Self‐Boosting Catalytic Nanoreactors Integrated with Triggerable Crosslinking Membrane Networks for Initiation of Immunogenic Cell Death by Pyroptosis

Synthetic polymer vesicles spur novel strategies for producing intelligent nanodevices with precise and specific functions. Engineering vesicular nanodevices with tunable permeability by a general platform without involving trade‐offs between structural integrity, flexibility, and functionality remains challenging. Herein, we present a general strategy to construct responsive nanoreactors based on polyion complex vesicles by integrating stimuli‐responsive linkers into a crosslinking membrane network. The formulated ROS‐responsive nanoreactor with self‐boosting catalytic glucose oxidation could protect glucose oxidase (GOD) to achieve cytocidal function by oxidative stress induction and glucose starvation, which is ascribed to stimuli‐responsive vesicle expansion without fracture and size‐selective cargo release behavior. The GOD‐loaded therapeutic nanoreactor induced an immunostimulatory form of cell death by pyroptosis, which has the great potential to prime anti‐tumor immune responses.     

Evaluation of CH3-DTPA-Gd (NMS60) as a new MR contrast agent: early phase II study in brain tumors and dual dynamic contrast-enhanced imaging

PURPOSE: A newly developed contrast material, CH3-DTPA-Gd (NMS60), a trimer containing 3 Gd(3+) atoms per molecule, has been shown to offer greater enhancement and longer vascular retention than gadopentetate dimeglumine (Gd-DTPA) in animals. We report on our early phase II study on NMS60 in brain tumor patients together with supplementary investigations. METHODS AND MATERIALS: The longitudinal relaxation rate (R(1)=1/T(1)) and the transverse relaxation rate (R(2)*=1/T(2)*) of NMS60 and Gd-DTPA were determined at 20 degrees C in water at 1.5 T. An NMS60 dose of 0.1 or 0.2 mmol (Gd)/kg was randomly assigned and administered to 10 patients (five women, five men; mean age: 49 years) with brain tumors. Safety and contrast-enhancing ability of NMS60 were evaluated. Dual dynamic contrast-enhanced T(1) and R(2)* studies (DUCE imaging) were also carried out in two patients. RESULTS: Regarding the relaxivity per Gd, R(1) and R(2)* of NMS60 were 9.5 and 11.0 (mmol/L x s)(-1), respectively, compared to 4.8 and 7.2 (mmol/L x s)(-1) for Gd-DTPA. Although a transient slight increase of alanine aminotransferase was observed in one case, no other adverse reactions were observed after administration of NMS60. Contrast enhancement by NMS60 was excellent at both concentrations, and when tumor detectability was assessed with a five-point scale, the diagnostic usefulness was 4 or higher in all cases. In DUCE imaging, NMS60 appeared to show high signal intensity, when compared with the data obtained separately for Gd-DTPA. CONCLUSION: NMS60 had a high contrasting effect and little toxicity, and is expected to be clinically useful.     

Preparation of Self-Organized Porous Polymer Masks for Si Dry Etching

Summary: Self-organized honeycomb-patterned polymer films were prepared by using condensed water droplet arrays as templates. Porous polymer masks for dry etching were easily prepared on Si substrates by peeling off the honeycomb-patterned films. After dry etching, hexagonally-arranged micro-pores were formed on the surface of Si substrates.     

VC Dimensions of Principal Component Analysis

Motivated by statistical learning theoretic treatment of principal component analysis, we are concerned with the set of points in ℝ ^d that are within a certain distance from a k-dimensional affine subspace. We prove that the VC dimension of the class of such sets is within a constant factor of (k+1)(d−k+1), and then discuss the distribution of eigenvalues of a data covariance matrix by using our bounds of the VC dimensions and Vapnik’s statistical learning theory. In the course of the upper bound proof, we provide a simple proof of Warren’s bound of the number of sign sequences of real polynomials.     

Thermo-responsive extraction of cadmium(II) ion with TPEN-NIPA gel. Effect of the number of polymerizable double bond toward gel formation and the extracting behavior

N,N,N′,N′-(Tetrakis-2-pyridylmethyl)ethylenediamine (TPEN) derivatives bearing the different number (1-4) of a double bond moiety on the pyridine ring are synthesized and subjected to copolymerization with N-isopropylacrylamide in the presence of AIBN. The obtained poly(TPEN-NIPA) gels show thermo-responsive swelling/shrinking behaviors and are employed for the extraction of cadmium(II) ion from the aqueous solution to examine the relationship of the gel characteristics and the extraction performance. The polymer gels composed of the TPEN derivative bearing three or four double bonds exhibit temperature-dependent change of swelling and shrinking in water. These gels extract Cd^II ion efficiently from the aqueous solution in the swelling state at 5 °C, while little extraction was observed at 45 °C with shrinking.     

Modification of flexible part in Cu(2+) interdigitated framework for CH(4)/CO(2) separation

The structural flexibility of Cu(2+) interdigitated layer type framework was controlled and the compound represented clear separation property of CH(4)/CO(2) at range of 0-1.0 MPa and recovery of adsorbed CO(2) above 0.1 MPa.     

Octapalladium Strings Trap C60 and C70 Fullerenes Affording Metal-Chain-Wired Bucky Balls

Reactions of Pd₈ strings supported by meso-Ph₂PCH₂P(Ph)CH₂P(Ph)CH₂PPh₂ (meso-dpmppm) ligands, [Pd₈(meso-dpmppm)₄(L)₂]⁴⁺ (L=CH₃CN ( 1 ), XylNC ( 2 )) with C₆₀ resulted in the exclusive formation of unprecedented metal-chain-wired C₆₀ bucky balls, [{Pd₄(meso-dpmppm)₂(L)}₂(C₆₀)]⁴⁺ (L=CH₃CN ( 11 ), XylNC ( 12 )), in which a C₆₀ fullerene is trapped in the central Pd–Pd junction, as unambiguously established by spectroscopic, X-ray crystallographic, and theoretical techniques. The similar reaction of Pd₈ strings supported by rac-dpmppm, [Pd₈(rac-dpmppm)₄(CH₃CN)₂]⁴⁺ ( 3 ) also afforded a racemic mixture of [{Pd₄((R*,R*)-dpmppm)₂(CH₃CN)}₂(C₆₀)]⁴⁺ ( 13 ) without scrambling the Pd₄ fragments with (R,R)- and (S,S)-dpmppm ligands. Consequently, those of enantiopure chiral Pd₈ strings, [Pd₈((R*,R*)-dpmppm)₄(CH₃CN)₂]⁴⁺, certainly afforded chiral bucky balls of [{Pd₄((R*,R*)-dpmppm)₂(CH₃CN)}₂(C₆₀)]⁴⁺ ( 13 _RR and 13 _SS ), that exhibit mirror-image circular dichroism spectra. The reactions of 1 and 2 were also applied for trapping a C₇₀ fullerene to give 2 : 1 adducts of [{Pd₄(meso-dpmppm)₂(L)}₂(C₇₀)]⁴⁺ (L=CH₃CN ( 21 ), XylNC ( 22 )). These results provide useful information for creating a platform to develop dimensionally and chirality controlled metal–carbon nanocomposite materials.     

Estimation of parameters for discretely observed diffusion processes with a variety of rates for information

A specific form of stochastic differential equation with unknown parameters are considered. We do not necessarily assume ergodicity or recurrency, and any moment conditions for the true process, but some tightness conditions for an information-like quantity. The interest is to estimate the parameters from discrete observations the step size of which tends to zero. Consistency and the rate of convergence of proposed estimators are presented. The rate is deduced naturally from the rate for the information-like quantities.