Sr(NO_3)_2·DCH18C6配合物晶体结构与辐射稳定性

二环己基-18-冠-6(DCH18C6)可以有效地从高放废液中分离90Sr,对于减小放射性废物的危害和实现高放废物的减容有重要意义.由于在实际应用中DCH18C6处于射线照射下,其结构可能会被破坏并引起络合能力的变化,因此有必要对该配合物的辐射稳定性进行研究.本文合成了Sr(NO3)2?DCH18C6配合物晶体,并通过单晶X射线衍射(XRD)与扩展X射线吸收精细结构谱(EXAFS)等方法进行了表征,确定Sr2+与周围氧原子的配位数为10,Sr―O平均键长约为0.268 nm/0.266 nm(XRD/EXAFS).配位原子来自DCH18C6的六个氧原子以及两个作为双齿配体的硝酸根的四个氧原子.对该配合物晶体在空气中进行γ辐照,EXAFS结果表明吸收剂量为400 kGy时,Sr―O键长及配位数没有发生变化,配位结构没有被破坏,具有很好的耐辐照稳定性.显微红外光谱(Micro-FTIR)结果进一步证明辐照后冠醚环的部分C―H键氧化为羟基或羰基,但并不影响DCH18C6与Sr2+的配位结构.     

Crystal Engineering of Multiple-component Organic Compound:Organic co-Crystals of the Functional Groups of Carboxyl and Amino with Persistent Hydrogen Bonding Motifs

Three small organic molecular co-crystal compounds (C₃N₆H₆)·(C₆H₁₀O₄)·H₂O(1), C₃H₈N₂O(3) and (H₄btec)₂·(4,4'-bipy)(4)(H₄btec=1,2,4,5-benzenetetracarboxylic acid, 4,4'-bipy=4,4'-bipyridine) and one coordination supramolecular compound [Mn(C₂O₄)(H₂O)₂]·C₆H₁₁NO₂(2) were synthesized by hydrothermal reaction. They were characterized by elemental analysis, infrared(IR) spectroscopy and single crystal X-ray diffraction(XRD). Structural analyses reveal that these 2D or 3D supramolecular networks of the compounds were formed by C―H···O, N―H···O, N―H···N, O―H···O and O―H···N hydrogen bonds. Therein, the functional groups of ―COOH, ―NH₂ and ―OH play important roles in constructing supramolecular architectures.     

Design,Synthesis and Antitumor Activity of Novel Indolin-2-one Derivatives Containing 4-Thiazolidinone Moiety

A series of novel indolin-2-one derivatives containing 4-thiazolidinone moiety(7a―7r) were synthesized and evaluated for their in vitro antitumour activities against MDA-MB-231(human breast cancer), H460(human lung cancer) and HT-29(human colon cancer) cell lines by standard 3-(4,5-dimethylthiazae-2-yl)-2,5-diphenyltetrazo- lium bromide(MTT) assay. Representative compounds(7d, 7k, 7m, 7p) with higher cytotoxicity were further examined against one normal cell line(WI-38, human fetal lung fibroblasts). The preliminary investigation shows that most of the compounds display moderate to excellent potency and high selectivity against different human cancer cell lines. In particular, the most potent compound 7m shows promising cytotoxicity against MDA-MB-231, H460 and HT-29 cell lines with IC₅₀ values of 0.78, 0.056 and 0.018 μmol/L, respectively. The potency is much higher than that of Sunitinib(IC₅₀=3.46 μmol/L against MDA-MB-231, IC₅₀=2.59 μmol/L against H460, IC₅₀=1.50 μmol/L against HT-29) by 4.4, 46.3 and 83.3 fold.     

Stereoselective Palladium-catalyzed Cross-coupling of (2-Amido-1-phenylpropyl)zinc Compounds with Aryl Bromides

A controllable diastereoselective C(sp²)―C(sp³) Negishi coupling reaction of secondary benzylic zinc reagents with aryl bromides to form medicinally important 2-arylphenylethylamines was demonstrated. In the presence of Pd(OAc)₂ and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl(S-phos), open-chain(2-amido-1-phenylethyl)zinc reagent bearing a β-NHAc or NHCHO group undergoes coupling reaction to give syn-1-arylphenylethylamine mainly, whereas the zinc reagent bearing a sterically hindered β-amido group, for example NHCOC(CH₃)₂OTBS undergoes the coupling reaction to yield anti-1-arylphenylethylamines with a configuration inversion. In addition, a working mechanism for the stereoselective Negishi cross-coupling was also proposed.     

