Objective: To compare the bone cement diffusion and clinical effects between conventional percutaneous vertebroplasty(PVP) and the application of positioning reduction and targeted puncture techniques in the treatment of elderly patients with osteoporotic vertebral compression fractures.
Methods: A retrospective comparative study was conducted, analyzing the clinical data of 268 elderly patients with single-level vertebral fractures admitted between January 2021 and March 2023. The patients were divided into two groups:the conventional PVP group (138 cases) and the targeted PVP group (130 cases).
J Chem Theory Comput
March 2025
We develop a multithreaded parallel coordinate descent full configuration interaction algorithm (mCDFCI) for the electronic structure ground-state calculation in the configuration interaction framework. The FCI problem is reformulated as an unconstrained minimization problem and tackled by a modified block coordinate descent method with a deterministic compression strategy. mCDFCI is designed to prioritize determinants based on their importance, with block updates enabling efficient parallelization on shared-memory, multicore computing infrastructure.
View Article and Find Full Text PDFDespite substantial progress in ligand engineering, the efforts in the field of Au nanoclusters have been concentrated almost exclusively on organic ligands. Halides, the most typical auxiliary inorganic ligands widely present in Au clusters, remain virtually unexplored, particularly regarding their effects on cluster construction. Herein, diphosphine PhP(CH)PPh (L, n = 1-6) is chosen as the co-protecting organic ligands and a comparative analysis on the influential roles of halide ions (Cl, Br, I) in guiding Au cluster synthesis is conducted.
View Article and Find Full Text PDFHematopoietic Progenitor Kinase 1 (HPK1, also known as MAP4K1) is a hematopoiesis-specific serine/threonine kinase that belongs to the MAP4K family of Ste20-related protein kinases. HPK1 has been identified as a negative regulator of T-cell receptor signaling. Recent studies have indicated that the inhibition or knockout of HPK1 kinase function can effectively alleviate T cell exhaustion, enhance T cell functionality, and improve the therapeutic efficacy of tumor immunotherapy.
View Article and Find Full Text PDFChitosan materials are much important in adsorption, separation and water treatment due to their hydrophilicity, biodegradability and easy functionalization. However, they were difficult to form structural materials, which limited its application in engineering. In this paper, a new type of chitosan porous materials was prepared with two-step strategy involving the freezing crosslinking of chitosan with glutaraldehyde to form cryogels, and their subsequent reduction with NaBH to transform CN bonds into CN bonds, resulting in remarkable improvement of mechanical property.
View Article and Find Full Text PDFWe propose a state-averaged orbital optimization scheme for improving the accuracy of excited states of the electronic structure Hamiltonian for use on near-term quantum computers. Instead of parameterizing the orbital rotation operator in the conventional fashion as an exponential of an antihermitian matrix, we parameterize the orbital rotation as a general partial unitary matrix. Whereas conventional orbital optimization methods minimize the state-averaged energy using successive Newton steps of the second-order Taylor expansion of the energy, the method presented here optimizes the state-averaged energy using an orthogonally constrained gradient projection method that does not require any expansion approximations.
View Article and Find Full Text PDFThe subvalent silver kernel represents the nascent state of silver cluster formation, yet the growth mechanism has long been elusive. Herein, two silver nanoclusters ( and ) coprotected by TC4A (HTC4A = --butylthiacalix[4]arene) and TBPMT (TBPMTH = 4--butylbenzenemethanethiol) containing 6e and 4e silver kernels are synthesized and characterized. The trimer of the 2e superatom Ag kernel in is built from a central Ag octahedron sandwiched by two orthogonally oriented Ag trigonal bipyramids through sharing vertexes, whereas a double-octahedral Ag kernel in is a dimer of 2e superatoms.
View Article and Find Full Text PDFHematopoietic progenitor kinase 1 (HPK1, MAP4K1) is a promising target for immune-oncology therapy. It has been recently demonstrated that loss of HPK1 kinase activity can enhance T cell receptor (TCR) signaling. However, many essential functions mediated by the HPK1 scaffolding role are still beyond the reach of any kinase inhibitor.
