However, Al anode suffers from hydrogen evolution side reactions in aqueous electrolyte due to its low equilibrium redox potential. Here, we developed a poly(vinylidene difluoride) (PVDF) coating that can inhibit free H2O/O2 and alleviate the corrosion problem. Theoretical calculations verify that PVDF and Al3+ have a strong interaction through the F-Al bond towards the observed uniform Al deposition. As a result, the cell of PVDF-Al/K2CoFe(CN)6 achieved 98.2% Coulombic efficiency after 400 cycles at a current density of 100 mA g−1. This work presents an effective and facile strategy to the development of high-performance and low-cost aqueous Al-ion batteries.

Tungsten(II) chloride hydrates with high solubility in chloroaluminate ionic liquids for the electrodeposition of Al–W alloy films

• Tungsten(II) chloride hydrates showed high solubility in AlCl 3 -based ionic liquids. • Al–W alloy films with high W contents were obtained at high current densities. • Current efficiencies close to 100% were achieved even in the baths with hydrates. • Spectroscopic techniques were used to identify the chemical species in the bath. The electrodeposition of Al alloys using chloroaluminate ionic liquids (ILs), such as 1-ethyl-3-methylimidazolium chloride (EMIC)–AlCl 3 , has been of significant interest as a surface coating technology. To minimize the contamination of the ILs with water, which can inhibit Al deposition, anhydrous metal chlorides were generally used as metal precursors in the previous studies on Al alloy electrodeposition. However, many anhydrous transition metal chlorides have limited solubility in ILs, making it difficult to obtain Al-based alloy films with a high alloy content at a high current density. This article describes the electrodeposition of Al–W alloy films using W(II) chloride hydrates, W 6 Cl 12 ·2H 2 O and (H 3 O) 2 [W 6 Cl 14 ]·7H 2 O, as W precursors. These hydrated salts were found to have much higher solubilities in EMIC–AlCl 3 ILs than anhydrous W 6 Cl 12 . Therefore, owing to the high solubility of the hydrated salts, Al–W alloy films with a high W content could be electrodeposited even at high current densities. Furthermore, the use of hydrated salts had no negative effect on the quality of the electrodeposited films or the current efficiency. A chemical speciation of the Al and W ions in the ILs was carried out using Raman spectroscopy, Fourier-transform infrared spectroscopy, extended X-ray absorption fine structure spectroscopy, and UV-visible spectroscopy. The spectral data conclusively indicated that the dissolved species derived from the hydrated salts were different compared to those derived from the anhydrous salt. The high solubility of the hydrated W salts and the success of Al–W alloy electrodeposition encourage the use of hydrated salts in chloroaluminate ILs.

Understanding the phytotoxic impact of Al3+, nano-size, and bulk Al2O3 on growth and physiology of maize (Zea mays L.) in aqueous and soil media

The release and accumulation of metal-oxide nanoparticles in soils have threatened terrestrial plants. However, limited knowledge is available on the accumulation of nano-Al2O3 (22 nm), bulk-Al2O3 (167 nm), and Al3+ by maize plants and the subsequent impact on its physiology and growth in agar (0.7% w/v), hydroponic (1X), and soil. Maize plants were cultivated with 0.05–2 mg g−1 or ml−1 of three Al types and their biological attributes, oxidative status, Al bioaccumulation, and translocation were measured. The ICP-MS results revealed a dose-dependent increase (P ≤ 0.05 or ≤0.01) in Al content in maize tissues following nano-Al2O3 and Al3+ exposure, however, plants exposed to bulk-Al2O3 showed no significant uptake of Al. Atomic mapping by EDX during SEM analysis and TEM revealed varied distributions of nano-Al2O3 from roots to aerial parts and intracellular transportation. Al deposition in tissues followed the order: Al3+ > nano-Al2O3 > bulk-Al2O3 and therefore, a similar trend of toxicity was observed for seed germination, the emergence of plant organs, length, biomass accumulation, total chlorophyll, phosphorus content, and total soluble protein. Oxidative stress was profoundly induced dose-dependently and was highest at 2 mg ml−1 or g−1 of Al3+ and nano-Al2O3 when superoxide radical formation, proline induction, activities of superoxide dismutase (SOD), catalase (CAT), peroxidase (GPX), and glutathione reductase (GR) and membrane lipid peroxidation were measured. Aluminum toxicity was found higher in hydroponically grown maize compared to soil-grown maize. Forty days exposure in soil showed greater inhibition of maize growth compared to 20 days exposure. This study is significant in understanding the maize response to different Al types in soil and soil-free media.

Unearthing the alleviatory mechanisms of hydrogen sulfide in aluminum toxicity in rice

Hydrogen sulfide (H2S) improves aluminum (Al) resistance in rice, however, the underlying mechanism remains unclear. In the present study, treatment with 30-μM Al significantly inhibited rice root growth and increased the total Al content, apoplastic and cytoplasm Al concentration in the rice roots. However, pretreatment with NaHS (H2S donor) reversed these negative effects. Pretreatment with NaHS significantly increased energy production under Al toxicity conditions, such as by increasing the content of ATP and nonstructural carbohydrates. In addition, NaHS stimulated the AsA-GSH cycle to decrease the peroxidation damage induced by Al toxicity. Pretreatment with NaHS significantly inhibited ethylene emissions in the rice and then inhibited pectin synthesis and increased the pectin methylation degree to reduce cell wall Al deposition. The phytohormones indole-3-acetic and brassinolide were also involved in the alleviation of Al toxicity by H2S. The transcriptome results further confirmed that H2S alleviates Al toxicity by increasing the pathways relating to material and energy metabolism, redox reactions, cell wall components, and signal transduction. These findings improve our understanding of how H2S affects rice responses to Al toxicity, which will facilitate further studies on crop safety.

Post-metallization annealing and photolithography effects in p-type Ge/Al2O3/Al MOS structures

In this work, the combined effect of negative tone photolithography and post-metallization annealing (PMA) on the electrical behavior of Al/Al2O3/p-Ge MOS structures are investigated. During photoresist development, the exposed upper part of the Al2O3 film weakens due to the reaction with the developer. Subsequent processes of Al deposition and PMA at 350 °C result in alumina thickness reduction. The gate electrode formation seems to involve at least three processes: (a) germanium substrate out-diffusion and accumulation at the top of the alumina layer that takes place during the alumina deposition, (b) alumina destabilization, and (c) germanium diffusion into the deposited Al metal and Al diffusion into the alumina. The overall effect is the reduction of the alumina thickness due to its partial consumption. It is shown that the germanium diffusion depends on the annealing duration, and not on the annealing ambient (inert or forming gas). Although PMA passivates interface traps near the valence band edge, the insulating properties of the stacks are degraded. This degradation appears as a low-level ac loss, attributed to a hopping current that flows through the Al2O3 layer. The results are discussed and compared to recently reported on Pt/Al2O3/p-Ge structures formed and treated under the same conditions.