Synthesis,Spectroscopic, Thermochemical Properties of Lanthanide Complexes with 3,4-Diethoxybenzoic Acid and 1,10-Phenanthroline

Three novel lanthanide complexes [Ln(3,4-DEOBA)₃phen]₂[Ln=Eu(1), Tb(2), Dy(3); 3,4-DEOBA=3,4- diethoxybenzoate; phen=1,10-phenanthroline] were synthesized and characterized by elemental analysis, molar conductance, X-ray diffraction and infrared spectrometry. The luminescence spectra of complexes 1 and 2 show the characteristic emission of Eu³⁺ ion(⁵D₀→⁷F_0-3) and Tb³⁺ ion(⁵D₄→⁷F_6-3). The thermal decomposition mechanism of the title complexes and the analysis of the evolved gases were investigated by thermogravimetry/differential scanning calorimetry-Fourier transform infrared(TG/DSC-FTIR) technology. The results indicate the complexes are thermally stable. In the thermal decomposition of the complexes, phen molecules lost firstly, and then 3,4-DEOBA ligand decomposed into H₂O, CO₂ and other gaseous molecules. Besides, several gaseous organic fragments were also detected. The heat capacities of complexes 1―3 were measured by DSC in a temperature range of 263.15―340.15 K. Based on the fitted polynomial and thermodynamic equations, the smoothed heat capacities and thermodynamic functions of the three complexes were calculated. The study on biological activity showed that the complexes exhibited good antibacterial activity against Candida albicans, Staphylococcus aureus and Escherichia coli.     

Judd-Ofelt Analysis on Trifluoroacetate Europium Complexes for Liquid Laser Media

Four europium trifluoroacetate complexes, Eu(CF₃COO)₃·bpy(bpy=2,2′-bipyridine)(1), Eu(CF₃COO)₃· phen(phen=1,10-phenanthroline)(2), Eu(CF₃COO)₃·2bp(bp=benzophenone)(3) and Eu(CF₃COO)₃·2tppo(tppo=triphenyl-phosphine oxide)(4) were synthesized and characterized by elemental analysis, Fourier transform infrared(FTIR) spectroscopy, photoluminescence(PL) spectroscopy and thermogravimetric analysis(TGA). The PL spectra of the complexes at room temperature show the strong typical Eu³⁺ ion red emission, due to the efficient energy “antenna absorption” of ligands and transitions of Eu³⁺ ion between ⁵D₀→⁷F_J(J=0―4). The long lifetime and high quantum yield reflect that the multiphonon relaxations by coupling to O―H and C―H vibrations were reduced. According to the photoluminescent spectra, the Judd-Ofelt parameters Ω₂ and Ω₄ of the complexes were calculated and the radiative properties were also presented. The ⁵D₀ radiative lifetime, quantum yield and the stimulated emission cross-section of the complexes are excellent, which prove that they have promising optical properties for liquid laser. The thermal analyses indicate that they are quite stable to heat.     

金属串配合物[Ni3(L)4(NCS)2](L = dpa-, mpta-, mdpa-, mppa-)结构和磁性的理论研究

应用密度泛函理论BP86方法结合自然键轨道分析方法对具有分子导线潜在应用前景的金属串配合物[Ni₃(L)₄(NCS)₂](L = dpa^- (1), mpta^- (2), mdpa^- (3), mppa^- (4))进行研究,分析了桥联配体L对Ni―Ni相互作用和磁耦合性质的影响.结果得到: (1)配合物的基态均是对应于五重态(HS)的反铁磁(AF)单重态, HS的能量和结构与AF态相近, Ni₃⁶⁺链形成了三中心四电子σ键(σ₂σ_nb¹σ^*1). (2) dpa^-引入甲基成为mdpa^-,对Ni―Ni、Ni―N距离影响不大; 3H-吡咯环和噻唑环取代吡啶环后, N1―N2、Ni―Ni距离增大, Ni2―N2键长缩短,但噻唑环的影响较小;故Ni―Ni相互作用强度为1 ≈ 3 > 2 > 4. (3)预测了3和4的J_ab值为-103和-88 cm^-1,随Ni―Ni相互作用增强磁耦合效应增大. Ni―Ni相互作用越大,通过Ni₃⁶⁺链σ型轨道的直接磁耦合越强; Ni2―N2键越强,通过涉及桥联配体的间接磁耦合越强,直接磁耦合比间接磁耦合更强.     