View Article and Find Full Text PDFJ Chem Theory Comput
November 2023
An efficient excited state method, named xCDFCI, in the configuration interaction framework is proposed. xCDFCI extends the unconstrained nonconvex optimization problem in coordinate descent full configuration interaction (CDFCI) to a multicolumn version for low-lying excited states computation. The optimization problem is addressed via a tailored coordinate descent method.
View Article and Find Full Text PDFLigand shells of gold nanoclusters play important roles in regulating their molecular and electronic structures. However, the similar but distinct impacts of the homologous analogues of the protecting ligands remain elusive. The symmetric monoarsine-protected cluster [Au(AsPh)Cl] (AuAs) was facilely prepared by direct reduction of (PhAs)AuCl with NaBH.
View Article and Find Full Text PDFJ Chem Theory Comput
February 2023
Near-term quantum computers will be limited in the number of qubits on which they can process information as well as the depth of the circuits that they can coherently carry out. To date, experimental demonstrations of algorithms such as the Variational Quantum Eigensolver (VQE) have been limited to small molecules using minimal basis sets for this reason. In this work we propose incorporating an orbital optimization scheme into quantum eigensolvers wherein a parametrized partial unitary transformation is applied to the basis functions set in order to reduce the number of qubits required for a given problem.
View Article and Find Full Text PDFThe composition of protection monolayer exerts great influence on the molecular and electronic structures of atomically precise monolayer protected metal nanoclusters. Four isostructural Ag/cyanurate/phosphine metallamacrocyclic monolayer protected Ag nanoclusters are synthesized by kinetically controlled in-situ ligand formation-driven strategy. These eight-electron superatomic silver nanoclusters feature an unprecedented interfacial bonding structure with diverse E-Ag (E=O/N/P/Ag) interactions between the Ag core and metallamacrocyclic monolayer, and displays thermally activated delayed fluorescence (TADF), benefiting from their distinct donor-acceptor type electronic structures.
View Article and Find Full Text PDFJ Chem Theory Comput
August 2022
We propose a quantum-classical hybrid variational algorithm, the quantum orbital minimization method (qOMM), for obtaining the ground state and low-lying excited states of a Hermitian operator. Given parametrized ansatz circuits representing eigenstates, qOMM implements quantum circuits to represent the objective function in the orbital minimization method and adopts a classical optimizer to minimize the objective function with respect to the parameters in ansatz circuits. The objective function has an orthogonality constraint implicitly embedded, which allows qOMM to apply a different ansatz circuit to each input reference state.
View Article and Find Full Text PDFThe structural transformations of metal nanoclusters are typically quite complex processes involving the formation and breakage of several bonds, and thus are challenging to study. Herein, we report a case where two lacunary Keggin polyoxometallate templated silver single-pods [PWO@Ag] (SD/Ag51b) fuse to a double-pod [(PWO)@Ag] by reacting with 4,4'-bipyridine (bipy) or 1,4-bis(4-pyridinylmethyl)piperazine (pi-bipy). Their crystal structures reveal the formation of a 2D 4-sql layer (SD/Ag72a) with bipy and a 3D pcu framework (SD/Ag72c) with pi-bipy.
View Article and Find Full Text PDFControllable syntheses of Au nanoclusters (NCs) with different nuclearities are of great significance due to the kernel-dependent physicochemical properties. Herein, two pairs of enantiomeric Au NCs [Au(/-BINAP)(PhC≡C)Cl] () and [Au(/-BINAP)(PhC≡C)]·Cl (), both with (rigid axial chirality) diphosphine BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) as the predominant organic ligands, were controllably synthesized through precursor engineering. The former was obtained by direct reduction of HAuCl·4HO, while the latter was obtained by reduction of [Au(SMe)Cl] instead.