Degradation of Hydrogenated Nitrile-butadiene Rubber in Aqueous Solutions of H2S or HCl

The degradation of hydrogenated nitrile-butadiene rubber(HNBR) soaped in aqueous solutions of H₂S and HCl was investigated. The samples unexposed and exposed to different solutions were characterized by ¹³C nuclear magnetic resonance(¹³C NMR), X-ray photoelectron and infrared spectroscopies. In contrast to those of unexposed samples and samples soaped in HCl solution, the mechanical properties of samples exposed to H₂S solution significantly deteriorated, in which the new groups of C(=O)―NH₂, C―S―C and C=S emerged. The mechanism of C=S and C―S―C formation was speculated, except for that of the formation of group C(=O)―NH₂, which was widely discussed in acidic condition such as HCl solution. The formation of C―S―C was due to radical reaction initiated by mercapto radical and that of C=S was due to nucleophilic reaction initiated by mercapto cations. This finding is helpful to understanding the seal failure of HNBR in working environment containing H₂S.     

Elution of 17α 25-Norhopanes and Triaromatic Steroids from Weathered Soils by Mixed Triton X-100/Na2SiO3 Surfactant Solution

Sodium silicate(Na₂SiO₃) was used to improve the elution of super heavy oil from weathered soil on an ultrasound-enhanced elution system by the solution containing 0―6000 mg/L surfactant Triton X-100. The removal extent of three markers[C_26―34 17α 25-norhopanes, C_26―28 triaromatic steroids(TAS), and C_27―29 methyl triaromatic steroids(MTAS)] was monitored. The average elution percentages of C_26―34 norhopanes, C_26―28 TAS, and C_27―29 MTAS by Triton X-100/Na₂SiO₃ solutions were increased by 11%―13%, 9%―11% and 8%―13% with increasing Triton X-100 concentrations from 150 mg/L to 6000 mg/L. All the concentrations of Triton X-100 improved the elution of TAS homologs containing fewer carbon atoms, whereas high concentrations improved the elution of larger 17α 25-norhopane and MTAS species. Addition of Na₂SiO₃ produced a noticeable increase in elution, particularly for lower-weight species. Scanning electron microscope(SEM) images and energy spectroscopy data reveal that surfactant solution of 6000 mg/L Triton X-100 and 4000 mg/L Na₂SiO₃ produced the greatest improvement in the elution of super heavy oil aggregates encapsulating the soil surface and the emulsification of particle dispersions. That is to say mixed solutions of Triton X-100 and Na₂SiO₃ in combination with ultrasound are a potential means of removing super heavy oil from weathered soils.     

Synthesis and Structure Description of a New Tetradecaborate [H_3N(CH_2)_2NH_3]_2[B_(14)O_(20)(OH)_6]

A new tetradecaborate, [H3N(CH2)2NH3]2[B14O20(OH)6](1), was synthesized by a boric acid ‘flux’ method, and characterized by X-ray powder diffraction, ICP, IR, TGA and DTA analyses. Single-crystal X-ray diffraction analysis showed that it crystallized in the monoclinic space group P1(No.2) with a=0.85092(10) nm, b=0.88678(11) nm, c=1.00724(13) nm, α=95.099(2)o, β=96.950(2)o, γ=116.845(2)o, V=0.66425(14) nm3, Z=2, R1=0.0625[I2σ(I)], and wR2=0.1172(all data). The molecule structure of compound 1 comprises the isolated polyanion clusters [B14O20(OH)6]4– and diprotonated ethylenediamine molecules. Each polyanion cluster contains an 8-ring enclosed by six B3O3 3-ring units. Adjacent clusters are further connected with each other through strong hydrogen-bonding interactions of N(O)―H···O to form a three dimensional(3D) supramolecular structure with 2D pseudo channels along the [010] and [001] directions. The diprotonated ethylenediamine molecules located in the channels interact with the host through extensive hydrogen-bonds. Compound 1 presents few example containing isolated polyborate anions synthesized by a boric acid ‘flux’ method.     