View Article and Find Full Text PDFAlthough chirality is an ever-present characteristic in biology and some artificial molecules, controlling the chirality and demystifying the chirality origin of complex assemblies remain challenging. Herein, we report two homochiral Ag nanoclusters with inherent chirality originated from identical rotation of six square faces on a Ag cube driven by intra-cluster π···π stacking interaction between pntp (Hpntp = p-nitrothiophenol) ligands. The spontaneous resolution of the racemic (SD/rac-Ag14a) to homochiral nanoclusters (SD/L-Ag14 and SD/R-Ag14) can be realized by re-crystallizing SD/rac-Ag14a in acetonitrile, which promotes the homochiral crystallization in solid state by forming C-H···O/N hydrogen bonds with nitro oxygen atoms in pntp or aromatic hydrogen atoms in dpph (dpph = 1,6-bis(diphenylphosphino)hexane) on Ag nanocluster.
View Article and Find Full Text PDFRapid Commun Mass Spectrom
May 2021
Rationale: Due to isotope fractionations during partial nitrogen release from minerals and rocks, the complete extraction of nitrogen for analysis is crucial to ensure high-quality nitrogen isotopic data. However, the appropriate nitrogen extraction conditions (e.g.
View Article and Find Full Text PDFTriple negative breast cancer (TNBC) has poor prognosis due to lack of biomarker and therapeutic target. Emerging research has revealed long noncoding RNAs (lncRNAs) are involved in breast cancer progression, but their functions and regulatory mechanisms remain poorly understood, especially in TNBC. In this study, we performed lncRNA microarray analysis of five TNBC samples and their matched normal tissues, and discovered a number of differentially expressed lncRNAs.
View Article and Find Full Text PDFDeep understanding of structure-property relationship between packing of chiral building units and their chiroptical behaviors would significantly facilitate the rational design and fabrication of the emerging chiroptical materials such as circularly polarized luminescence (CPL) emissive materials. In this paper, we unveil the universal existence of supramolecular tilt helical superstructures in self-assembled π-conjugated amino acid derivatives. A series of coded amino acid methyl esters were conjugated to anthracene segments at N-terminus, which afforded 2 and 3 symmetry supramolecular tilt chirality in solid-states.
View Article and Find Full Text PDFJ Chem Theory Comput
October 2020
Full configuration interaction (FCI) solvers are limited to small basis sets due to their expensive computational costs. An optimal orbital selection for FCI (OptOrbFCI) is proposed to boost the power of existing FCI solvers to pursue the basis set limit under a computational budget. The optimization problem coincides with that of the complete active space SCF method (CASSCF), while OptOrbFCI is algorithmically quite different.
View Article and Find Full Text PDFFirst-principles electronic structure calculations are now accessible to a very large community of users across many disciplines, thanks to many successful software packages, some of which are described in this special issue. The traditional coding paradigm for such packages is monolithic, i.e.
View Article and Find Full Text PDFWe present an efficient way to compute the excitation energies in molecules and solids within linear-response time-dependent density functional theory (LR-TDDFT). Conventional methods to construct and diagonalize the LR-TDDFT Hamiltonian require ultrahigh computational cost, limiting its optoelectronic applications to small systems. Our new method is based on the interpolative separable density fitting (ISDF) decomposition combined with implicitly constructing and iteratively diagonalizing the LR-TDDFT Hamiltonian and only requires low computational cost to accelerate the LR-TDDFT calculations in the plane-wave basis sets under the periodic boundary condition.
View Article and Find Full Text PDFWe develop an efficient algorithm, coordinate descent FCI (CDFCI), for the electronic structure ground-state calculation in the configuration interaction framework. CDFCI solves an unconstrained nonconvex optimization problem, which is a reformulation of the full configuration interaction eigenvalue problem, via an adaptive coordinate descent method with a deterministic compression strategy. CDFCI captures and updates appreciative determinants with different frequencies proportional to their importance.
View Article and Find Full Text PDFAtomically precise Au nanoclusters stabilized by stibines catalyze the aldehyde-alkyne-amine coupling reaction more efficiently than those stabilized by thiols or phosphines. The nature of the catalytic activity is also different, and may be attributed to the weaker coordinating ability of the stibine ligands.
View Article and Find Full Text PDF