Sr(NO3)2·DCH18C6配合物晶体结构与辐射稳定性

二环己基-18-冠-6（DCH18C6）可以有效地从高放废液中分离⁹⁰Sr,对于减小放射性废物的危害和实现高放废物的减容有重要意义. 由于在实际应用中DCH18C6处于射线照射下,其结构可能会被破坏并引起络合能力的变化,因此有必要对该配合物的辐射稳定性进行研究. 本文合成了Sr（NO₃）₂·DCH18C6 配合物晶体,并通过单晶X射线衍射（XRD）与扩展X射线吸收精细结构谱（EXAFS）等方法进行了表征,确定Sr²⁺与周围氧原子的配位数为10,Sr―O平均键长约为0.268 nm/0.266 nm（XRD/EXAFS）. 配位原子来自DCH18C6 的六个氧原子以及两个作为双齿配体的硝酸根的四个氧原子. 对该配合物晶体在空气中进行γ辐照,EXAFS结果表明吸收剂量为400 kGy时,Sr―O键长及配位数没有发生变化,配位结构没有被破坏,具有很好的耐辐照稳定性. 显微红外光谱（Micro-FTIR）结果进一步证明辐照后冠醚环的部分C―H 键氧化为羟基或羰基,但并不影响DCH18C6与Sr²⁺的配位结构.     

微波辅助无催化剂高效串联环化合成吡啶[2,3⁃d]嘧啶衍生物

建立了一种吡啶[2,3-d]嘧啶类化合物的高效合成方法. 以α,β?不饱和酮类化合物和1,3-二甲基-6-氨基脲嘧啶为原料, 在微波辅助无催化剂条件下, 于5~15 min内高效串联环化合成了28个具有分子多样性的吡啶[2,3-d]嘧啶类化合物, 其中21个化合物未见文献报道. 该方法具有原料简单易得、 高效绿色、 成键效率高及后处理简单等优点.     

Effect of Magnetic Carrier NiFe2O4 Nanoparticles on Physicochemical and Catalytic Properties of Magnetically Separable Photocatalyst TiO2/NiFe2O4

A series of magnetically separable photocatalyst TiO₂/NiFe₂O₄(TN) with different mass ratios of NiFe₂O₄ to TiO₂ was prepared by sol-gel method. The X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), ultraviolet-visible spectroscopy(UV-Vis), Brunauer-Emmett-Teller(BET) surface analysis and photoluminescence spectroscopy(PL) were used to characterize the photocatalyst TN. The XRD patterns of TN indicate that adulterating a smidgen of NiFe₂O₄ into TiO₂(about 0.1%, mass ratio) can promote the phase transformation of TiO₂, however, when the doped amount of NiFe₂O₄ surpasses 1%, the introduction of NiFe₂O₄ can inhibit the growth of TiO₂ crystal grain and reduce the size of TiO₂ crystal grain. The XPS results of TN indicate that some Fe³⁺ replace Ti⁴⁺ of the TiO₂ lattice forming Fe―O―Ti bonds. The PL analysis of TN shows that the NiFe₂O₄ nanoparticles in photocatalyst TN play the role of the effective recombination centre of the photogenerated electrons and holes, leading to the decrease in photocatalytic activity.     

Synthesis of Dihydrobenzofuran Neoligans Licarin A and Dihydrocarinatin as Well as Related Triazolylglycosides

Two natural dihydrobenzofuran neolignans licarin A（1） and dihydrocarinatin（2） were systhesized from isoeugenol with Ag20-catalyzed biomimetic oxidative coupling as the key step. Four novel dihydrobenzofuran triazolylglycoside（3--6） were achieved in good yields via Cu（I）-catalyzed azide-alkyne cycloadditions of licarin A terminal alkynes with different azide acetylated sugar and deacetylation with sodium methoxide in anhydrous methanol. The structures of all the compounds synthesized were determined by elemental analysis, MS, 1H NMR and ~3C NMR. And the inhibition activity of synthesized compounds on a-glucosidase was determined by in vitro experiments. The results show that triazolyglycosides 3, 4, 5 and 6 show moderate inhibitory activity on a-glucosidase.     

二维铁电材料ABP2X6内在极高的负泊松比

Recently, ferroelectric materials have attracted considerable research attention. In particular, two dimensional (2D) ferroelectric materials have been considered as most crucial for next-generation circuit designs because of their application as novel electric memory devices. However, a 2D ferroelectric material is very rare. The ferroelectric materials with the form ABP₂X₆ (A = Ag, Cu; B = Bi, In; X = S, Se) are of interest because of their ferroelectric property maintained in their ultrathin structures. Within the ABP₂X₆ monolayer, the P―P bonds form the pillars that hold the top and bottom X planes, while the off-center A―B atoms between the X layers induce a spontaneous ferroelectric polarization. If the two off-center A―B sites are equally aligned, this would lead to the appearance of the paraelectric state. Such intriguing structures must impart novel mechanical properties to the materials. Until now, there has been no report on the mechanical properties of monolayer ABP₂X₆. Based on first-principles calculations, we studied the structural, electronic, mechanical as well as the electromechanical coupling properties of monolayer ABP₂X₆ (A = Ag, Cu; B = Bi, In; X = S, Se). We found that they are all semiconductors with wide bandgaps of 2.73, 2.17, 3.00, and 2.31 eV for CuInP₂Se₆, CuBiP₂Se₆, AgBiP₂S₆, and AgBiP₂Se₆, respectively, which are calculated based on the Heyd-Scuseria-Ernzerhof (HSE) exchange correlation functional model. The conduction band minimum is mainly from p orbitals of X and B atoms, whereas the valence band maximum is due to the hybridization of the p orbital of X atoms and the d orbital of A atoms. Moreover, there are three short and three long A/B―X bonds due to the A―B off-center displacement. Together with the d-p orbital hybridization, the main reason for the distorted ferroelectric structure in ABP₂X₆ monolayers is the Jahn-Teller effect. ABP₂X₆ monolayers are predicted to be a new class of auxetic materials with an out-of-plane negative Poisson's ratio, i.e., the values of the negative Poisson's ratio are in the order AgBiP₂S₆ (−0.805) < AgBiP₂Se₆ (−0.778) < CuBiP₂Se₆ (−0.670) < CuInP₂S₆ (−0.060). This is mainly due to the tensile strain applied in the x/y direction enlarging the angle between P―P bonds and top layer X atoms, thereby enhancing the bucking height of monolayer ABP₂X₆. Moreover, external strain has a significant impact on the A―B off-center displacement, rendering an out-of-plane piezoelectric polarization. The values of e₁₃ for CuInP₂S₆, CuBiP₂Se₆, AgBiP₂S₆, AgBiP₂Se₆ monolayers are calculated to be −3.95 × 10⁻¹², −5.68 × 10⁻¹², −3.94 × 10⁻¹², −2.71 × 10⁻¹² C∙m⁻¹, respectively, which are comparable to the only experimentally confirmed 2D out-of-plane piezoelectric Janus system (piezoelectric coefficient = −3.8 × 10⁻¹² C∙m⁻¹). This unusual auxetic behavior, ferroelectric polarization, and the electromechanical coupling in monolayer ABP₂X₆ could potentially lead to enormous technologically important applications in nanoelectronics, nanomechanics, and piezoelectrics.     

Synthesis and Herbicidal Activities of 2-Methylpropan-2-aminium O-Methyl 1-（Substituted Phenoxyacetoxy）alkylphosphonates

A series of 2-methylpropan-2-aminium O-methyl 1-（substituted phenoxyacetoxy）alkylphosphonates （5a-5o） was selectively synthesized by reacting the corresponding O,O-dimethyl l-（substituted phenoxyacetoxy）-alkylphosphonates with an excess of 2-methylpropan-2-amine.The results of preliminary bioassays show that the title compounds exhibit moderate to good herbicidal activities against Brassica napus and Echinochloa crusgalli.Furthermore,compounds 5a-5j,which show much higher activities than compounds 5k-5o,were selected to further evaluate their post-emergence herbicidal activity at a dosage of 150 g/ha（l ha=10000 m2）.Especially,2-methylpropan-2-aminium O-methyl 1-[2-（4-chloro-2-methylphenoxy）acetoxy]butylphosphonate（5h） shows 100％ inhibitory effect on the growth of Brassica juncea and Amaranthus retroflexus,which is comparable with the commercial herbicide 2,4-dichlorophenoxy acetic acid（2,4-D）.     

Synthesis and Characterization of Novel Schiff Base Macrocyclic Compounds Containing Thiophene

Several novel Schiff base macrocyclic compounds containing thiophene were synthesized from d/ethyl 3,4-dialkoxythiophene-2,5-dicarboxylate, cyanuric chloride, diethylarnine and p-nitrophenol by reduction, oxidation, substitution and cyclization, and their structures were characterized by IR, NMR and electrospray ionization-rnass spectrorneter（ESI-MS）. The studies on their UV-Vis absorption spectra show that Schiff base rnacrocycles 6-10 have selective recognition for Fe^3＋.     

非晶态镍硼酸盐结构的EXAFS研究(英文)

由摩尔比分别为1:2和1:8的NiCl2·6H2O和Na2B4O7·10H2O作为反应物,合成两种非晶态镍硼酸盐,同时通过水热法合成β-Ni(OH)2.化学分析和热重-微商热重法(TG-DTG)分析结果确定两种非晶态镍硼酸盐的分子组成分别为NiO·0.8B2O3·4.5H2O和NiO·B2O3·3H2O.激光拉曼(Raman)实验结果表明镍硼酸盐样品中主要存在的硼氧阴离子为B3O3(OH)52-和B2O(OH)62-.同步辐射扩展X射线吸收精细结构(EXAFS)方法对样品进行结构解析,通过数据拟合给出样品中Ni原子周围近邻配位原子种类、配位数以及原子间距离.用不同晶体结构作为标准对两种非晶态镍硼酸盐进行拟合的结果表明,样品中Ni原子周围局域结构与Ni3B2O6晶体(ICSD No.31387)中的吻合较好.Ni原子周围配位原子为O、B和Ni,对于NiO·0.8B2O3·4.5H2O,配位数分别为5.7、3.8和3.8,配位距离分别为0.208、0.263和0.311 nm;对于NiO·B2O3·3H2O,配位数分别为6.0、4.0和4.0,配位距离分别为0.207、0.262和0.310 nm.     

固体核磁共振研究碱土金属磷硅酸盐玻璃的六配位硅结构

Phosphate glass is widely used in optical applications; however, its generally low chemical stability and poor thermal mechanical properties hinder the application of phosphate glass to the rapidly evolving laser industry. The addition of a small amount of silicon can form a six-coordinate Si (Si⁽⁶⁾) network and improve the above-mentioned poor properties of phosphate glass. Therefore, it is important to characterize and understand the structural details of phosphosilicate glasses. It is difficult to investigate the glass structure because of its complicated and disordered characteristics. However, solid-state nuclear magnetic resonance (NMR) spectroscopy can provide detailed local structural information, regardless of the presence of its long-range order. To study the effect of alkaline earth metals on Si⁽⁶⁾ species formation, we prepared phosphosilicate glasses (2MO-3P₂O₅)_(1−x)·(SiO₂)_x (M = Ca, Sr, Ba) by conventional melt-quenching, and the glass structure was investigated by solid-state NMR and Raman spectroscopy. The ³¹P and ²⁹Si NMR spectra indicated that the glass networks consisted of P⁽²⁾ and P⁽³⁾ tetrahedrons linked via four- and six-fold coordinated silicon units (Si⁽⁴⁾ and Si⁽⁶⁾). The fraction of six-coordinated silicon Si⁽⁶⁾ decreased with increasing SiO₂ content. Similarly, the Raman spectra showed that the vibration band of the P＝O stretching mode in P⁽³⁾ linked with Si⁽⁶⁾ neighbors reduced as the silica content increased. The connectivities between various phosphorus species were probed by ³¹P one- and two-dimensional refocused INADEQUATE experiments. This experimental technique is based on homonuclear J-coupling and yields correlation peaks between nuclei engaged in P―O―P linkages (P⁽²⁾ and P⁽³⁾ units). The signals from isolated ³¹P nuclei are suppressed because of the absence of J-coupling, which precludes the formation of double quantum coherences. The results indicated the segregation of P⁽²⁾ and P⁽³⁾ units in the prepared glass, which were also compared with those in the previously reported Na₂O-P₂O₅-SiO₂ glasses. They differed from alkali phosphosilicate glasses, where each P⁽³⁾ unit exhibited a maximum average of one Si⁽⁶⁾―O―P⁽³⁾ linkage, and in the alkaline earth phosphosilicate glasses, the average was approximately 0.4–0.7. When the content of Si⁽⁶⁾ units reached its maximum, further increase in the SiO₂ content did not increase the Si⁽⁶⁾ content, and the surplus Si were present as Si⁽⁴⁾. Alkaline earth metal ions exhibit weaker stabilizing effects for Si⁽⁶⁾ species. Based on the results presented herein, we constructed sketches to illustrate the local structural organization of the glass. The relationships between the compositions and structures are important for glass composition and property design. It is important to improve the performance of phosphate glass by changing its composition, particularly for large laser device applications.